Bathocuproine-Mediated Copper Transport through Liquid Membrane Driven by Redox Potential

Abstract

A new type of carrier-mediated copper transport system driven by redox potential was studied. The two aqueous solutions of different redox potentials were separated by a polymer-supported organic liquid membrane in which Bathocuproine (L) was dissolved as a “carrier”. Copper(II) was reduced in the reducing phase to form [Cu¹L₂]⁺·X^? type complex at the membrane interface and extracted. The copper complex diffused to the other side of the membrane and decomposed to form the copper(II) species in the oxidizing phase, leaving the carrier in the membrane phase. The nature of the system under various operational conditions (pH, redox agents, pairing anions X^?, coexisting metals, etc.) was studied and compared with the metal transport system which can take place without the intervention of redox reaction. An extension of these transport reactions to water-in-oil-in-water type emulsion system was studied.     

Transport of cadmium and iron through a carboxylic membrane based on a poly(vinyl chloride)/poly(methyl methacrylate‐co‐divinyl benzene) system

The transport of cadmium and iron through a poly(vinyl chloride)/poly(methyl methacrylate‐co‐divinyl benzene) carboxylic ion‐exchange membrane was investigated with a system containing HCl as the receiver solution and CdCl₂ or FeCl₃ as the feed solution. Transport of the ions through the membrane depended on the H⁺ concentration in the receiver solution and the metal concentration in the feed solution. The rate of transfer for cadmium was about 35% higher than that for iron under the same conditions (0.5 mol/dm³ of HCl, 0.1 mol/dm³ of CdCl₂ or FeCl₃, and 5 h of dialysis). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 705–707, 2005     

Hemiprotonated dafone,a new cationic species. The novel di-dafonium iron(III) complex: [(dafone)2H]+[FeCl4]−

The reaction of dafone (4,5-diazafluoren-9-one, 1) and iron(III) chloride in concentrated hydrochloric acid medium yields an unusual complex containing hemiprotonated dafone, [(dafone)₂H]⁺[FeCl₄]⁻. The crystal structure reveals that two coordinating ligands share a single proton to form the new cation [(dafone)₂H]⁺ while the accompanying tetrachloroferrate(III) anion stabilizes the ion pair. The [FeCl₄]⁻ anion is close to tetrahedral in geometry with four chloro ligands in the first coordination sphere which is only slightly affected by the interactions with the di-dafonium unit.     

Kinetics of armco iron dissolution in an anhydrous methanol and hydrochloric acid solution

The polarization behaviour of Armco iron in anhydrous solutions of CH₃OH+HCl and CH₃OH+HCl+LiCl was studied by the potentiostatic method. The following reaction orders were found for the anodic process: Z_a(Cl^?) = 1.7 –1.82 and Z_a(H⁺) = 0. The following mechanism of dissolution is proposed: Fe+Cl^? ? FeCl^?_ads, FeCl^?_ads+Cl^? → FeCl₂+2e (rate-determining step), FeCl₂?FeP²⁺ + 2Cl^?.     

The influence of chloride ions on the kinetics of iron dissolution

The anodic dissolution of pure iron was studied in oxygen-free solutions at high concentrations of chloride and hydrogen ions at 25°C under potentiostatic steady-state conditions. In the range c_H⁺ ? 1 M the following kinetic data were obtained: Tafel slope b₊ ? +100 mV, electrochemical reaction order related to C_H⁺, n_+.H⁺ = +1·1, and electrochemical reaction order related to the chloride ion concentration, n_+,Cl^? = +0·6. These values cannot be correlated to the currently proposed mechanisms of iron dissolution, another mechanism is suggested for the described conditions. The correlations to known mechanisms are discussed.     

Coupled Transport of Zr(IV) through Tri-n-butylphosphate-Xylene-Based Supported Liquid Membranes

Abstract

The transport of Zr(IV) through tri-n-butylphosphate-xylene-based liquid membranes, supported in a polypropylene hydrophobic microporous film, has been studied. The concentration of HNO₃ in the feed solution and tri-n-butylphosphate (TBP) carrier in the membrane were varied, and the flux and permeability coefficients were determined. The optimum conditions found for maximum flux were determined to be 10 mol/dm³ HNO₃ and 2.93 mol/dm³ TBP with a flux value of 12.9 × 10^?6 mol · m^?2 · s^?1. The solvent extraction study revealed that 1.25 to 3.5 protons are involved in zirconium transport, and that two molecules of TBP are involved in the complex formation. The value of protons involved varies with acid concentration. The zirconium ion transport is coupled with nitrate ions transport.     

