Selectivity of Transport of Sodium, Magnesium, and Calcium Ions through a Sulfo-Cationite Membrane in Mixtures of Solutions of Their Chlorides

The transport numbers and the selectivity of transport of sodium, magnesium, and calcium ions through a heterogeneous sulfo-cationite membrane in solutions of sodium, magnesium, and calcium chlorides and their mixtures are studied at various current densities. Equations for calculating the selectivity of transport of the ions through the membrane are suggested for two extreme cases. One case corresponds to low currents, when one can assume that the membrane is at equilibrium with the outside solution. The selectivity of transport of the ions is defined in this case by their migration through the membrane. The other case occurs at currents that are close to a limiting value. Under these conditions the transport of the ions through the membrane is defined by their transport through a diffusion layer that forms near the membrane surface. Calculations with the aid of these equations satisfactorily conform to experiment. The deviation from calculation in the case of the magnesium cation is connected probably with its hydration being substantially greater as compared with sodium and calcium. It is established that the selectivity of transport of the ions through the membrane may be controlled to a certain extent by varying the current density.__________Translated from Elektrokhimiya, Vol. 41, No. 8, 2005, pp. 997–1000.Original Russian Text Copyright © 2005 by Greben’, Rodzik.     

Characteristics of Proton-Conducting Electrolytes BaCe1 ? xNdxO3 ? δ (0 ≤ x ≤ 0.16) in Moist Air

Electroconductance, overall transport number for ions, and transport number for protons in BaCeO₃ doped with neodymium in the cerium sublattice (0–16%) are measured in moist air (pH₂O = 2.6 kPa) at 550– 1000°C. Partial (by protons, oxygen, and holes) conductances and appropriate effective activation energies are determined. Literature sources are reviewed. __________ Translated from Elektrokhimiya, Vol. 41, No. 9, 2005, pp. 1125–1132. Original Russian Text Copyright ? 2005 by Sharova, Gorelov.     

Ionic Transport in Dilute Solid Polymer Electrolytes with Amorphous Structure

The ionic structure and transport properties of amorphous solid polymer electrolytes in the system copolymer of acrylonitrile and butadiene (40 : 60)—lithium hexafluoroarsenate (SPE) is studied in the region of small salt concentrations (up to 0.37 mol dm⁻³) at 298–368 K. In conditions studied, LiAsF₆ is dissociated predominantly to ions. Macroscopic models of ion transport are used to analyze the results of measurements of transport characteristics of SPE. Transport of anions free of the polymer matrix is realized activationlessly and resembles the Stokes drift in viscous media. Transport of cations solvated by electron-donating groups of the polymer turns possible only at temperatures in excess of a critical value (T _crit ≈ 333 K), when the statistical mean of molecules in the first coordination sphere of the lithium cation becomes less than four (which is the coordination number for solvation) and requires the overcoming of an energy barrier of ∼6 kJ mol⁻¹. Below T _crit, the SPE are unipolar anionic conductors.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 537–545.Original Russian Text Copyright © 2005 by Bushkova, Sofronova, Lirova, Zhukovskii.     

Electrochemical Methods for Studying Transport Properties and the Type of Ionic Conduction in Solid Electrolytes Based on CaPr<Subscript>2</Subscript>S<Subscript>4</Subscript> and Ca(Ba)Sm<Subscript>2</Subscript>S<Subscript>4</Subscript>

The theoretical feasibility of sulfide ion transport in phases based on MeLn₂S₄ (Me = Ca, Ba; Ln = Sm, Pr) is considered. Regions of solid solutions on the basis of ternary compounds are determined. A systematic investigation of phases is performed with the application of a variety of electrochemical methods, specifically, the conductimetry, emf in chemical concentration cells with and without transport, and Tubandt methods.__________Translated from Elektrokhimiya, Vol. 41, No. 6, 2005, pp. 707–713.Original Russian Text Copyright © 2005 by Ushakova, Kalinina, Fominykh, Yurlov, Murin.Published on the basis of a report delivered at the VII Meeting on Fundamental Problems in Solid-State Ionics (Chernogolovka-2004).     

