Liquid-membrane

A liquid membrane consists of a solvent immiscible with water and a reagent that acts as extractant and complexing agent for an ion. If such a liquid membrane separates two solutions, ion selectivity is achieved through preferential extraction of 

If the complexes is and js are highly associated and the sites (or complexing agent) are only slightly mobile, then 

If the exchange sites are highly mobile, the expression derived by Eisenman is 

For the calcium electrode the most serious interferences are hydrogen ions (useful pH range 5.5 to 11), strontium (Ac+ + + + = 0.014), magnesium (Ai ,+ +Mg+ + = 0.005), and barium ( ca++sa++ = 0.0016). The selectivity coefficients with sodium and potassium are about 3 x 10 . Anions have little effect on the membrane potential. 

For a copper-sensitive liquid ion-exchanger electrode, hydrogen (il ++H+ = 10) and iron(II) (il ++Fe++ = 140) interfere seriously, whereas nickel(II) (Kca i = 0.01) interferes only moderately. 

The basic liquid membrane consists of some liquid ion-exchange resin which is restrained by an inert support. It suffers from several faults. The liquid-liquid interface is poorly defined and is subject to stirring effects and pressure differentials. It is mechanically fragile which can lead to mutual contamination of the two liquid phases. 

The utility of liquid membranes as ion-selective electrodes lies in the mobility of their exchange sites. These are of molecular size, however, so that it is possible to immobilize an exchanger liquid in a bulk matrix. The constraint on the matrix is that it be permeable to microscopic charge carriers. Collodion is one such bulk material. 

Two basically Afferent types of liquid membrane can be distinguished (see figure VI - 

The two phases (phase 1 and phase 2) are generally aqueous solutions, while the liquid membrane phase is an organic phase which is immiscible with water. The solubility is a very important factor with respect to the stability of these system. This stability effect will be discussed below. 

The liquid membranes illustrated here are only used in some specific applications because of the rather low selectivities obtained. Selectivities are mainly based on differences in the distribution coefficients of the components of phase 1 with the liquid. If the components are similar these differences are generally not very high. The diffusivities of components of comparable size are similar so that the selectivity, which is determined 

Far higher selectivities can be obtained by adding a carrier molecule to the liquid (membrane) which has a high affinity for one of the solutes in phase 1. The carrier accelerates the transport of this specific component. This type of transport is called carrier mediated transport or facilitated transport. The mechanism of facilitated transport can be demonstrated by the simple experiment dqpicted schematically in figure VI 32. 

One arm of the U-tube is filled with an aqueous potassium chloride solution whereas the 

In supported liquid membranes, a chiral liquid is immobilized in the pores of a membrane by capillary and interfacial tension forces. The immobilized film can keep apart two miscible liquids that do not wet the porous membrane. Vaidya et al. [10] reported the effects of membrane type (structure and wettability) on the stability of solvents in the pores of the membrane. Examples of chiral separation by a supported liquid membrane are extraction of chiral ammonium cations by a supported (micro-porous polypropylene film) membrane [11] and the enantiomeric separation of propranolol (2) and bupranolol (3) by a nitrate membrane with a A/ -hexadecyl-L-hydroxy proline carrier [12]. 

In the classical set-up of bulk liquid membranes, the membrane phase is a well-mixed bulk phase instead of an immobilized phase within a pore or film. The principle comprises enantioselective extraction from the feed phase to the carrier phase, and subsequently the carrier releases the enantiomer into the receiving phase. As formation and dissociation of the chiral complex occur at different locations, suitable conditions for absorption and desorption can be established. In order to allow for effective mass transport between the different liquid phases involved, hollow fiber 

With regard to the enantioselective transport through the membrane, one advantage of liquid membrane separation is the fact that the diffusion coefficient of a solute in a liquid is orders of magnitude higher as compared to the diffusion coefficient in a solid. The flux through the membrane depends linearly on the diffusion coefficient and concentration of the solute, and inversely on the thickness of the membrane [7]. 

Addition of a chiral carrier can improve the enantioselective transport through the membrane by preferentially forming a complex with one enantiomer. Typically, chiral selectors such as cyclodextrins (e.g. (4)) and crown ethers (e.g. (5) [21]) are applied. Due to the apolar character of the inner surface and the hydrophilic external surface of cyclodextrins, these molecules are able to transport apolar compounds through an aqueous phase to an organic phase, whereas the opposite mechanism is valid for crown ethers. 

