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.     

Selective Transport of Cu2+ Ions through Bulk Liquid Membrane System Mediated by Erythromycin Ethyl Succinate

The carrier mediated transport of Cu²⁺ ions from an aqueous medium has been examined. The ability of Erythromycin Ethyl Succinate (EES) as a carrier to form a complex with Cu²⁺ ions and transport them to the receiving phase is reported. The fundamental parameters influencing the transport of Cu²⁺ ions such as the pH in the source and receiving phases and concentration of the stripping agent in the receiving phase have been optimized and accordingly, the amount of Cu²⁺ transported across the liquid membrane after 5 h was 94.3 ± 1.8% in the presence of L-histidine as a suitable stripping agent. Moreover, the selectivity and efficiency of Cu²⁺ ions transport from aqueous solution over other cations in ternary and quaternary mixtures have been investigated. The results indicate that our fabricated membrane is very sensitive toward Cu⁺² ions in the presence of heavy metal ions.     

Selective Transport of Bismuth Ions through Supported Liquid Membrane

A new supported liquid membrane (SLM) system was prepared for the selective transport of bismuth ions from the aqueous feed into the aqueous permeate phase. The support of the SLM was a thin porous polypropylene or polyvinylidene fluoride membrane impregnated with diisooctyldithiophosphinic acid (Cyanex 301) as mobile carrier in 4‐chloroacetophenon as organic solvent. Cyanex 301 acts as a highly selective carrier for the uphill transport of bismuth ions through the SLM. In the presence of HNO₃ as a metal ion acceptor in the strip solution, the transport of bismuth ions into the strip side reached 70 % of the initial feed concentration after 3.5 hours. The selectivity and efficiency of bismuth transport from aqueous solutions containing different mixtures of cations were investigated. In the presence of P₂O₇^2– ions as suitable masking agent in the feed solution, the interfering effects of other cations were completely eliminated. The selective transport of bismuth through SLM is superior to liquid‐liquid extraction or through bulk liquid membranes. This is due to the high efficiency. The SLM reduces the solvent requirements, combines extraction and stripping operations in a single process and allows the use of highly selective extractants. The system may be applied to samples containing very low bismuth concentrations.     

Studies of Ion Transport through a Liquid Membrane by Using Crown Ethers

Abstract

Studies on ion transport through a liquid membrane system composed of two extraction processes have been carried out. Kinetic models based on extraction processes with consideration of the controlled parameters were developed for mediated ion transport through liquid membranes, especially those using crown ethers as the ion carrier. A study of the concentration change in the receiving or source phase envisages the determination of the equilibrium constant by a kinetic method corresponding to the chemical reaction at the interface as well as the maximum initial flux through the membrane. The equilibrium constant values determined by the kinetic process were checked by the solvent extraction method.     

Transport Studies of Monovalent Ions through Nafion-117 Ion Exchange Membrane in Presence of Polyacrylate

The results of equilibrium distribution and transport kinetics of monovalent (Li⁺, Na⁺, and Cs⁺) ions through Nafion-117 ion exchange membrane in presence of polyacrylate anion have been presented. For Na⁺-Li⁺ system, equilibrium distributions in the presence and absence of polyacrylate have been found to be the same indicating that the Donnan membrane equilibrium is not affected by the presence of polyacrylate. For the Na⁺-Cs⁺ system, a favored transport of Cs⁺ ion to the polyacrylate compartment has been observed, indicating the binding of Cs⁺ ion with polyacrylate is stronger than other monovalent ions. This is due to the lower hydration radius of Cs⁺ ions. The deviation from Donnan membrane equilibrium condition has been used to obtain information about the fraction of counter-ions bound to the polyacrylate. The transport profile in the presence of polyacrylate has also been calculated based on the modified Nernst Planck (NP) approach, taking into account the fraction of counter-ions bound to the polyacrylate ion. The Donnan relation has been used to obtain the concentration of ions at the solution/membrane interface. The self-diffusion coefficients of ions and membrane ion exchange capacity have been given as input parameters in the calculations. The calculated time profile has been found to agree well with the experimental time profile.     

Studies on Carbonate Ion Transport through Supported Liquid Membrane Using Primene JMT and Tributyl Phosphate

Abstract

A supported liquid membrane system consisting of source, receiving and membrane phases, in which mixed extractants were used in the membrane phase, was explored for the carbonate ion transport from source to receiving through membrane phase. Primary amine Primene JMT and TBP were used as extractants (carriers) in liquid membrane phase. Different experimental variables such as concentration of carbonate ion, carriers, alkali and hydrogen peroxide, stirring speed, etc have been investigated. Primary amine Primene JMT and TBP mixed carriers show the synergistic effect for the transport of carbonate ions through supported liquid membrane system. The stability of the supported liquid membrane system has been explored for 50 h. The pre-concentration of carbonate ions from dilute solutions were also demonstrated. The effect of different alkalis on the permeability coefficient of transport of carbonate ions through supported liquid membrane system has been investigated. The primary amine in combination with TBP shows more effective for the transport of carbonate ions through supported liquid membrane system in comparison with that of secondary and tertiary amines.     