Energies of transport of individual ions out of water into aprotic solvents: Specific features of the acetate ion transport

An analysis of techniques used for the determination of the free energy of the transport of an individual ion out of water into an aprotic solvent shows that the most reliable technique at present seems to be a method based on the determination of potentials relative to a cobalticenium electrode in combination with the energy required for the transport of the cobalticenium ion calculated after Born. This method is combined with relevant original and literature data to determine the transport energies for more than thirty ions out of water into propylene carbonate, dimethyl sulfoxide, dimethylformamide, acetonitrile, and acetone. The solubility of anhydrous sodium acetate in the above solvents are measured and the obtained data are used to determine the transport energies for the acetate ion and a neutral molecule of acetic acid. It is shown that, because of a large contribution of short-range interactions, especially the hydrogen bonds, the energies in question cannot be calculated with the aid of continuum electrostatics. This proves that the purely electrostatic method, which has been extensively used in biophysics for calculating pK of acid groups of proteins, is fallacious.Translated from Elektrokhimiya, Vol. 41, No. 3, 2005, pp. 325–332.Original Russian Text Copyright © 2005 by Bunakova, Khanova, Krishtalik.     

Simulation of concurrent transport of counterions through a heterogeneous ion-exchange membrane

Numerical solutions of the problem of concurrent transport of two counterions in an ion-exchange membrane are presented and discussed with allowance made for the membranes heterogeneous structure. Densities of fluxes of co-ions and competing counterions are computed as a function of the current density and boundary concentrations on either side of the membrane. The obtain result is viewed as the initial product for solving multilayered problems containing membranes of other nature and diffusion layers surrounding the membrane.Translated from Elektrokhimiya, Vol. 41, No. 3, 2005, pp. 356–366.Original Russian Text Copyright © 2005 by Gnusin.     

Synthesis and Electrolytic Properties of Phases Based on Calcium Thiogadolinate as a Function of Method of the Precursor Synthesis

Differently treated phases based on CaGd₂S₄ are studied by electrochemical methods. The range of solid solutions, electrolytic temperature interval, and averaged transport numbers for ions and electrons are determined. Compositions with best electrolytic properties are established. The origin of conduction in a CaGd₂S₄-based solid electrolyte is investigated. The obtained data show the phases to be sulfide-conducting solid electrolytes with a small share of cationic conduction.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 633–639.Original Russian Text Copyright © 2005 by Medvedeva, Kalinina, Metlin, Ushakova.     

Conduction and Transport Numbers in Metacomposites MeWO<Subscript>4</Subscript> ⋅ WO<Subscript>3</Subscript> (Me = Ca,Sr, Ba)

The conduction and transport numbers of charge carriers for composites in the systems MeWO₄-WO₃ (Me = Ca, Sr, Ba) are studied as a function of the temperature and the activity of oxygen in a gas phase. The transport numbers are determined by an emf method and are estimated from dependences of conductance on the activity of oxygen in a gas phase. The deficiencies of the given procedure as applied to investigation of properties of composite phases are analyzed. The materials under study are classified with a class of metacomposites. The concentration intervals of the ionic, mixed, and electronic conductions are determined. The conduction of composites of compositions (100 − x)MeWO₄ ⋅ xWO₃ is predominantly ionic at x ≤ 10 (Me = Ca), x ≤ 60 (Me = Sr), and x ≤ 45 (Me = Ba). The obtained data are explained in the framework of a model that represents a composite as a distributed matrix system where a film of surface phase MeW-s with a high mobility of oxygen ions plays the role of a connected matrix. It is presumed that the surface phase MeW-s possesses double-sided surface activity (α _MeW-s ≤ ) and a higher mobility with respect to MeWO₄ and WO₃. The discovered anomalies of dependences (T) and partial dependences , σ_el(T) are explained by a change in the stoichiometry, morphology, and the degree of connectedness of surface phase MeW-s caused by with a change in the temperature and composition of composites.__________Translated from Elektrokhimiya, Vol. 41, No. 6, 2005, pp. 680–693.Original Russian Text Copyright © 2005 by Neiman, Pestereva, Sharafutdinov, Kostikov.Published on the basis of a report delivered at the VII Meeting on Fundamental Problems in Solid-State Ionics (Chernogolovka-2004).     

Azacrown ethers modified with germanium‐containing side‐chains as heteroditopic hosts

The cation capture/transport ability of diazacrowns, one with side chains containing germanium ( 5a ), another with side chains not containing germanium ( 7 ), and 4,13‐diaza‐18‐crown‐6 ( 8 ), was found to decrease in the order 5a > 7 > 8 . Titration experiment and ⁷³Ge NMR failed to give an unequivocal rationalization of the results. Copyright © 2005 John Wiley & Sons, Ltd.     

