1.

1 GENERAL DISCUSSION

The term ion exchange is generally understood to mean the exchange of ions of like sign between a solution and a solid highly insoluble body in contact with it. The solid (ion exchanger) must, of course, contain ions of its own, and for the exchange to proceed sufficiently rapidly and extensively to be of practical value, the solid must have an open, permeable molecular structure so that ions and solvent molecules can move freely in and out. Many substances, both natural (e.g. certain clay minerals) and artificial, have ion exchanging properties, but for analytical work synthetic organic ion exchangers are chiefly of interest, although some inorganic materials, e.g. zirconyl phosphate and ammonium 12-molybdophosphate, also possess useful ion exchange capabilities and have specialised applications.' All ion exchangers of value in analysis have several properties in common, they are almost insoluble in water and in organic solvents, and they contain active or counter-ions that will exchange reversibly with other ions in a surrounding solution without any appreciable physical change occurring in the material. The ion exchanger is of complex nature and is, in fact, polymeric. The polymer carries an electric charge that is exactly neutralised by the charges on the counter-ions. These active ions are cations in a cation exchanger and anions in an anion exchanger. Thus a cation exchanger consists of a polymeric anion and active cations, while an anion exchanger is a polymeric cation with active anions. A widely used cation exchange resin is that obtained by the copolymerisation of styrene (A) and a small proportion of divinylbenzene (B), followed by sulphonation; it may be represented as (C): -CH-CH2-CH-CH2-CHCH=C112 (A) SO; l e SOH CH2-CH-CH2 CH=CH2
(B)

CH2=CH

-CH2-CH

CH-CH 2 -

SOiH

SO; H'

(C)

CHELATING ION EXCHANGE RESINS

7.6

The formula enables us to visualise a typical cation exchange resin. It consists of a polymeric skeleton, held together by linkings crossing from one polymer chain to the next: the ion exchange groups are carried on this skeleton. The physical properties are largely determined by the degree of cross-linking. This cannot be determined directly in the resin itself: it is often specified as the moles per cent of the cross-linking agent in the mixture polymerised. Thus 'polystyrene sulphonic acid, 5 per cent DVB' refers to a resin containing nominally 1 mole in 20 of divinylbenzene: the true degree of cross-linking probably differs somewhat from the nominal value, but the latter is nevertheless useful for grading resins. Highly cross-linked resins are generally more brittle, harder, and more impervious than the lightly cross-linked materials; the preference of a resin for one ion over another is influenced by the degree of cross-linking. The solid granules of resin swell when placed in water to give a gel structure, but the swelling is limited by the cross-linking. In the above example the divinylbenzene units 'weld' the polystyrene chains together and prevent it from swelling indefinitely and dispersing into solution. The resulting structure is a vast sponge-like network with negatively charged sulphonate ions attached firmly to the framework. These fixed negative charges are balanced by an equivalent number of cations: hydrogen ions in the hydrogen form of the resin and sodium ions in the sodium form of the resin, etc. These ions move freely within the water-filled pores and are sometimes called mobile ions; they are the ions which exchange with other ions. When a cation exchanger containing mobile ions C is brought into contact with a solution containing cations B + the latter diffuse into the resin structure and cations C diffuse out until equilibrium is attained. The solid and the solution then contain both cations C + and B + in numbers depending upon the position of equilibrium. The same mechanism operates for the exchange of anions in an anion exchanger. Anion exchangers are likewise cross-linked, high-molecular-weight polymers. Their basic character is due to the presence of amino, substituted amino, or quaternary ammonium groups. The polymers containing quaternary ammonium groups are strong bases; those with amino or substituted amino groups possess weak basic properties. A widely used anion exchange resin is prepared by copolymerisation of styrene and a little divinylbenzene, followed by chloromethylation (introduction of the CH2C1 grouping, say, in the free para position) and interaction with a base such as trimethylamine. A hypothetical formulation of such a polystyrene anion exchange resin is given as (D).
CHCH2CHCH2CHCH2

CH2NMeIC1CH2 CH2CH CH

CH2NMe2FC1?H2

CHCH2

CH2NM4C1(D)

