V O L U M E 28, NO. 4, A P R I L 1 9 5 6 (102) McBryde, W. A. E., Analyst 8 0 , 5 0 3 (1955). (103) Mahlman, H. A , , Leddicotte, G. W., hloore, F. L., ANAL. CHEM.26, 1939 (1954). (104) iCIann, R . L., Gale, R. M., Van Abeele, F. R., Antibiotics Ann. I, 167 (1953). (105) hletzsch, F. A. V., A n g e w . Chem. 65, 586 (1953). (106) hletzsch, E’. A. V., Chem. 2 . 78, 391, 423 (1954). (107) Mills, G. F., Whetsel, H. B., J . Am. Chem. SOC. 77, 4690 (1955). (108) Nonier, R., Jutisa, M., Biochim. Biophys. Acta 15, 62 (1954). Chem. (109) Morrison, G. H., Dorfman, E. G., Cosgrove, J. F.. J . ,417~. SOC. 7 6 , 4 2 3 6 (1954). (110) Olley, J., Biochem. et Biophys. Acta 10, 493 (1953). (111) Olley, J., Lavern, J. rl., Biochem. J . 57, 610 (1954). Saito, Y., Proc. J a p a n Acad. 30, 991 (1954) (112) Otani, S., (113) Paladini, A . , Craig, L. C., J . Am. Chem. Soc. 76, 688 (1954). (114) Patterson, E. L., Pierce, J. V., Stokstad, E. L. R., Hoffmann, C. E., Brockman, J. A , , Jr., Day, F. P., Macchi, 11. E., Jukes, T. H., Ibid., 76, 1823 (1954). (115) Pearson, D. E., Levine, hI., J . Org. Chem. 17, 1351 (1952). (116) Ibid., p. 1356. (117) Peppard, D. F., Peppard, JI. A., I n d . Eng. Chem. 4 6 , 34 (1954). (118) Perry, E. S., Weber, W.H., ANAL.CHmr. 2 6 , 4 9 8 (1954). (119) Pettinga, C. TV., Stark, IT’.hl., Van Abeele, F. R., J . Am. Chem. SOC. 76, 569 (1954). (120) Pierce, J. G., Biochem. J . 57, 16 (1954). (121) Rao, K. V., Peterson, W. H., J . Am. Chem. S O C . 76, 1335 (1954). (122) Ressler, C., Du Vigneaud, V., Ibid., 76, 3107 (1964). (123) Rigby, F. L., Bethune, J. L., Ibid., 77, 2828 (1955). (124) Sanger, F., Bull. SOC. chim. b i d . 37, 23 (1955). (125) Sanger, F., Smith, L.F., Kitai, R., Biochem. J . 58,Proc. vi (1954). (126) Schaffner, C. P., Antibiotics Ann. 2 , 153 (1954). (127) Scheibel, E. G., Chem. Ing. Tech. 2 7 , 341 (1955). (128) Scheibel, E. G., I n d . Eng. Chem. 46, 16 (1954). (129) Ibid., p. 42. (130) Schofield, C. R., Dutton, H. J., J . Biol. Chem. 2 0 8 , 4 6 1 (1964). (131) Schofield, C. R., Dutton, H. J., J . Am. 0 2 1 Chemists’ SOC.31, 258 (1954).
