Polymer-supported liquid membranes

Meanwhile, the science of chemical sensors was developing fast. The technology of polymer-supported liquid membranes was already a mature science, as it was more than 15 years since it was first reported. The use of plasticized PVC allowed for the construction of membrane-based sensors with great ease, and gave sensor technology a new boost. It was the same basic technology that was subsequently used for the development of liquid-polymeric-based ISEs. 

C.Y. Zhu and R.M. Izatt, Macrocyclic-mediated separation of Eu2+ from trivalent lanthanide cations in a modified thin-sheet-supported liquid membrane system, J. Membr. Sci., 1990, 50, 319 P.R. Brown, J.L. Hallman, L.W. Whaley, D.H. Desai, M.J. Pugia and R.A. Bartsch, Competitive, proton-coupled, alkali metal cation transport across polymer-supported liquid membranes containing s>yn(decyl-dibenzo-16-crown-5-oxyacetic acid) Variation of the alkyl 2-nitrophenyl ether membrane, ibid., 1991, 56, 195. 

In the present paper, we examine the influence of structural variation within series of crown ether carboxylic acid and crown ether phosphonic acid monoalkyl ester carriers upon the selectivity and efficiency of alkali metal transport across three types of liquid organic membranes. Structural variations within the carriers include the polyether ring size, the lipophilic group attachment site and the basicity of ethereal oxygens. The three membrane types are bulk liquid membranes, liquid surfactant (emulsion) membranes and polymer-supported liquid membranes. 

Figure 10. Competitive Alkali Metal Transport Across a Polymer-supported Liquid Membrane by an Analog of 5.

Enantioselective transport of several amino-acids through a polymer-supported liquid membrane containing the chiral crown ether (83) has been reported. The best result was observed with the racemic mixture of phenylglycine the D-enantiomer was transported 22.7 times faster than the L-enantiomer <85CL1549>. 

With respect to the sensing membrane, Na -sensitive glass membranes have found wide use in clinical analysis. However, today polymer-supported liquid membranes based on a neutral earner as a sensory element are also employed since they can easily be manufactured in different sizes and shapes, and are less affected by the presence of biological substrates such as proteins. 

Zougagh, M., Valcarcel, M., and Rios, A., Automatic selective determination of caffeine in coffee and tea samples by using a supported liquid membrane-modified piezoelectric flow sensor with molecularly imprinted polymer. Trends Anal. Chem., 23, 399, 2004. 

For the sake of discussion, we have divided the separators into six types—microporous films, non-wovens, ion exchange membranes, supported liquid membranes, solid polymer electrolytes, and solid ion conductors. A brief description of each type of separator and their application in batteries are discussed below. 

These types of separators consist of a solid matrix and a liquid phase, which is retained in the microporous structure by capillary forces. To be effective for batteries, the liquid in the microporous separator, which generally contains an organic phase, must be insoluble in the electrolyte, chemically stable, and still provide adequate ionic conductivity. Several types of polymers, such as polypropylene, polysulfone, poly(tetrafluoroethylene), and cellulose acetate, have been used for porous substrates for supported-liquid membranes. The PVdF coated polyolefin-based microporous membranes used in gel—polymer lithium-ion battery fall into this category. Gel polymer... 

The term Supported Liquid Membranes (SLM) usually defines solid (polymer or ceramic) porous membranes, the open pores of which are soaked with the... 

Figure 5.9 A supported liquid membrane (SLM) a porous polymer membrane whose pores are filled with the organic liquid and a carrier, set in between the aqueous source phase and the aqueous receiving phase, which are being gently stirred.

Kemperman, A.J.B., Damink, B., Vandenboomgaard, T. and Strathmann, H. (1997) Stabilization of supported liquid membranes by gelation with PVC. Journal of Applied Polymer Science, 65, 1205. 

Dense inorganic or metallic membranes for gas separation are usually ion-conducting materials, while membranes with carriers are polymers or supported liquid membranes (SLM). For transport through these materials, different flux equations should be applied. Figure 4.2 sums up and generalizes the various types of transport, which may take place in gas-separation membranes [21]. 

Nonporous membrane techniques involve two or three phases separated by distinct phase boundaries. In three-phase membrane systems, a separate membrane phase is surrounded by two different liquid phases (donor and acceptor) forming a system with two phase-boundaries and thus two different extraction (partition) steps. These can be tailored to different types of chemical reactions, leading to a high degree of selectivity. The membrane phase can be a liquid, a polymer, or a gas, and the donor and acceptor phases can be either gas or hquid (aqueous or organic). Liquid membrane phases are often arranged in the pores of a porous hydrophobic membrane support material, which leads to a convenient experimental system, termed supported liquid membrane (SLM). There are several other ways to arrange a hquid membrane phase between two aqueous phases as described below. 

