Reverse permeation of sodium ions driven by pH difference across a liquid membrane: time dependencies of membrane resistance and membrane potential in a reverse permeation system

The diffusional flux of sodium ions across a liquid membrane was observed as a reverse permeation phenomenon: sodium ions were transported across the membrane against their own concentration difference. A supported liquid membrane having stearic acid as an ionic carrier was used. The internal aqueous phase contained NaCl and HCl and the external aqueous phase contained NaOH of the same initial concentration as NaCl in the internal aqueous phase. The reverse permeation occurred with a long time delay. During the delay, sodium ions flowed from the acidic to alkaline solution. The diffusion coefficient of sodium ion estimated from the flux equation taking into account the Donnan equilibrium at the interface was found to be much greater than that in the membrane solvent, 1-octanol. In the same membrane system as for the flux measurement, the membrane conductance and the membrane potential were measured as a function of time. The time dependence of the membrane potential in the presteady state showed a biphasic behavior. The initial rapid phase could be attributed to the change in the phase boundary potential and the subsequent slow step to the change in the diffusion potential within the membrane. Before the steady membrane potential had been reached, the reverse permeation of sodium ions against their own concentration difference was not observed. During the slow relaxation process of the membrane potential, the membrane resistance decreased to approach the steady state. Moreover, the oscillation of membrane potential abruptly started at a time in the slow step of the potential change and continued during the steady state. It was suggested that, at the presteady state, the increase in the amount of water in the membrane would drive a drastic change in the state of the liquid membrane in the filter pore, e.g. an inverted micellar structure making.     

Nonisothermal membrane phenomena across perfluorosulfonic acid-type membranes,Flemion S: Part II. Thermal membrane potential and transported entropy of ions

Thermal membrane potentials across the perfluorosulfonic acid-type membrane, Flemion S, were measured for HCl, alkali metal chlorides, and ammonium and methyl ammonium chlorides. The difference between the mean molar transported entropy of the counterions in the membrane and the partial molar entropy of the counterions in the external solution was determined from the experimental data on thermal membrane potential, thermoosmosis and electroosmosis. The sign of the thermal membrane potential in HCl solution varies from positive to negative with the concentration. In HCl and alkali metal chloride solutions, the order of their thermal membrane potentials (–/T) is H⁺>Li⁺=Na⁺>K⁺ which is roughly the inverse of that of the crystallographic radii of the ions. However, the order of their entropy differences is H⁺>Na⁺>K⁺>Li⁺ which is just the inverse of that of their thermoosmotic coefficients (D) or the entropy difference of water in thermoosmosis. For the ammonium and methyl ammonium ion forms, the orders of both –/T and increase with an increasing number of methyl groups: (CH₃)₄N⁺>(CH₃)₃NH⁺>(CH₃)₂NH ₂ ⁺ > CH₃NH ₃ ⁺ >NH ₄ ⁺ , which is also the inverse of that ofD or .     

Study on the liquid membrane oscillation of water/oil/water system containing TTAB and picric acid

The liquid membrane oscillation of a novel water （aqueous tetradecyl trimethyl ammoniumbromide, TTAB and alcohol solution）/oil （picric acid in chloroform solution）/water （aqueous glucose solution） system was investigated. By using homemade device, the curves of various liquid membranes oscillation with different concentration of TTAB and picric acid, types of alcohol and other organic solvents at different temperature were measured. The results show that the water （aqueous 7 mmol/L of TTAB and 0.5 mol/L of n-propanol solution）/oil （0.5 mmol/L of picric acid in chloroform solution）/water （aqueous glucose solution） system performed sustained and stable oscillation at 30 ℃. And the novel system can recognise added amino acid.     

Study on a novel antifouling polyamide–urea reverse osmosis composite membrane (ICIC–MPD): III. Analysis of membrane electrical properties

In this study, the electrical properties of the new polyamide–urea (ICIC–MPD) reverse osmosis composite membrane were analyzed via two self-made test cells. The electrical potential difference across membrane was measured via a perpendicular flow through mode potential difference measurement cell, and the electrical conductivity of membrane was tested by a tangential flow across mode conductivity measurement cell. Both streaming potential coefficient and gap between the upward and downward curves were determined by the plot of electrical potential difference versus up-loading and down-loading external pressure difference at both sides of membrane. It was found that pH of electrolyte solution has strong impact on streaming potential coefficient and electrical conductivity due to the dissociation of COOH group and protonation of NH₂ group of the active layer of ICIC–MPD membrane. It was also observed that both concentration of monomer 5-isocyanato-isophthaloyl chloride (ICIC) in the organic phase and contact time of organic phase with aqueous phase play an important role in salt rejection rate, gap between curves and electrical conductivity of the prepared ICIC–MPD membrane, and experimental results indicate that salt rejection rate of ICIC–MPD membrane is closely correlated to gap between curves at either polymerization condition. In addition, the effects of fouling behaviors on electrical potential difference and electrical conductivity of membrane were also discussed.     