Transport of Cadmium(II) Ion through a Supported Liquid Membrane Containing a Bathocuproine

Abstract

The active transport of cadmium ions across a supported liquid membrane (SLM) containing a ligand based on a driving force supplied by the concentration gradient of the chloride ion is described. The SLM used is a microporous polypropylene membrane impregnated with a bathocuproine (4,7-diphenyl-2.9-dimethyl-1,10-phenanthroline) solution in dibenzyl ether as a carrier. The characteristics of the cadmium ion transport system are examined under various experimental conditions. The active transport of cadmium ions through an SLM is dependent on the concentrations of the cadmium ion, ligand, and chloride ion. An equation for the permeation velocity of cadmium ions, consisting of three important factors for this transport system, is proposed.     

Flux and Characteristic Parameters in Mediated Transport through Liquid Membranes. II. A Model for Co-transport and Experimental Study of Kl Transport through a Bulk Liquid Membrane

Abstract

In this article we establish a steady-state theoretical model for cotransport through liquid membranes. Integration of the flux equation gives the concentration in the receiving phase as a linear function of time under certain conditions. From this, an expression for the relative permeability of the carrier-permeant complex with respect to the carrier is obtained; this permeability depends on the equilibrium constant of the interphases reaction and on another parameter related to the initial concentration of permeant in extramembrane phases. An experimental study of the variation of permeant concentration in the receiving phase allows determination of several characteristic transport parameters.     

Carrier-Mediated Transport of Rare Earth Ions through Supported Liquid Membranes

Abstract

Fluxes of rare earth ions (Sc³⁺, Y³⁺, La³⁺, Sm³⁺, and Lu³⁺) across supported liquid membranes using mixtures of nitrophenyl octyl, heptyl, or phenyl ethers and tris(2-n-butoxyethyl) phosphate (TBEP) as solvents and some β-diketones as carriers were determined. The effects of membrane composition, pH of the source phase, and carrier concentration on the flux are demonstrated. The effect of membrane composition is further discussed from the values of the membrane potential and the viscosity and electrical conductivity of the solvents. A maximal flux of lanthanum is observed for the membranes by using mixtures consisting of equal volumes of the nitrophenol derivative and TBEP. The fluxes of the rare earths, except scandium, decrease rapidly with decreasing pH difference between the source and receiving phases. The difference in flux among the rare earths, except scandium, is small. The flux increases in the carrier order benzoyl- > thenoyl- > furoyltrifluoroacetones. The lanthanum flux is proportional to the carrier concentration.     

Study on Competitive Transport of Heavy Metal Ions Through Liquid Surfactant Membrane

Abstract

In the present work an attempt has been made to develop a mathematical model for competitive transport of Cr(VI) and Mo(VI) through liquid surfactant membrane from acidic solution using Alamine‐336 and Caustic Soda as extractant and stripping reagent respectively. A reaction front has been assumed to exist within the emulsion globule in the proposed model. It has been assumed that, an instantaneous and irreversible reaction takes place at the membrane‐internal stripping phase interface between the solute and internal stripping reagent. Experiments on simultaneous extraction of Cr(VI) and Mo(VI), in batch mode, from aqueous solutions of Potassium Dichromate and Ammonium Molybdate have been carried out with the initial concentration of the solutes between 50–100 mg/l. Experiment on emulsion stability has also been performed to arrive at a reasonably stable emulsion composition. Effect of initial solute concentration on distribution coefficient has also been found experimentally and fitted by a semiemperical model that has been used in the computer simulation of the simultaneous extraction process. It has been found that the experimental results are within reasonably close proximity with the simulated curves.     

Cu2+在支撑液膜中的传质过程

研究了以疏水性多孔聚丙烯膜(Celgard 2500)为支撑体和LIX984的煤油溶液为膜液的支撑液膜体系萃取Cu2+的传质过程. 采用双膜理论描述Cu2+通过平板支撑液膜的传质过程,建立了其在稳态下的传质动力学方程,且当反萃取侧酸浓度大于2 mol/L时,反萃取侧的传质阻力可以忽略;利用膜内分传质系数km表征支撑液膜膜液的流失行为,在传质过程中,km先增大而后逐渐减小,且载体的流失速率大于稀释剂煤油的流失速率. 考察了操作条件对传质和膜液流失速率的影响,结果表明,Cu2+初始传质通量随载体初始浓度、料液初始pH值和料液初始Cu2+浓度的增大而增大;载体初始浓度越大,膜液流失越快;料液初始Cu2+浓度增大,膜液流失越慢;料液相pH值的改变对膜液流失速率没有影响.     