729 (132) Schroeder, W., Voigt, K. D., Van der Werth, H., Beckmann, I., Acta Endocrinol. 14, 14 (1953). (133) Skeggs, L. T., Jr., Marsh, W. H., Kahn, J. R., Shumway, K.P., J . Ezptl. M e d . 99, 275 (1954). (134) Ibid., 100, 363 (1954). (135) Steinbach, J. F., Freiser, H., AXAL.CHEM.26, 375 (1954). (136) Sudo, E., Sci. liepts. Tohoku C‘niu. A 6 , 137 (1954). (137) Ibid., p. 142. (138) Ibid., p. 253. (139) Ibid., p. 324. (140) Ibid., A 7 , 306. (141) Ibid., p. 312. (142) Synge, R.L. RI., Wood, J. C., Biochem. J., 56, Proc. xix (1954). (143) Taber, J. J., Dissertation Abstr. 15, 727 (1955). (144) Talbot, N. B., Ulick, S.,Koupreianow, A, Zygrnuntowics, A., J . Clin. Endocrinol. and Metabolism 15, 301 (1955). (145) Tavel, P. V., Helu. Chim. Acta 38, 520 (1955). (146) Titus, E., Weiss, H., J . Biol. Chem. 214, 807 (1955). (147) Treybal, R. E., I n d . Eng. Chem. 46, 91 (1954). (148) Ibid., 47, 536 (1955). (149) Versele, M., Bull. soc. chim. Belg. 62, 619 (1953). I n d . chim. Belge. 19, 135 (1954). (150) Verzele, M., (151) Versele, LI., Alderweireldt, F., Nature 174, 702 (1954). (152) Vigneron, M,, “Fractionnernents par Solvents,” Vigot Frhres, Paris, 1954. (153) Voigt, K . D., Schroeder, W., Beckmann, I., Van der Werth, H., Acta Endocrinol. 14, 1 (1953). (154) Wagner, R. L., Hochstein, F. A,, hlurai, K., Messina, N., Regna, P., J . Am. Chem. SOC.7 5 , 4 6 8 4 (1953). (155) Weisiger, J. R., in ”Organic Analysis,” vol. 11, pp. 277-326, Interscience, Ken- York, 1954. (156) Weisiger, J. R., Hausmann, W., Craig, L. C., J . Am. Chem. S O C 77, . 731 (1955). (157) Ibid., p. 3123. (158) Reiss, D. E., I n d . Chemist 31, 230 (1955). (159) Werning, J. R., Higbie, K. B., Grace, J. T., Speece, B. F., Gilbert, H. L., I n d . Eng. Chem. 46, 644 (1954). (160) Wright, L. D., Cresson, E. L., Valiant, J., Wolf, D. E., Folkers, K., J . Am. Chem. Soc. 76, 4163 (1954).
I
REVIEW OF FUNDAMENTAL DEVELOPMENTS IN ANALYSIS
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Ion Exchange ROBERT KUNIN, FRANCES X. MCGARVEY, and ANN FARREN Rohm & Haas Co., Philadelphia, Pa.
F ONE judges the value of ion exchange techniques to the
analytical chemist b y the number of published articles and books on the use of ion exchange in analytical chemistry, as well as b y the number of commercially available ion exchange resins tailored specifically for the analyst, one must concede that this analytical principle or technique is well accepted b y the majority of analytical chemists. This status has been achieved only recently, as it has been only during the past few years t h a t specific procedures and quantitative principles for ion exchange techniques were available to the analyst. T h e continued development of ion exchange techniques in analytical chemistry must be accompanied b y a better understanding on the part of the analytical chemist of t h e physical chemistry involved and of the nature and properties of the ion exchange resins. Steps in this direction are now evident, judging by the fact t h a t many undergraduate and graduate analytical chemistry courses in many universities and colleges include the subject of ion exchange. A review of the developments in this field of activity during the past 2 years reveals several important facts. T h e number of detailed quantitative procedures involving the use of ion exchange resins is gradually increasing. In addition, the availability of
ion exchange resins tailored for the analyst has improved considerably and the resins can now be obtained readily from several sources of supply. Simplification of the chromatographic theory as applied to ion exchange columns has resulted in a set of equations less cumbersome, although less rigorous, t h a n those available previously; and these are readily employed by the analytical chemist in developing and modifying procedures. It is obvious to those familiar with ion exchange in analytical processes t h a t ion exchange techniques function primarily a8 a means for separating and concentrating various ionic substances and are used where conventional qualitative or quantitative measurements cannot be directly applied t o the system in question. REVIEWS
During the past 2 years, many developments in ion exchange of interest t o the analytical chemist have appeared. Several reviews summarize these advances. Deuel ( / A) reviewed rather extensively the properties of ion exchange resins from a structural standpoint. Kunin ( 1 1 A ) outlined progress in the use of ion exchange in a highly condensed but comprehensive article. A