Rotating disc electrode study of anodic dissolution or iron in concentrated chloride media

The anodic dissolution of iron in concentrated neutral and acid chloride media was investigated by measuring anodic potentionstatic polarization curves on a rotating disc electrode. Well defined mass transport limited current plateaux were observed, the diffusion limiting species being the Fe²⁺ ion. Experiments performed in binary FeCl₂ electrolytes showed that the FeCl₂ concentration at the anode at limiting current was equal to the saturation concentration. A semiempirical method for estimating the magnitude of the plateau current in different chloride media is outlined.     

Transport of Co(II) Ions through Di(2-ethylhexyl) Phosphoric Acid-CCl4 Supported Liquid Membranes

Abstract

A liquid membrane transport study of Co(II) using di(2-ethylhexyl) phosphoric acid (D2EPHA) as carrier and CCl₄, as diluent supported on polypropylene microporous film has been carried out. The carrier concentration in the membrane and HCl concentration in the stripping phase have been varied to see the effect on transport of Co(II) ions across the membrane. Maximum flux and permeability values of 1.23 × 10^?5 mol · m^?2 · s^?1 and 7.66 × 10^?11 m²/s, respectively, at a 0.87 mol/dm³ carrier concentration in the membrane have been found. At 1 mol/dm³ HCl concentration in the stripping phase the flux and permeability have maximum values of 1.4 mol · m^?2 · s^?1 and 5.27 × 10^?11 m²/s, respectively. The distribution coefficient of Co(II) ions into organic phase has been found to increase with increasing carrier concentration. The diffusion coefficient determined varies from 13.73 × 10^?11 to 0.83 × 10^?11 m²/s, which is the reverse order of the values of the distribution coefficient and explains the permeability of the Co(II) D2EPHA complex through the membrane.     

High Diffusion Permeability of Anion-Exchange Membranes for Ammonium Chloride: Experiment and Modeling

It is known that ammonium has a higher permeability through anion exchange and bipolar membranes compared to K⁺ cation that has the same mobility in water. However, the mechanism of this high permeability is not clear enough. In this study, we develop a mathematical model based on the Nernst–Planck and Poisson’s equations for the diffusion of ammonium chloride through an anion-exchange membrane; proton-exchange reactions between ammonium, water and ammonia are taken into account. It is assumed that ammonium, chloride and OH⁻ ions can only pass through membrane hydrophilic pores, while ammonia can also dissolve in membrane matrix fragments not containing water and diffuse through these fragments. It is found that due to the Donnan exclusion of H⁺ ions as coions, the pH in the membrane internal solution increases when approaching the membrane side facing distilled water. Consequently, there is a change in the principal nitrogen-atom carrier in the membrane: in the part close to the side facing the feed NH₄Cl solution (pH < 8.8), it is the NH₄⁺ cation, and in the part close to distilled water, NH₃ molecules. The concentration of NH₄⁺ reaches almost zero at a point close to the middle of the membrane cross-section, which approximately halves the effective thickness of the diffusion layer for the transport of this ion. When NH₃ takes over the nitrogen transport, it only needs to pass through the other half of the membrane. Leaving the membrane, it captures an H+ ion from water, and the released OH⁻ moves towards the membrane side facing the feed solution to meet the NH₄⁺ ions. The comparison of the simulation with experiment shows a satisfactory agreement.     

Performance and cycling of the iron-ion/hydrogen redox flow cell with various catholyte salts

A redox flow cell utilizing the Fe²⁺/Fe³⁺ and H₂/H⁺ couples is investigated as an energy storage device. A conventional polymer electrolyte fuel cell anode and membrane design is employed, with a cathode chamber containing a carbon felt flooded with aqueous acidic solution of iron salt. The maximum power densities achieved for iron sulfate, iron chloride, and iron nitrate are 148, 207, and 234 mW cm^?2, respectively. It is found that the capacity of the iron nitrate solution decreases rapidly during cycling. Stable cycling is observed for more than 100 h with iron chloride and iron sulfate solutions. Both iron sulfate and iron chloride solutions display moderate discharge polarization and poor charge polarization; therefore, voltage efficiency decreases dramatically with increasing current density. A small self-discharge current occurs when catholyte is circulating through the cathode chamber. As a result, a current density above 100 mA cm^?2 is required to achieve high Coulombic efficiency (>0.9).     