Armstrong and Jin [15] reported the separation of several hydrophobic isomers (including (l-ferrocenylethyl)thiophenol, 1 -benzylnornicotine, mephenytoin and disopyramide) by cyclodextrins as chiral selectors. A wide variety of crown ethers have been synthesized for application in enantioselective liquid membrane separation, such as binaphthyl-, biphenanthryl-, helicene-, tetrahydrofuran and cyclohex-anediol-based crown ethers [16-20]. Brice and Pirkle [7] give a comprehensive overview of the characteristics and performance of the various crown ethers used as chiral selectors in liquid membrane separation. 

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This experiment describes the preparation and evaluation of two liquid-membrane Na+ ion-selective electrodes, using either the sodium salt of monensin or a hemisodium ionophore as ion exchangers incorporated into a PVG matrix. Electrodes prepared using monensin performed poorly, but those prepared using hemisodium showed a linear response over a range of 0.1 M to 3 X 10 M Na+ with slopes close to the theoretical value. 

PhenoHc-based resins have almost disappeared. A few other resin types are available commercially but have not made a significant impact. Inorganic materials retain importance in a number of areas where synthetic organic ion-exchange resins are not normally used. Only the latter are discussed here. This article places emphasis on the styrenic and acryHc resins that are made as small beads. Other forms of synthetic ion-exchange materials such as membranes, papers, fibers (qv), foams (qv), and Hquid extractants are not included (see Extraction, liquid-liquid Membrane technology Paper.). 

Ceramic, Metal, and Liquid Membranes. The discussion so far implies that membrane materials are organic polymers and, in fact, the vast majority of membranes used commercially are polymer based. However, interest in membranes formed from less conventional materials has increased. Ceramic membranes, a special class of microporous membranes, are being used in ultrafHtration and microfiltration appHcations, for which solvent resistance and thermal stabHity are required. Dense metal membranes, particularly palladium membranes, are being considered for the separation of hydrogen from gas mixtures, and supported or emulsified Hquid films are being developed for coupled and facHitated transport processes. 

Liquid Membranes. A number of reviews summarize the considerable research effort ia the 1970s and 1980s on Hquid membranes containing carriers to faciUtate selective transport of gases or ions (58,59). Although stiU being explored ia a number of laboratories, the mote recent development of much mote selective conventional polymer membranes has diminished interest ia processes using Hquid membranes. 

Because the facilitated transport process employs a specific reactive carrier species, very high membrane selectivities can be achieved. These selectivities are often far higher than those achieved by other membrane processes. This one fact has maintained interest in facilitated transport since the 1970s, but the problems of the physical instability of the liquid membrane and the chemical instability of the carrier agent are yet to be overcome. 

Liquid Membranes Se eral types of liquid membranes exist molten salt, emulsion, irnmobilized/siipported, and hollow-fiber-contained liquid membranes, Arald and Tsiikiibe (Liquid Membranes Chemical Ajijilieafions, (JR(J Press, 1990) and Sec, IX and (Jhap, 42 in Ho and Sirlcar (eds,) (op, cit, pp, 724, 764-808) contain detailed information and extensi -e bibliographies. 

Liquid membranes are a specialty, either adsorbed in capillaries or erniilsiFied. Thev are much studied, but little commercial application is Found. 

The paper presents the experimental and theoretical data regarding the realization and characterization of three liquid-membrane electrodes, which have not been mentioned in the specialized literature so far. The active substances whose solutions in nitrobenzene have constituted the membranes on a graphite rod, are simple complex combinations of the Cu(II) and Ni(II) ions with Schiff base N-[2-thienylmethylidene]-2-aminothiophenol (TNATPh). 

In this presentation prineiples and applieations of liquid membrane extraetion teehniques for sampling and sample pretreatment in environmental analytieal ehemistry will be deseribed. 

The liquid membrane (thickness 0.2 cm) was separated from the aqueous solutions by two vertical cellophane films.The electrode compartments were filled with 0.05 M sulfuric acid solutions and were separated by the solid anion-exchange membranes MA-40. Binary mixtures contained, as a mle, 0.04 M Cu(II) and 0.018 M Pt(IV) in 0.01 M HCl. 0.1 M HCl was used usually as the strip solution. 

The copper(II) transport rate increases, as a rule, as Cu + initial concentration in the feed solution increases. The increase of the caiiier s concentration from 10 to 30 vol.% results in a decrease of both metal fluxes and in an increase of Cu transport selectivity. The increase of TOA concentration in the liquid membrane up to 0.1 M leads to a reduction of the copper(II) flux, and the platinum(IV) flux increases at > 0.2 M. Composition of the strip solution (HCl, H,SO, HNO, HCIO, H,0)does not exert significant influence on the transport of extracted components through the liquid membranes at electrodialysis. 