CH2NMeIC1-

Numercius types of both cation and anion exchange resins have been prepared, but only a few can be mentioned here. Cation exchange resins include that prepared by the copolymerisation of methacrylic acid (E) with glycol CH 2 =C(CH 3 )COOH (E) CH 2 -C (CH 3 )-COOCH 2 CH2=C(CH3)COOCH2 (F)

bismethacrylate (F) (as the cross-linking agent); this contains free COOH groups and has weak acidic properties. Weak cation exchange resins containing free COOH and OH groups have also been synthesised. Anion exchange resins containing primary, secondary, or tertiary amino groups possess weakly basic properties. We may define a cation exchange resin as a high-molecularweight, cross-linked polymer containing sulphonic, carboxylic, phenolic, etc., groups as an integral part of the resin and an equivalent number of cations: an anion exchange resin is a polymer containing amine (or quaternary ammonium) groups as integral parts of the polymer lattice and an equivalent number of anions, such as chloride, hydroxyl, or sulphate ions. The fundamental requirements of a useful resin are: 1. the resin must be sufficiently cross-linked to have only a negligible solubility; 2. the resin must be sufficiently hydrophilic to permit diffusion of ions through the structure at a finite and usable rate; 3. the resin must contain a sufficient number of accessible ionic exchange groups and it must be chemically stable; 4. the swollen resin must be denser than water. A new polymerisation technique yields a cross-linked ion exchange resin having a truly macroporous structure quite different from that of the conventional homogeneous gels already described. An average pore diameter of 130 nm is not unusual and the introduction of these macroreticular resins (e.g. the Amberlyst resins developed by the Rohm and Haas Co.) has extended the scope of the ion exchange technique. Thus, the large pore size allows the more complete removal of high-molecular-weight ions than is the case with the gel-type resins. Macroporous resins are also well suited for non-aqueous ion exchange applications. /8 New types of ion exchange resins have also been developed to meet the specific needs of high-performance liquid chromatography (HPLC) (Chapter 8). These include pellicular resins and microparticle packings (e.g. the Aminex-type resins produced by Bio-Rad). A review of the care, use and application of the various ion exchange packings available for HPLC is given in Ref. 19. Some of the commercially available ion exchange resins are collected in Table 7.1. These resins, produced by different manufacturers, are often interchangeable and similar types will generally behave in a similar manner. For a more comprehensive list of ion exchange resins and their properties, reference may be made to the booklet published by BDH Ltd (see the Bibliography, Section 9.10). Finally, mention should be made to the development of silica-based ion exchange packings for HPLC. Their preparation is similar to that for the
3

CHELATING ION EXCHANGE RESINS

7.6

Table 7.1 Comparable ion exchange materials Type Duolite International Ltd Strong acid cation exchangers Weak acid cation exchangers Strong base anion exchangers Weak base anion exchangers Duolite C225 Duolite C255 200* Duolite C26C* Duolite C433 Duolite C464* Duolite A113 Duolite A116 Duolite A161* 900* Duolite A303 Duolite A378*
Rohm & Haas

Dow Chemical Dowex 50 Co., USA

Bio-Rad AG5OW Labs AGMP-50* Ltd, Watford, UK Bio-Rex 70*

Co., USA Amberlite 120 Amberlite

Amberlite 84 Amberlite 50 Amberlite 400 Amberlite 410 Amberlite Amberlite 45 Amberlite 68 Amberlite 93 *

Dowex 1 Dowex 2

AG1 AGMP-1* AG3-X4A

Chelex 100

ACTION OF ION EXCHANGE RESINS

7.2

Chelating Amberlite 718*

Duolite ES466* resins

* Macroporous/macroreticular resins.

bonded-phase packings (Chapter 8) with the ion exchange groups being subsequently introduced into the organic backbone. The small particle size (5-10m diameter) and narrow distribution of such packings provide high column efficiencies and typical applications include high-resolution analysis of amino acids, peptides, proteins, nucleotides, etc. These silica-based packings are preferred when column efficiency is the main criterion but, when capacity is the main requirement, the resin microparticle packings should be selected. The chromatographic properties of ion exchange packings for analytical separations have been compared.2