ANALYTICAL CHEMISTRY
730 special issue of the Annals of the S e w York Academy of Science was devoted to ion exchange studies, particularly in biological systems. I n this issue Bregman ( 1 A ) described the phenomena of cation exchange processes; Craig ( 3 A ) reported on the factors involved in ion exchange resin synthesis; Ezrin and Cassidy (6A) commented on some work on electron exchange polymers prepared from hydroquinone; and Sollner (14A) reviewed the properties of ion elchange membranes. Hiester and Phillips ( 8 A ) summarized many of the more recent developments in ion exchange. Spiegler (16A) reviewed ion exchange resins from a n electrochemical standpoint, emphasizing the specific conductances and ionic mobilities in resins and membranes. Griessbach ( 6 A ) summarized the published work t o date on the prepnration of ion exchange resins having unusual selectivities. ri conference on ion exchange technology was held in London in January 1954 ( 2 A ) . Several reviews were presented which were more specific with respect t o analytical problems. Pallaud (12A), for example, summarized the use of ion exchange resins in analytical problems; a n d in Japan, Honda (SA) covered much the same ground. T h e use of resins in microchemistry was reviewed by Kulberg and Lenskaya (10A). A4n excellent collection of papers on chromatography has been issued by the British Medical Society. Several other reviews on chromatography of interest to those employing ion exchange techniques were prepared b y Williams (16A), Hesse ( 7 3 ) )and Ryabchikov ( 1 3 A ) .
Table I. Cation
Selectivity Scale for Monovalent Cations (Sulfonated styrene-DVB copolymers) 8% DVB 4% DVB
1670 DVB
THEORY
Several noteworthy advances were made in the theory of ion exchange, and particularly outstanding has been the increase in the amount of experimental data which is now available t o test several of the theoretical approaches. Helfferich (22B) summarized many of the important basic problems in ion eschange theory, emphasizing the role of ionic hydration in equilibrium studies. Ongaro ( 2 9 B ) studied ionic selectivity from a n electrochemical point of vien-. Duncan ( I @ ) summarized the thermodynamic properties of ion exchange resins and has calculated the enthalpies and entropies for ion exchange reactions involving the sodium-hydrogen and the barium-hydrogen exchange systems. Boyd, Soldano, and Bonner ( 7 B ) determined by means of tracers the diffusion rates in cation exchange resins. Boyd and Soldano ( 6 B ) extended this study to include a series of sulfonic acid cation exchange resins of varying degrees of cross linking. T h e self-diffusion constant was found t o be dependent upon the ionic charge and was reduced markedly by increasing the degree of cross linking. Bctivation energies varied from 4700 to 10,000 cal. per mole and were dependent upon the degree of cross linking. T h e same authors ( 6 B ) studied the diffusion of water into the exchanger. Bonner and coworkers ( 4 B ) estimated the activity coefficient within the resin phase by means of a n analogy with soluble benzenesulfonic acids. Soldano, Boyd, and Larson (35B,36B, 38B, S9B) investigated the osmotic properties of a series of resins of varying degrees of cross linking for a large number of ions. T h e selectivities calculated from the osmotic data were in good agreement with those obtained by other methods. Bonner ($23) developed a relative selectivity scale of some monovalent cation exchange reactions
for a series of sulfonated cross-linked styrene-divinylbenzene copolymers (see Table I). Whitcombe, Banchero, and White ( 4 2 B ) studied the equilibrium between sodium and potassium chloride and a strongly acidic cation exchange resin, and Wilson (43%) determined t’he effect of ionic strength on silver-sodium exchange equilibrium. Pauley (SOB) developed a method for the calculation of cation exchange equilibria based upon a consideration of coulombic forces in an exchange system. I n this method, the resin is considered as a series of negative point charges randomly distributed and surrounded by cations held a t the distance of closest hydrated approach. Free energies for the exchange reactions were