STUDIES ON A Pb -SELECTIVE ELECTRODE WITH MACROCYCLIC LIQUID MEMBRANE. POTENTIOMETRIC DETERMINATION OF Pb + IONS... 

Enantioselective transport processes can be achieved either with solid or liquid membranes (Fig. 1-5). In this latter case, the liquid membrane can be supported by a porous rigid structure, or it can simply be an immiscible liquid phase between two solutions with the same character (aqueous or nonaqueous), origin and destination... 

Liquid membranes can be constituted by liquid chiral selectors used directly [170] or by solutions of the chiral molecules in polar or apolar solvents. This later possibility can also be an advantage since it allows the modulation of the separation con-... 

Most of the chiral membrane-assisted applications can be considered as a modality of liquid-liquid extraction, and will be discussed in the next section. However, it is worth mentioning here a device developed by Keurentjes et al., in which two miscible chiral liquids with opposing enantiomers of the chiral selector flow counter-currently through a column, separated by a nonmiscible liquid membrane [179]. In this case the selector molecules are located out of the liquid membrane and both enantiomers are needed. The system allows recovery of the two enantiomers of the racemic mixture to be separated. Thus, using dihexyltartrate and poly(lactic acid), the authors described the resolution of different drugs, such as norephedrine, salbu-tamol, terbutaline, ibuprofen or propranolol. 

Liquid-liquid extraction is a basic process already applied as a large-scale method. Usually, it does not require highly sophisticated devices, being very attractive for the preparative-scale separation of enantiomers. In this case, a chiral selector must be added to one of the liquid phases. This principle is common to some of the separation techniques described previously, such as CCC, CPC or supported-liquid membranes. In all of these, partition of the enantiomers of a mixture takes place thanks to their different affinity for the chiral additive in a given system of solvents. 

L. J. Brice, W. H. Pirkle, Enantioselective transport through liquid membranes in Chiral separations, applications and technology, S. Ahuja (Ed.), American Chemical Society, Washington... 

In general, a liquid membrane for chiral separation contains an enantiospecific carrier which selectively forms a complex with one of the enantiomers of a racemic mixture at the feed side, and transports it across the membrane, where it is released into the receptor phase (Fig. 5-1). 

Feed solution Liquid membrane Receiving solution Fig. 5-1. Schematic representation of a liquid membrane for chiral separation. 

The carrier should not dissolve in the feed liquid or receptor phase in order to avoid leakage from the liquid membrane. In order to achieve sufficient selectivity, minimization of nonselective transport through the bulk of the membrane liquid is required. Liquid membranes can be divided into three basic types [6] emulsion supported and bulk liquid membranes, respectively (Fig. 5-2). 

Fig. 5-2. Three types of the liquid membrane eonfiguration (a) emulsion liquid membrane (b) supported liquid membrane (e) elassieal bulk liquid membrane set-up.

In general, high selectivities can be obtained in liquid membrane systems. However, one disadvantage of this technique is that the enantiomer ratio in the permeate decreases rapidly when the feed stream is depleted in one enantiomer. Racemization of the feed would be an approach to tackle this problem or, alternatively, using a system containing the two opposite selectors, so that the feed stream remains virtually racemic [21]. Another potential drawback of supported enantioselective liquid membranes is the application on an industrial scale. Often a complex multistage process is required in order to achieve the desired purity of the product. This leads to a relatively complicated flow scheme and expensive process equipment for large-scale separations. 

As the main disadvantage of liquid membrane systems is the instability over a longer period of time, another approach would be to perform separation through a solid membrane [22]. Enantioselective polymer membranes typically consist of a nonse-lective porous support coated with a thin layer of an enantioselective polymer. This... 

Possible applications of MIP membranes are in the field of sensor systems and separation technology. With respect to MIP membrane-based sensors, selective ligand binding to the membrane or selective permeation through the membrane can be used for the generation of a specific signal. Practical chiral separation by MIP membranes still faces reproducibility problems in the preparation methods, as well as mass transfer limitations inside the membrane. To overcome mass transfer limitations, MIP nanoparticles embedded in liquid membranes could be an alternative approach to develop chiral membrane separation by molecular imprinting [44]. 

Nonselective membranes can assist enantioselective processes, providing essential nonchiral separation characteristics and thus making a chiral separation based on enantioselectivity outside the membrane technically and economically feasible. For this purpose several configurations can be applied (i) liquid-liquid extraction based on hollow-fiber membrane fractionation (ii) liquid- membrane fractionation and (iii) micellar-enhanced ultrafiltration (MEUF). 

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