Supported Liquid Membrane Extraction Study of (MoO4)2- Ions using Tri-n-octylamine as Carrier

Abstract

The transport of (MoO₄)^2- ions across a tri-n-octylamine (TOA) xylene-based supported liquid membrane has been studied at various HCl concentrations in the feed, TOA concentrations in the membrane, and NaOH concentrations in the strip solution. The distribution coefficient and flux of the Mo(VI) ion species vary with the HCl concentration, indicating that different polymeric species of this metal ion are present in the aqueous solution. A TOA concentration increase of up to 1.308 mol/dm³ enhances flux and permeability of this metal ion, which beyond this concentration is reduced due to an increase in carrier liquid viscosity. An increase in NaOH solution concentration has been found to increase flux and permeability values. The continuous increase in pH of the feed with the transport of metal ions indicates that the (MoO₄)^2- transport does not involve a decrease or increase in concentration as a result of association of lower to higher or decomposition of higher to lower metal ions polymeric species. The optimum conditions of transport of Mo(VI) metal ions across these membranes have been found to be HCl = 0.01, [NaOH] = 1, and [TOA] = 1.308, furnishing flux and permeability values of the order of 2.49 × 10^?4 mol·m^?2·s^?1 and 2.32 × 10^?10 m²·s^?1, respectively.     

Komplexe des Eisens mit aromatischen Liganden

Complexes of Iron with Aromatic Ligands The reaction of FeCl₃ · 6 H₂O with several substituted o-phenylene diamines forms complexes of the Fe(II)-ion with o-quinone diimines. Before the formation of these complexes there are a few of redox reactions between Fe(III)ions and the diamines. The Fe(III)/o-quinone diimine-complex is an intermediate which was characterized by means of spectroscopic methods. The two forms of 6-oxy-7-nitrosobenzthiazoline produce only one 1:3 complex with Fe(II)ions. Also the N-methyl-6-oxy-7-nitrosobenzthiazolium iodide forms a 1:3 complex. In the former complex the quinone-oxim-form is the ligand. The isolated complexes were characterized through elemental analysis and physical methods.     

Selective and Efficient Liquid Membrane Transport of Thallium (III) Ion by Potassium‐dicyclohexyl‐18‐crown‐6 as Specific Carrier

Abstract

Potassium‐dicyclohexyl‐18‐crown‐6 was used as a selective and efficient carrier for the uphill transport of thallium (III) ion as [TlCl₄]^? complex ion through a chloroform bulk liquid membrane. By using oxalate anion as a metal ion acceptor in the receiving phase, the amount of thallium (III) transported across the liquid membrane after 120 min was 96±2%. The selectivity and efficiencies of thallium transport from aqueous solutions containing Cu²⁺, Zn²⁺, Ni²⁺, Cd²⁺, Pb²⁺, Co³⁺, Mn²⁺ _, Cr³⁺, Mg²⁺, Ca²⁺, K⁺, Na⁺, and Fe³⁺ ions were investigated. In the presence of Na₃PO₄ (0.01 M) at pH=3 as a suitable precipitation agent in the source phase, the interfering effect of Pb²⁺ ion were diminished drastically.     

Macromolecular complexes consisting of poly(aluminum chloride), [2-(diethylamino)ethyl]dextran hydrochloride,and potassium poly(vinyl sulfate)

The mixture of poly(aluminum chloride) (PAC) and [2-(diethylamino)ethyl]dextran hydrochloride (EA) were allowed to react with potassium poly(vinyl sulfate) (PVSK) to form many different water-insoluble macromolecular complexes (MCs) in aqueous solution at various hydrogen ion concentrations. According to elemental analyses, IR spectroscopy, and solubilities of MCs, molecular structures of each MC depend on [H⁺]. It is suggested that the MCs obtained at pH 1.0 are products consisting of EA, PVSK, and aluminum aquo-complex having coordination water whereas the MCs at pH 4.0 are higher molecular products consisting of EA, PVSK, and basic aluminum maltidentate complex. This result is attributable to change with [H⁺] in the degree of dissociation and conformation of EA, PVSK, and the dissociation of hydrated coordination of PAC. MC membranes were made by casting solutions of all kinds of MCs, and active, selective transport phenomena through a membrane of the MC prepared in a solution of pH 1.0 HCl were investigated under various conditions. Transport ratio of Na⁺ and the electric potential difference between the left and right sides of the membrane were measured, with a result that the higher value the membrane potential difference was long allowed to maintain, the higher the transport ratio became. According to this result, the driving force of transport is dependent on the membrane potential, Donnan potential, and diffusion potential, between both sides of the membrane. The Cl^? exclusion (Donnan exclusion), however, is small due to the small cation-exchange capacity, so that the membrane potential difference is caused to decrease rather rapidly by Cl^? permeation. It was also suggested that the affinity of the carrier and both the chemical and physical properties of the MC membrane controlled the selective transport through the membrane.     

