Membrane, ion exchange

Liquid ion-exchange membranes may also be used as membrane electrodes. These membranes function in a manner analogous to the 

These compounds are relatively insoluble in water and to form a membrane, are dissolved in water-insoluble solvents such as benzene, toluene, kerosene, or various higher alcohols. The water-insoluble fluid thus formed is used, in a thin layer, to separate the two aqueous solutions of differing ionic concentrations (reference solution and test solution). The organic solvent provides the barrier preventing mixing while the transport molecules carry the selected ions across the boundary. 

A wide variety of ion exchange membrane chemistries has been developed. Typically each electrodialysis system manufacturer produces its own membrane tailored for the specific applications and equipment used. An additional complication is that many of these developments are kept as trade secrets or are only described in the patent literature. Komgold [16] gives a description of ion exchange membrane manufacture. 

A number of early homogeneous membranes were made by simple condensation reactions of suitable monomers, such as phenol-formaldehyde condensation reactions of the type  

The mechanical stability and ion exchange capacity of these condensation resins were modest. A better approach is to prepare a suitable crosslinked base membrane, which can then be converted to a charged form in a subsequent reaction. Ionics is believed to use this type of membrane in many of their systems. In a typical preparation procedure, a 60 40 mixture of styrene and divinyl benzene is cast onto a fabric web, sandwiched between two plates and heated in an oven to form the membrane matrix. The membrane is then sulfonated with 98 % sulfuric acid or a concentrated sulfur trioxide solution. The degree of swelling in the final membrane is controlled by varying the divinyl benzene concentration in the initial mix to control crosslinking density. The degree of sulfonation can also be varied. The chemistry of the process is  

Anion exchange membranes can be made from the same crosslinked polystyrene membrane base by post-treatment with monochloromethyl ether and aluminum chloride to introduce chloromethyl groups into the benzene ring, followed by formation of quaternary amines with trimethyl amine  

A particularly important category of ion exchange polymers is the perfluoro-carbon type made by DuPont under the trade name Nafion [17,18], The base 

---

Separation of the anode and cathode products in diaphragm cells is achieved by using asbestos [1332-21 -4] or polymer-modified asbestos composite, or Polyramix deposited on a foraminous cathode. In membrane cells, on the other hand, an ion-exchange membrane is used as a separator. Anolyte—catholyte separation is realized in the diaphragm and membrane cells using separators and ion-exchange membranes, respectively. The mercury cells contain no diaphragm the mercury [7439-97-6] itself acts as a separator. 

The vinyl ether in the latter part of the equation is copolymetized with tetrafluoroethylene, and then the sulfonyl fluoride group is hydrolyzed under basic conditions in order to produce the ion-exchange membrane (44—46). 

The porous electrodes in PEFCs are bonded to the surface of the ion-exchange membranes which are 0.12- to 0.25-mm thick by pressure and at a temperature usually between the glass-transition temperature and the thermal degradation temperature of the membrane. These conditions provide the necessary environment to produce an intimate contact between the electrocatalyst and the membrane surface. The early PEFCs contained Nafton membranes and about 4 mg/cm of Pt black in both the cathode and anode. Such electrode/membrane combinations, using the appropriate current coUectors and supporting stmcture in PEFCs and water electrolysis ceUs, are capable of operating at pressures up to 20.7 MPa (3000 psi), differential pressures up to 3.5 MPa (500 psi), and current densities of 2000 m A/cm. ... 

Membranes and Osmosis. Membranes based on PEI can be used for the dehydration of organic solvents such as 2-propanol, methyl ethyl ketone, and toluene (451), and for concentrating seawater (452—454). On exposure to ultrasound waves, aqueous PEI salt solutions and brominated poly(2,6-dimethylphenylene oxide) form stable emulsions from which it is possible to cast membranes in which submicrometer capsules of the salt solution ate embedded (455). The rate of release of the salt solution can be altered by surface—active substances. In membranes, PEI can act as a proton source in the generation of a photocurrent (456). The formation of a PEI coating on ion-exchange membranes modifies the transport properties and results in permanent selectivity of the membrane (457). The electrochemical testing of salts (458) is another possible appHcation of PEI. 

A newer technology for the manufacture of chromic acid uses ion-exchange (qv) membranes, similar to those used in the production of chlorine and caustic soda from brine (76) (see Alkali and cm ORiNE products Chemicals frombrine Mep rane technology). Sodium dichromate crystals obtained from the carbon dioxide option of Figure 2 are redissolved and sent to the anolyte compartment of the electrolytic ceU. Water is loaded into the catholyte compartment, and the ion-exchange membrane separates the catholyte from the anolyte (see Electrochemical processing). 

Process Description lectrodialysls (ED) is a membrane separation process in which ionic species are separated from water, macrosolutes, and all uncharged solutes. Ions are induced to move by an electrical potential, and separation is facilitated by ion-exchange membranes. Membranes are highly selective, passing either anions or cations andveiy little else. The principle of ED is shown in Fig. 22-56. 

Membranes Ion-exchange membranes are highly swollen gels containing polymers with a fixed ionic charge. In the interstices of the polymer are mobile counterions. A schematic diagram of a cation-exchange membrane is depicted in Fig. 22-57. 

Membrane Efficiency The permselectivity of an ion-exchange membrane is the ratio of the transport of electric charge through the membrane by specific ions to the total transport of electrons. Membranes are not strictly semipermeable, for coions are not completely excluded, particularly at higher feed concentrations. For example, the Donnan eqmlibrium for a univalent salt in dilute solution is ... 

Dijfusion Dialy The propensity of and OH" to penetrate membranes is useful in diffusion dialysis. An anion-exchange membrane will block the passage of metal cations while passing hydrogen ions. This process uses special ion-exchange membranes, but does not employ an applied electric current. 

By the time the next overview of electrical properties of polymers was published (Blythe 1979), besides a detailed treatment of dielectric properties it included a chapter on conduction, both ionic and electronic. To take ionic conduction first, ion-exchange membranes as separation tools for electrolytes go back a long way historically, to the beginning of the twentieth century a polymeric membrane semipermeable to ions was first used in 1950 for the desalination of water (Jusa and McRae 1950). This kind of membrane is surveyed in detail by Strathmann (1994). Much more recently, highly developed polymeric membranes began to be used as electrolytes for experimental rechargeable batteries and, with particular success, for fuel cells. This important use is further discussed in Chapter 11. 

Compact, ready-prepared calomel electrodes are available commercially and find wide application especially in conjunction with pH meters and ion-selective meters. A typical electrode is shown in Fig. 15.1(h). With time, the porous contact disc at the base of the electrode may become clogged, thus giving rise to a very high resistance. In some forms of the electrode the sintered disc may be removed and a new porous plate inserted, and in some modern electrodes an ion exchange membrane is incorporated in the lower part of the electrode which prevents any migration of mercury(I) ions to the sintered disc and thus... 

Commercial forms of the electrode are available and in general are similar to the calomel electrode depicted in Fig. 15.1(h) with the replacement of the mercury by a silver electrode, and calomel by silver chloride. The remarks concerning clogging of the sintered disc, and the use of ion exchange membranes and double junctions to reduce this are equally applicable to the silver-silver chloride electrode. 

The salt ions are captured by the ion exchange membranes that are present. The applications are limited to desalting amino add solutions, eg removal of HQ from L-glutamic add solution. 

---