Transport efficiency in femtosecond laser ablation inductively coupled plasma mass spectrometry applying ablation cells with short and long washout times

Relative mass transport efficiencies of near infrared (λ = 795 nm) femtosecond laser generated brass aerosols in helium were measured by ICP-MS applying different ablation cells with short and long washout times. It was found that the transport efficiencies are independent of the cell used within the mutual experimental uncertainties. This finding was confirmed by additional measurements providing the absolute particle mass transport efficiencies of femtosecond laser ablation in He. Here, the transport efficiencies were determined by weighing the samples before and after ablation with a micro-balance, collecting the particles by low-pressure impaction, and evaluating the impacted masses quantitatively by total reflection X-ray fluorescence. Within the experimental uncertainties (± 9–19%) the same absolute transport efficiency (about 77%) was found for all cells applied. This efficiency value can be regarded as a lower limit of the absolute mass transport efficiency since mass losses in the impactor are difficult to quantify.     

Syntheses and properties of a thiacrown ether and its acyclic model compound modified with germanium moieties

A thiacrown ether (1) and its acyclic model compound (2), modified with germanium moieties, were synthesized and their structures confirmed by NMR spectrometry and elemental analysis. The germanium atom, located in one of the side chains of 2, is pentacoordinated by virtue of a weak hypervalent O → Ge interaction. The cation capture/transport ability is almost null for both compounds, probably owing to the proximity of the cation and anion binding sites. Copyright © 2005 John Wiley & Sons, Ltd.     

Utilizing Sulfide-Selective Membranes with Regenerated Properties in Sensors of Sulfur-Containing Gases

The feasibility of utilizing sulfide-conducting solid electrolytes MeS-Ln₂S₃ (Me = Ca, Ba; Ln = Y, Nd, Gd, Sm, Tm) in sensors intended for analysis of sulfur-containing media is investigated. The design parameters and operation regimes of the sensors are selected. The effect of many-component impurities on the sensors’ selectivity is investigated. It is established that the ageing is linked to operation parameters of the sensors and the possibility of regeneration of their optimum characteristics.__________Translated from Elektrokhimiya, Vol. 41, No. 6, 2005, pp. 714–720.Original Russian Text Copyright © 2005 by Kalinina, Shirokova, Ushakova, Fominykh, Medvedeva, Murin.Published on the basis of a report delivered at the VII Meeting on Fundamental Problems in Solid-State Ionics (Chernogolovka-2004).     

Differential transport and dispersion of colloids relative to solutes in single fractures

This work employed numerical experiments simulating colloid and solute transport in single parallel-plate fractures, using the random walk particle tracking method, to demonstrate that (1) there exists an aspect ratio of the colloid radius to half the fracture aperture, δ_o, where the average velocities of colloids and solutes are similar. When δ > δ_o, the velocity distribution assumption is satisfied, and the fact that the ratio of the colloid transport velocity to the solute transport velocity, τ_p, decreases as δ increases is well documented in the literature. However, when δ < δ_o, the velocity distribution assumption is violated, and τ_p increases as δ increases and (2) the Taylor dispersion coefficient and its extension by James and Chrysikopoulos [S.C. James, C. V. Chrysikopoulos, J. Colloid Interface Sci. 263 (2003) 288] will overestimate the colloid dispersion coefficient significantly. Additionally, numerical experiments simulating colloid and solute transport in variable-aperture fractures demonstrated that τ_p and D_L,coll/D_L,solute decrease with increasing CoV, and the anisotropy ratio only plays a minor role compared to the CoV. These observations have important implications towards the interpretation of colloid transport in both porous and fractured media.     

Multistep electrochemical reactions involving transport of intermediates between the near-electrode layer and the bulk solution: A kinetics analysis based on theory of generalized variables (theory of similarity)

A kinetic analysis of multistep electrochemical reactions involving partial diffusion transport of intermediates between the near-electrode layer and the bulk electrolyte is performed within theory of generalized variables (theory of similarity). Dimensionless complexes (similarity criteria) that characterize such reactions are obtained, and their values corresponding to the transport of intermediates are determined.Translated from Elektrokhimiya, Vol. 41, No. 1, 2005, pp. 121–125.Original Russian Text Copyright © 2005 by Protsenko, Danilov.     

Synthesis of a calix[4]crown modified with germanium‐containing side chains

A germacalix‐crown, 25,27‐bis[1‐(3‐trimethylgermylpropyl)oxy]calix[4]arene‐crown‐6, 1,3‐alternate ( 1a ), and its carbon analog, 25,27‐bis‐[1‐(4,4‐dimethylpentyl)oxy]calix[4]arene‐crown‐6, 1,3‐alternate ( 1b ), were prepared and their structures were confirmed by elemental analysis and ¹H and ¹³C NMR spectroscopy. A cation transport test indicated that both compounds exhibited much the same cation transport ability, so that the role of the germanium moiety in capturing and transporting counteranions is not yet clear. Copyright © 2005 John Wiley & Sons, Ltd.     