Transport of Palladium(II) through Trioctylamine Liquid Membrane

Abstract

The permeation behavior of palladium(II) through a supported liquid membrane (SLM) impregnated with trioctylamine (TOA) in kerosene has been investigated. By selecting perchloric or nitric acid as a stripping agent, Pd(II) was transported through the SLM containing 0.5 M TOA and 20% 1-octanol without remaining in the liquid membrane. The permeation rate (k _{f. obs}) of Pd(II) for HNO₃ was faster than that for HClO₄. Palladium(II) was concentrated across the SLM from the 0.5 M CHI solution into the HClO₄ or HNO₃ solution.     

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.     

Analysis of Transport Rate of Zinc Extraction through Liquid Surfactant Membrane

Abstract

Analysis of the transport rate of a metal ion through a liquid surfactant membrane is important for understanding an extraction system. A facilitated transport model for zinc extraction through a liquid surfactant membrane is proposed for the analysis of the transport rate. Based on the model, the transport rates, including the interfacial reaction rates and the diffusion rate of the zinc ion, are analyzed. From an analysis of the model, it is shown that the reactions at both interfaces are not in equilibrium before extraction is complete. It is also shown that the transport rates are not equal value in the early stage of a run. Parametric effects on the transport rates are also illustrated.     

Transport of Europium through Supported Liquid Membrane Containing Dihexyl-N,N-diethylcarbamoylmethylphosphonate

Abstract

The transport of europium has been studied through a supported liquid membrane (SLM) impregnated with dihexy-N,N-diethylcarbamoylmethylphosphonate (CMP). Europium was effectively extracted from the perchlorate solution into SLM, but was insufficiently stripped to a dilute acid solution. The addition of 1-decanol improved the stripping process, and quantitative transport of europium was achieved. By the combination of two SLM systems consisting of diiso-decylphosphoric acid and CMP, europium was transported from the feed solution (0.1 M HNO₃) through the intermediate solution (1 M HclO₄ + 4 M NaClO₄) to the product solution (0.1 M HNO₃) and effectively concentrated by a factor of about 20.     

The Transport of Copper(II) through Hollow Fiber Renewal Liquid Membrane and Hollow Fiber Supported Liquid Membrane

Abstract

In this paper, hollow fiber renewal liquid membrane (HFRLM) and hollow fiber supported liquid membrane (HFSLM) were used to simultaneously remove and recover copper(II) from aqueous solutions, and the transport performance of these two techniques were compared under the similar conditions for the system of CuSO₄ +D2EHPA in kerosene +HCl. The results showed that the HFRLM process was more stable than the HFSLM process. The HFRLM process had a higher overall mass transfer coefficient than that of HFSLM process in single-pass experiments. These were because the renewal effect of the liquid membrane layer could reduce the mass transfer resistance of the lumen side and replenish the loss of the membrane liquid in the HFRLM process. The transport results were better in the HFRLM process than that in the HFSLM process with recycling experiments. Therefore, HFRLM technique is a promising method for simultaneous removal and recovery of heavy metal from aqueous solutions.     

Transport Behavior of Basic Amino Acids through an Organic Liquid Membrane System

Abstract

The transport behavior of basic amino acids (BAA), such as arginine (Arg), histidine (His), and ornithine (Orn), through an organic liquid membrane system (LMS) was investigated. The LMS was composed of two aqueous phases (Phases I and II) separated by an organic phase of chloroform containing sodium di-(2-ethylhexyl) sulfosuccinate (Aerosol OT, AOT). The amount of BAA that moved from Phase I at pH 3 into the organic phase increased with increasing AOT concentration (2–10 mM). The relative amount of extracted BAA was in the following order: Arg > His > Orn. On the other hand, the release of BAA from the organic phase into Phase II at pH 10 did not depend upon their amount in the organic phase. Arg was difficult to release. The relative amount of released BAA was in the following order: Arg = His > Orn. BAA were extracted from Phase I at pH 5 into the organic phase containing 4 mM AOT because they exist as cationic species. Other amino acids possessing nonionic residues were untransportable under these conditions except leucine, tryptophan, and phenylalanin, which have highly hydrophobic residues. However, they were transportable in their cationic forms at pH 1. These transport phenomena are essentially controlled by the interaction of the anionic group of AOT and a cationic form. These results suggested that BAA can be separated from most amino acids under an appropriate pH by using AOT.     

Highly Selective Li+ Ion Transport by Porous Molybdenum-Oxide Keplerate-Type Nanocapsules Integrated in a Supported Liquid Membrane

Porous Keplerate-type molybdenum-oxide nanocapsules – encapsulated into cationic surfactants – act as transporting systems for alkali cations through supported liquid membranes. The transport is based on the ability of the nanocapsules containing water molecules inside their cavities to attract and release the cations. This results in specific nanoscaled translocation pathways, based on corresponding dynamic diffusional domains within the liquid bulk membrane phase, due to the self-assembly of the capsules. Li⁺ cations are preferentially extracted and transported, thus allowing separation from Na⁺ and K⁺ cations, which are not transported to the receiving phase.