Study of the effect of the membrane composition on ion transfer across a supported liquid membrane

The rate of ion transfer across the supported liquid membrane (SLM) is studied in the rotating diffusion cell (RDC), varying the chemical composition of the SLM from net-cloth supported gel membranes to radiation-grafted polymer membranes. Steady-state current–voltage curves are measured as a function of the rotation rate, and values for the standard rate constant, k⁰, are determined for a series of tetraalkylammonium cations from the analysis of the initial slopes and the diffusion limiting currents. The analysis gives values for k⁰ of the order of 10⁻²–10⁻⁴ cm s⁻¹, which is in rather good agreement with the values found in the literature for this type of the system. As controlled delivery of ionic drugs can be achieved by control of the electric current, whereby the SLM acts as a drug reservoir, the study is extended to the release of the anti-Alzheimer drug Tacrine, where ion-exchange fibers are embedded in the membrane as the drug carrier. Our previous transient experiments are also discussed, and it is suggested that their interpretation is seriously hampered by the non-uniform potential distribution, which brings about high capacitive currents.     

Thermal membrane potential across cation-exchange membranes for various halide solutions

Thermal membrane potential across cation-exchange membranes was measured for various halide solutions. Linear relationships between thermal membrane potential () and temperature difference (T) were observed, and the temperature coefficient of thermal membrane potential (/T) decreases with increase in the molality of the external solution as predicted by a theory reported. When counterions of membranes are hydrogen ions, the sign of the coefficients turns into minus near 0.01 mol/kg of the external solution for all membranes, although the coefficients are always positive for all the other forms. The dependence of the coefficients on the molality of the external solutions sometimes deviated slightly from the theory. This deviation is attributed to some change in water content of the membranes. A reproducible method of measuring water content of membranes was applied to discuss the change in the state of the membranes.     

Selective transport of copper(II) ions across a liquid membrane mediated by Piroxicam

Piroxicam was found to be a highly selective carrier for uphill transport of Cu²⁺ ions through a chloroform liquid membrane. The transport occurs via a counterflow of protons from the receiving phase to the source phase. The effects of several parameters on the transport of Cu²⁺ ions, such as the carrier concentration, pH of the source phase, composition of the receiving phase, and duration are described. A high transport efficiency (98±2%) was provided by the carrier for Cu²⁺ ions in a receiving phase of 0.01 mol l⁻¹ sulfuric acid after 4 h. Different metal ion transport experiments showed that Cu²⁺ ions were selectively transported over other ions, such as Co²⁺, Ni²⁺, Cd²⁺, Pb²⁺, Zn²⁺, UO₂²⁺ and ZrO₂²⁺. In the presence of fluoride ions (used as a suitable masking agent in the source phase), the interfering effects of UO₂²⁺ and ZrO₂²⁺ ions were eliminated. The applicability of the method was tested on a real sample, and the results obtained show that it is potentially useful for solvent extraction of copper.     

Drop-to-drop microextraction across a supported liquid membrane by an electrical field under stagnant conditions

Electromembrane extraction (EME) of basic drugs from 10 μL sample volumes was performed through an organic solvent (2-nitrophenyl octyl ether) immobilized as a supported liquid membrane (SLM) in the pores of a flat polypropylene membrane (25 μm thickness), and into 10 μL 10 mM HCl as the acceptor solution. The driving force for the extractions was 3–20 V d.c. potential sustained over the SLM. The influence of the membrane thickness, extraction time, and voltage was investigated, and a theory for the extraction kinetics is proposed. Pethidine, nortriptyline, methadone, haloperidol, and loperamide were extracted from pure water samples with recoveries ranging between 33% and 47% after only 5 min of operation under totally stagnant conditions. The extraction system was compatible with human urine and plasma samples and provided very efficient sample pretreatment, as acidic, neutral, and polar substances with no distribution into the organic SLM were not extracted across the membrane. Evaluation was performed for human urine, providing linearity in the range 1–20 μg/mL, and repeatability (RSD) in average within 12%.     