十字交叉型π共轭分子3,6-二苯-1,2,4,5-(2′,2″-二苯基)-苯并二噁唑的电子结构和电荷传输性质的理论研究

采用密度泛函理论的B3LYP方法, 在6-31G(d)基组水平下研究了以三联苯和二苯基苯并噁唑构成的十字交叉型共轭分子3,6-二苯基-1,2,4,5-(2′,2″-二苯基)-苯并二噁唑的电子结构和电荷传输性质. 通过对分子的重组能和晶体中分子间电荷传输积分的计算得到该分子的空穴迁移率为0.31 cm²·V^-1·s^-1, 电子迁移率为0.11 cm²/(V·s). 计算结果表明, 空穴的传输主要是通过三联苯方向上两端苯环的“边对面”的相互作用以及分子中心π体系的错位重叠相互作用来实现的. 而电子的传输路径主要是通过苯并噁唑方向的π-π重叠相互作用来实现. 通过分析分子正负离子态的Mulliken电荷发现, 正电荷较多分布在三联苯方向上, 而负电荷较多分布在苯并噁唑方向上. 计算结果表明, 电子和空穴的传输分别在分子相互交叉的不同方向上, 有利于电子和空穴的平衡传输.     

Water transport coefficient distribution through the membrane in a polymer electrolyte fuel cell

The net water transport coefficient through the membrane, defined as the ratio of the net water flux from the anode to cathode to the protonic flux, is used as a quantitative measure of water management in a polymer electrolyte fuel cell (PEFC). In this paper we report on experimental measurements of the net water transport coefficient distribution for the first time. This is accomplished by making simultaneous current and species distribution measurements along the flow channel of an instrumented PEFC via a multi-channel potentiostat and two micro gas chromatographs. The net water transport coefficient profile along the flow channels is then determined by a control-volume analysis under various anode and cathode inlet relative humidity (RH) at 80 °C and 2 atm. It is found that the local current density is dominated by the membrane hydration and that the gas RH has a large effect on water transport through the membrane. Very small or negative water transport coefficients are obtained, indicating strong water back diffusion through the 30 μm Gore-Select^® membrane used in this study.     

Electrochemical Properties of Membranes Based on Associates of Beta-Lactam Antibiotics with Tetradecilammonium

The electrode and transport properties of liquid and plasticized membranes based on associates of beta-lactam antibiotics with tetradecilammonium are studied. Rates of transport, penetrability, and ion flux of antibiotics are evaluated in conditions of self-diffusion and applied potential. Apparent dissociation constants are calculated for organic ion exchangers from steady-state resistances of membranes.__________Translated from Elektrokhimiya, Vol. 41, No. 8, 2005, pp. 981–986.Original Russian Text Copyright © 2005 by E. Kulapina, Baraguzina, O. Kulapina, Chernov.     

Competitive bulk liquid membrane transport of Co(Ⅱ),Ni(Ⅱ),Zn(Ⅱ),Cd(Ⅱ),Ag(Ⅰ),Cu(Ⅱ)and Mn(Ⅱ),cations using 2,2'-dithio(bis)benzothiazole as carrier

A series of competitive metal-ion transport experiments has been performed.Each involved transport from an aqueous source phase across an organic membrane phase into an aqueous receiving phase.The source phase contained equimolar concentration of Co（Ⅱ）,Ni（Ⅱ）,Zn（Ⅱ）,Cd（Ⅱ）,Ag（Ⅰ）,Cu（Ⅱ） and Mn（Ⅱ） metal cations.The transport experiments of metal cations were carried out by 2,2’-dithio（bis）benzothiazole（DTB） in chloroform（CHCl₃）.The source phase being buffered at range pH of 4-6.5 and receiving phase being buffered at pH 3.The obtained results show that the selectivity and the efficiency of Ag（I） transport from aqueous solutions are observed in this investigation.The effect of concentration of palmitic acid in the transport efficiency of Ag（Ⅰ） ion was also conformed.     

The Soret effect with chemical reaction in aqueous sulfuric acid solutions

The Soret coefficient of aqueous sulfuric acid has been determined conductimetrically from 0.0005 to 0.2m at 25°C. The derived enthalpies of transport increase sharply as the concentration drops, approaching a limiting value near 35 kJ-mol^–1. The increase, in the enthalpy of transport at low concentrations is due to the large intrinsic enthalpies of transport of the hydrogen and sulfate ions that are produced by the dissociation of bisulfate ions. The enthalpy of dissociation of the bisulfate ions reduces the acid's enthalpy of transport by up to 1.8 kJ-mol^–1.