Evaluation of Transport Capacity through Liquid Membranes of Some Crown Ether‐Siloxane Copolymers

The complexation ability of some linear crown ether‐siloxane copolymers of ester or amide type with cations as K⁺ and NH₄⁺ was investigated spectrophotometrically in order to select the polysiloxane receptors that achieve good ion transport ability by bulk liquid membrane systems. The transport properties of the potassium picrate through a liquid membrane using siloxane‐crown ether polyamide as carrier were discussed.     

Selective Transport of Alkali and Alkaline Earth Metallic Ions through a Supported Liquid Membrane Containing Tripentyl Phosphate as a Carrier

Abstract

A selective transport system for alkali and alkaline earth metallic ions with a perchlorate ion as a pairing ion species through a supported liquid membrane (SLM) containing tripentyl phosphate (TPP) as a carrier is described. The SLM used is a porous polypropylene membrane impregnated with TPP solution in o-nitrophenyloctylether. The effects of the pairing ion species, the initial perchlorate concentration, and the TPP concentration on metallic ion transportability are examined under various experimental conditions. The permeation velocities of the metallic ions in the transport system followed the sequence Li⁺?Na⁺>K⁺>Mg²⁺; that is, a highly selective transport for Li⁺ ion was observed. Compared with the transport rates of alkali metallic ions, those of transition metallic ions such as Cu²⁺ and Fe³⁺ ions are very low. The permeation velocities of alkali and alkaline earth metallic ions through an SLM are dependent on the concentrations of perchlorate and TPP. Equations for the permeation velocities of Li⁺, Na⁺, K⁺, and Mg²⁺ ions through an SLM, based on two concentrations of perchlorate and TPP, are proposed.     

Electrochemical behavior of several iron complexes in hydrophobic room-temperature ionic liquids

The electrochemical behavior of FeCp₂⁺/FeCp₂ (Cp⁻, cyclopentadienyl), FeCl₄⁻/FeCl₄²⁻, FeBr₄⁻/FeBr₄²⁻ and Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ couples was studied in the hydrophobic room-temperature ionic liquids based on bis(trifluoromethylsulfonyl)imide (TFSI⁻) with 1-n-butyl-1-methylpyrrolidinium (BMP⁺) and other quaternary ammonium cations. The cyclic voltammetric data indicated that these complexes were stable in BMPTFSI and that the redox reactions between trivalent and divalent iron species of these complexes are electrochemically reversible. The diffusion coefficients of these complexes were found to be affected mainly by the size of the species. On the other hand, the redox potential of Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ couple depended on organic cations reflecting the difference in the acceptor properties of the organic cations.     

The Mutual Effect of Iron(III) and Silver(I) Species in Concentrated Chloride Medium

Abstract

Earlier studies carried out to evaluate the selectivity of solvating extractants towards silver(I) in concentrated chloride media revealed that an intriguing situation occurs if a given excess of iron(III) concentration is present in the aqueous solution: the extraction of silver(I) becomes almost quantitative and independent of the initial chloride content. On the assumption that this effect may be due to a phenomenon occurring in the aqueous phase, a systematic study involving solutions containing different Ag(I), Fe(III), and HCl concentrations was carried out by solvent extraction and capillary electrophoresis. Capillary electrophoresis suggests that the AgCl₃ ^2? amount in solution decreases in the presence of Fe(III), whereas FeCl₃ seems to be partially converted onto FeCl₄ ^?. From the experiments performed, it can be concluded that the presence of Fe(III) seems to facilitate the formation of less anionic Ag(I) species, which are in turn more easily extracted by solvating extractants. Furthermore, the presence of FeCl₄ ^? has been detected in the organic phase of triisobutylphosphine sulfide (TIBPS) by UV‐Vis spectrophotometry, after equilibration with HCl solutions containing both Ag(I) and Fe(III), which was not identified during similar experiments carried out in the absence of Ag(I). Speciation of silver(I) and iron(III) in concentrated chloride medium has also been worked out by a numerical methodology.     

Faradaic rectification study of the metal/metal ion reactions

The kinetic parameters for Ag⁺/Ag and Cu²⁺/Cu reactions at the equilibrium potential and in the absence of dc polarisation have been obtained using the faradaic rectification method at audio frequencies. The values of transfer coefficients, ion exchange current densities and apparent rate constants, obtained for the two reactions at 27°C using 1·0mM of each of the Ag⁺ and Cu²⁺ in 1·0M KNO₃, are respectively 0·22; 7·3mA/cm²; 3·6·10^?3 cm/s and 0·45; 10·7 mA/cm²; 1·1×10^?4cm/s. These data are comparable to those reported in the literature. For obtaining reliable and reproducible results for the studies with metal/metal ion reactions suitable experimental conditions have been described.