Facilitated transport of CO2 across a liquid membrane: Comparing enzyme, amine, and alkaline

In this work we compare the efficiency of facilitated transport of CO₂ across a liquid membrane by different facilitators as tested in either a supported liquid membrane (SLM) or a hollow fiber contained liquid membrane (HFCLM) configuration. Permeance and selectivity were evaluated by both experimental test and numerical simulation. These comparisons were used to define the best liquid membrane composition to maximize separation performance. We also consider other factors that affect the choice of the facilitator, e.g. operation temperature and cost. Under ambient operating conditions, carbonic anhydrase (CA) combined with an alkaline carbonate gives better performance than does diethanolamine (DEA).     

一种新的液膜振荡体系的振荡规律

本文报道一种 新的液膜振荡体系.该体系的二水相分别是结晶紫的水溶液(含有一定浓度的醇)和蔗糖溶液,介于二水相之间的油相为2,6-二硝基苯酚的硝基苯溶液.本文对这一新的体系的液膜电势振荡机理作了初步的探讨.     

Impact of an ionic surfactant on the ion transfer behaviors at meso-liquid/liquid interface arrays

The influence of ionic surfactants,cetyltrimethylammonium bromide(CTAB),self-assembled within silica-nanochannels of a hybrid mesoporous silica membrane(HMSM) on simple ion transfer(IT)behaviors at the meso-water/1,2-dichloroethane(W/DCE) interface arrays supported by such a HMSM was investigated by voltammetry for the first time.Significantly,it is found that the CTAB in HMSM can dramatically enhance the peak-current responses corresponding to ITs of some anions and even lower their Gibbs transfer energies from W to DCE,which could be ascribed to an anion-exchange process between anions and the bromide of CTAB associated with partial ion-dehydration induced by the CTAB.This work will provide a new strategy to study anion transfer processes and improve the electroanalytical performance for anion detection at the liquid/liquid interface.     

水溶性聚合物和两亲聚合物19．磺化液体聚丁二烯──种新型液膜用表面活性剂

一种新的聚工二烯型表面活性剂ＬＹＦ经液体聚了二烯磺化方法制备而得，并应用于液膜分离研究之中。发现无论内水相是酸性还是碱性，由该表面活性剂制得的Ｗ／Ｏ型乳状液在稳定性、溶胀率和破乳诸方面均具有令人满意的综合性能。为深入了解液膜的稳定性，我们测定了处于两种水相间的双分子膜的强度。发现由ＬＹＦ所形成的双分子膜具有最大的膜强值，优于聚异丁烯型的表面活性剂ＥＣＡ４３６０和ＥＭ３０１．     

Analytical treatment of the oscillating Yukawa potential

Using a suitable Laguerre basis set that ensures a tridiagonal matrix representation of the reference Hamiltonian, we were able to evaluate in closed form the matrix elements of the generalized Yukawa potential with a complex screening parameter. This enabled us to treat analytically both the cosine and sine-like Yukawa potentials on equal footing and compute their bound states spectrum as the eigenvalues of the associated analytical matrix representing their Hamiltonians. Finally we used a carefully designed complex scaling method to evaluate the resonance energies and compared our results satisfactorily with those obtained in the literature for the cosine-like Yukawa potential.     

Carrier-mediated extraction of bipyridilium herbicides across the hydrophobic liquid membrane

Supported liquid membrane (SLM) method for preconcentration and enrichment of the two bipyridilium herbicides, namely diquat and paraquat, from environmental water samples has been developed. The permanently charged cationic herbicides were extracted from a flowing aqueous solution to a stagnant acidic acceptor solution across a liquid membrane containing 40% (v/v) di-(2-ethylhexyl) phosphoric acid dissolved in di-n-hexyl ether. The mass transfer of analytes is driven by the counter-coupled transport of hydrogen ions from the acceptor to the donor phase. The efficiency of the extraction process depends on the donor solution pH, the amount of the mobile carrier added to the liquid membrane and the concentration of the counter ion in the acceptor solution. The applicability of the method for extraction of these quaternary ammonium herbicides from environmental waters was also investigated by spiking analyte sample solutions in river water. With 24 h sample enrichment concentrations of diquat and paraquat down to ca. 10 ng/L could be detected in environmental waters.     

Electrical transport properties of some liquid metals

In the present article, we report the electrical transport properties viz. the electrical resistivity (ρ), the thermoelectric power and thermal conductivity (σ) of several monovalent, divalent and polyvalent liquid metals of the different groups of the periodic table on the basis of model potential formalism. The well-known empty core model potential of Ashcroft is used for the first time with seven local field correction functions proposed by Hartree, Hubbard–Sham, Vashishta–Singwi, Taylor, Ichimaru–Utsumi, Farid et al. and Sarkar et al. in the present computation and found suitable for such study. In the calculation of these properties we have used the values of the theoretical structure factors due to hard core fluid theory. It is concluded that the comparisons of present and theoretical or experimental findings wherever exists are highly encouraging.     

