Fully Ionised Resin Systems

All ion exchange resins, whether cation or anion exchangers, strongly or weakly ionised, gel or macroporous, spherical or granular, can be viewed as solid solutions. The 2 phases in ion exchange (i.e. the solution and the immobile solid) can be referred to simply as the outside phase and the inside phase. Transfer of components takes place across the interface between the phases, which is the surface of the bead or granule. The inside phase of an ion exchange resin contains 4 necessary components:
A 3-dimensional polymeric network Ionic functional groups permanently attached to this network Counter-ions A solvent

Under certain conditions there may be other components inside the resin such as a second solvent, co-ions and non-ionic solutes.

Polymeric network Most ion exchange resins in commercial use are based on an organic polymer network, but inorganic polymers are also used. Regardless of the composition of the network, its primary function is to limit the solubility of the resin. The chemical nature of the polymer network is a major factor in determining the physical and chemical stability of the resin. The majority of strong-acid cation exchange resins and strong-base anion exchange resins are based on the co-polymerisation of styrene and a cross-linking agent, divinylbenzene (DVB) to produce a 3-dimensional cross-linked structure. The structure is relatively well defined and is fully ionised over the entire pH range.

The degree of cross-linking is governed by the ratio of DVB to styrene. These cross-linked co-polymers swell in the presence of organic solvents, but have no ion exchange

properties. To convert the co-polymers to water-swellable gels with ion exchange properties, ionic functional groups are added to the polymeric network.

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Functional Groups Ionic sites, which give the polymer ion exchange properties, are added to the styreneDVB polymer network by one or more chemical reactions.
Strong-acid cation exchange resins are prepared by sulfonating the benzene rings in the

polymer. The SO3- groups are permanently fixed to the polymer network to give a negatively charged matrix and exchangeable, mobile positive hydrogen ions.

The hydrogen ions can be exchanged on an equivalent basis with other cations such as Na+ , Ca2+ , K+ or Mg2+ , to maintain neutrality of the polymer. For example, 2 H + ions are exchanged for 1 Ca2+ ion. The exchangeable ions are called counter-ions. The liquid whose ions are being exchanged also contains other ions of unlike charge, such as Cl- for a solution of NaCl, where Na+ is exchanged. These other ions are called coions.
Strong-base anion exchange resins require 2 reactions: chloromethylation and amination:

The Cl- ions can be exchanged for other anions such as OH - , HCO3- , SO42- and NO3- .

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The Figure below showed a cation exchanger with fixed and mobile ions.

The ionised functional group converts the oil-swellable styrene-DVB copolymer to a waterswellable structure. A relatively low degree of functional substitution may be sufficient to give the copolymer some water swellability. The greater the degree of substitution, the more tendency there is for the bead to pull in water. The higher the cross-linking, the greater the resistance to uptake of water. At equilibrium, the amount of water taken up by the bead is a function of the type and amount of ionic substitution, and the effective cross-linking of the polymer structure. For most separation applications, the water content of the swollen bead varies from 30 to 80%.

The maximum ion exchange capacity of a strong-acid cation or strong-base anion exchanger is stoichiometric, based on the number of equivalents (eq) of mobile charge in the resin. Thus, 1 mole H+ is one eq, whereas 1 mole Ca2+ is 2 eq. The exchanger capacity is usually quoted as eq/kg of dry resin or eq/L of wet resin, depending on whether wet or dry basis is used.
Fully ionised resins have a wet-volume capacity that varies with the water content, which is expressed as equivalents per litre (eq/L). Volume capacity is a measurement of

the maximum usefulness of the resin in a stoichiometric exchange. When all the available exchange sites have been used, the ion-exchange process must be interrupted and the resin regenerated. On the other hand, the dry-weight capacity is a measure of the extent of functional group substitution in the resin. Fully ionised resins contains a fixed number of functional groups per unit weight, and therefore have a constant dry-weight capacity. Most commercial resins have dry weight capacities of 5.0 0.1 milliequivalents per dry gram (meq/g) Commercial ion exchangers in the hydrogen, sodium and chloride form are available under trade names of Amberlite, Duolite, Dowex, Ionac and Purolite. Typically they are in the form of spherical beads from about 40 m to 1.2 mm in diameter. When saturated with water, the beads have typical moisture content from 40 - 65 wt%. When packed into a bed, they have bulk densities from 0.56 - 0.96 g/cm3 with fractional bed porosities of 0.35 - 0.40.

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Counter-ions Fixed ionic sites in the resin structure must be balanced by a like number of ions of the opposite charge to maintain electrical neutrality. These ions are called counter-ions. True ion exchange is the transfer of counter-ions between the outside and inside phases. Such an exchange is always on an equivalent basis. Equivalency of exchange may be obscured if the exchange is accompanied by chemical reaction. The most common case is exchange of an acid solution with the hydroxide form of a resin. The anion of the acid enters the resin in exchange for a hydroxide ion which reacts with the hydrogen ion to form water. Other reasons for an apparent lack of equivalency include the formation of precipitate or the formation of a poorly ionised component which is physically adsorbed by the resin.

Solvent Often water is the solvent in the resin. The amount of water in the inside phase is an important factor in determining relative selectivity of the resin for different ions. The higher the water content of the resin phase, the more the inside phase starts to resemble the outside phase. As a general rule, as the water content increases, the difference in selectivity between ion species becomes less. Any change in the solvent away from water changes the nature of the system.