Note SLM, supported liquid membrane (aq/org/aq) MMLLE, microporous membrane liquid-liquid extraction (aq/org) PME, polymer membrane extraction (aq/polymer/org) MESI, membrane extraction with sorbent interface (aq (or gas)/polymer/gas/sorbent) CFLME, continuous flow liquid membrane extraction (aq/org (in flow)/aq) LPME2, two-phase liquid phase microextraction in hoUow fibers (aq/org) LPME3, three-phase liquid phase microextraction in hollow fibers (aq/org/aq). 

SILP systems have proven to be interesting not only for catalysis but also in separation technologies [128]. In particular, the use of supported ionic liquids can facilitate selective transport of substrates across membranes. Supported liquid membranes (SLMs) have the advantage of liquid phase diffusivities, which are higher than those observed in polymers and grant proportionally higher permeabilities. The use of a supported ionic liquid, due to their stability and negligible vapor pressure, allow us to overcome the lack of stability caused by volatilization of the transport liquid. SLMs have been applied, for example, in the selective separation of aromatic hydrocarbons [129] and CO2 separation [130, 131]. 

Facilitated or carrier-mediated transport is a coupled transport process that combines a (chemical) coupling reaction with a diffusion process. The solute has first to react with the carrier to fonn a solute-carrier complex, which then diffuses through the membrane to finally release the solute at the permeate side. The overall process can be considered as a passive transport since the solute molecule is transported from a high to a low chemical potential. In the case of polymeric membranes the carrier can be chemically or physically bound to the solid matrix (Jixed carrier system), whereby the solute hops from one site to the other. Mobile carrier molecules have been incorporated in liquid membranes, which consist of a solid polymer matrix (support) and a liquid phase containing the carrier [2, 8], see Fig. 7.1. The state of the art of supported liquid membranes for gas separations will be discussed in detail in this chapter. 

If solvent extraction may be considered a source technique, derived liquid-liquid separation techniques include configurations in which an extraction solvent is physically immobilized by a coating or impregnation process onto a solid support such as silica, porous resin beads, or foam [13,84—87]. Other derived techniques include membranes of various configurations bulk liquid membranes, supported liquid membranes, emulsion membranes, and polymer-impregnated membranes [88]. Many derived liquid-liquid techniques have been developed, especially for use in analytical applications [13,60,62,64,75,84,85,87]. In each of these derived techniques, the... 

It has been demonstrated that with the appropriate choice of membrane (hydro-phobic or hydrophilic polymers) the per-evaporation procedure can be efficiently applied for the quantitative and selective recovery of organic solutes, such as naphthalene, water, ethyl hexanoate and chlorobutane, from [C4CjIm]PF, IL [110]. It was also reported that the same ILs can be used as supported liquid membranes for the selective transport of secondary amines over tertiary amines with similar boiling points, and this was attributed to the higher hydrogen bond affinity of the secondary derivative with the imidazoHum cation [111,112]. 

Actinides, in nitric acid waste, 182 Advancing-front model, ELMs, 18,68 Alkali metal cations transport across bulk liquid membranes, 89-92 transport across liquid surfactant membranes, 93-95 transport across polymer-supported liquid, 95-96... 

The liquid membrane (LM) concept combines solvent extraction (SX) and membrane-based technologies, enabling both extraction and back-extraction in a single step with reduced consumption of extractants and diluents. For these reasons, separation based on LMs can be viewed as a promising alternative to traditional SX. The LM separation approach involves mass transfer of a target chemical species between two solutions (i.e., feed and receiver solutions) separated by an immiscible LM [1]. The main types of LMs are bulk liquid membranes (BLMs), emulsion liquid membranes (ELMs), supported liquid membranes (SLMs), and polymer inclusion membranes (PIMs). 

The liquid membranes most often employed in analytical and industrial separation are supported liquid membranes, polymer liquid membranes, emulsion liquid membranes, and bulk liquid membranes. 

Polymer liquid (PL) membranes The PL membrane is a relatively new type of self-supporting liquid membrane, which resembles the SL membrane. Similarly to the SL membrane, the PL membrane incorporates a liquid extractant in the membrane polymeric structure. In some cases the incorporation of additional organic compounds (plasticizers) is required to achieve homogeneity and sufficient flexibility of the membrane. 

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