基于细胞膜表面电势探讨Ca与毒性离子在植物根膜表面的相互作用

有毒重金属离子的自由离子活度已被广泛认为是重金属最直接的活性形态,可以用来预测重金属的生物效应,而事实上生物体表的重金属离子浓度由于细胞表面膜电势的静电效应而与本体溶液中重金属的自由离子活度存在显著差异.细胞膜表面电势随溶液中离子组成变化而发生变化,本体介质中钙离子能通过电荷屏蔽和离子键结合来降低膜表面电势的电负性,从而减少阳离子如Al3+、Cu2+和Ni2+在膜表面的活度,增加阴离子如SeO42-和H2AsO4-在膜表面的活度,这种电负性降低的程度能通过Gouy-Chapman-Stern模型来量化.基于植物根表重金属离子活度可以更好地预测其生物效应.细胞膜表面电势为研究离子之间交互作用机制及其与植物效应之间的关系提供了一个全新的角度.     

The syntheses of phenol-containing diazamacrocycles and liquid membrane transports of alkali cations

Two new bisphenol-containing diazacrown ether derivatives, 7,16-bis(2-hydroxy-5-ethylbenzoatebenzyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (1) and 7,16-bis(2-hydroxy-3,4-dimethylbenzyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (2), have been synthesized via one-pot Mannich reaction. The compound 1 is structurally characterized. The liquid membrane transports of alkali metal cations using these two new diazamacrocycles and the other previously prepared diazamacrocyclic derivative 7,16-bis(3-hydroxy-6-methyl-2-pyridylmethyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (3) as ion-carriers are also studied. The results show that the rates of cation transports are closely related to the number of nitrogen donors and the steric effect of the substituted groups. Compared with other macrocyclic compounds, compound 1 shows a good selectivity for Li⁺, therefore providing a new efficient carrier for Li⁺ extraction.     

Span80-TBP-NaOH体系破乳方法及膜内反应研究

采用Span80-TBP-NaOH体系乳状液膜法提取红土矿浸出液中的镍,对提取分离后的乳液进行破乳实验,经过加热-离心联合破乳法,破乳率可达90%.通过比较提取镍前后,乳液的红外光谱图,证明了膜内反应的发生;通过比较原始油相和破乳后油相的红外光谱图,证明了破乳后油相的重复利用性.     

Applicability of a liquid membrane in enrichment and determination of nickel traces from natural waters

In this work, a bulk liquid membrane method has been applied for Ni enrichment and separation from natural waters. The carrier-mediated transport was accomplished by pyridine-2-acetaldehyde benzoylhydrazone dissolved in toluene as a complexing agent. The preconcentration was achieved through pH control of source and receiving solutions via a counterflow of protons. The main variables were optimized by using a modified simplex technique. High transport efficiencies (101.2 ± 1.8–99.7 ± 4.2%) were provided by the carrier for nickel ions in a receiving phase of 0.31 mol L⁻¹ nitric acid after 9–13 h depending on sample salinity. The precision of the method was 2.05% (without a saline matrix) and 4.04% (with 40 g L⁻¹ NaCl) at the 95% confidence level and the detection limit of the blank was 0.015 μg L⁻¹ Ni for detection by atomic absorption spectroscopy. The applicability of the method was tested on certified reference and real water samples with successful results, even for saline samples. The relative errors were −0.60% for certified reference materials and ranged from −0.39 to 2.90% and from 0.3 to 11.05% for real samples, obtained by comparison of inductively coupled plasma mass spectrometry and adsorptive cathodic stripping voltammetry measurements, respectively.     

An electrical impedance spectroscopic (EIS) study on transport characteristics of ion-exchange membrane systems

This study aimed at investigating ion-exchange membrane systems using impedance spectroscopy. Nyquist plots showed that the impedance obtained in this study described the ion-exchange membrane system well, as consisting of (i) an ion-exchange membrane immersed in solution, (ii) electrical double layers at the membrane surface, and (iii) diffusion boundary layers arising from the interface between the ion-exchange membrane and the electrolyte solutions. Taking into account the physical and electrochemical understanding of the ion-exchange membrane system, an equivalent circuit was suggested to quantitatively analyze each component of the ion-exchange membrane system. To confirm the reliability of the proposed equivalent circuit, the resistance and capacitance were estimated from the impedance data and the values were compared with other experimental results (e.g., I-V curves). The comparison showed good agreement and validated the equivalent circuit. Moreover, the impedance measurements made it possible to confirm the electroconvective effects in the over LCD region.