calculated by use of classical electrodynamics, Davies and Yeoman (11B) derived a method for prediction of cation equilibria based upon a n estimate of activity coefficients in the resin phase. Diamond ( 1 2 B ) reported equilibrium data for beryllium, calcium, strontium, barium, radium, sodium, rubidium, and cesium cations in acid solutions. Hiigfeldt (23B) extended his study of the silver-hydrogen exchange on a cation exchanger and Davidson and Argereinger ( 9 B )collected and correlated equilibrium constants for many cation exchange processes. Equilibrium studies for anion exchange systems have not been so numerous as those of cation exchange systems; however, some noteworthy contributions have been made. Gregor, Belle, and Marcus (2OB) determined select,ivity coefficients for strongly basic anion exchange resins for univalent anions and Gottlieb and Gregor (18B) measured the mean activity coefficients for a variety of materials diffusing into strongly basic anion exchangers. Soldano and Chesnut (37B)employed osmotic measurements t o estimate the selectivities of strong base anion exchangers for the systems bromide-fluoride, bromide-chloride, and bromide-iodide. Peterson and Gowen (31B ) presented equilibrium data for the adsorption of aromatic acids on weakly basic anion exchange resins. T h e effect of mixed solvents on the volume changes of ion exchange resins for the water-methanol, water-ethanol, naterisopropyl alcohol, and water-dioxane systems was investigated by Gregor, Sobel, and Gottlieb (19B). Sundheim, Waxnian, and Gregor (40B) obtained data for moisture sorption on resins a s a function of resin structure. Bafna (5%) conducted several ion exchange equilibrium studies in a n aqueous-acetone system. Davies and Yeoman (1OB)illustrated the effect of swelling on equilibrium values for certain cation exchange systems. Because the rate of exchange is important for processes involving chromatographic separations, a consideration of the developments in this field is most important. Wells (41B) reviewed this subject for inorganic ions, and several other excellent papers deal with advances in the mathematics of fixed bed theory. Rosen (33B)presented a general numerical solution to the problem of solid diffusion in fixed beds, and Goldstein ( I 7 B )extended the theory of such processes with a basic review of ion exchange columnill theory. Dickel and Meyer (13B) evaluated these processes from the standpoint of temperature effects. Conway, Green, and Reichenberg ( 8 B ) determined the rates for reactions involving a carboxylic cation exchanger. Freiling ( 1 6 B ) found that one could improve upon standard chromatographic techniques by using a gradient elution procedure. Lakshmanan and Lieberman ( 2 8 B ) extended this technique t o biochemical systems. Glueckauf (16B) extended the “theoretical plate” concept for various column separations, and Baddour, Goldstein, and Epstein ( 1 B ) applied Goldstein’s earlier theoretical analysis to the nonequilibrium elution of partially saturat,edion exchange beds, Rieman ( S 2 B )contributed a n ion exchange experiment to demonstrate ion exchange chromatography t o high school students. T h e kinetics of ion exchange reactions between two ion exchange resins has been the subject of a n extensive study by Krishnamoorthy (dSB-27B). This work included a study of the exchange of univalent ions between two different cation exchange
V O L U M E 28, NO. 4, A P R I L 1 9 5 6 resins, between two like anion exchangers, and between mixtures of anion a n d cation exchangers. Simpson a n d Wheaton (3413) summarized their studies to date on ion exclusion technique$. Gregor ( S I B ) and Kressman ( 2 4 B ) employed ion exchangr membranes to measure ionic activities in solution. INORGANIC SEPARATIONS
Several interesting analytical procedures are based on the separation of cations by ion exchange and the elimination of interfering cations. 1he use of cation exchange resin techniques in the separation and analysis of the alkalies and alkaline earths was the subject of many contributions to the technical literature. Okuno, Honda, and Ishimori (832)reported some results on the separation of lithium, sodium, and potassium by a ptrongly acidic cation exchanger. hshton and Killiams (2C) developed a n analytical method for the determination of pot Sutton and A41my( 1 1 4 C ) devised a rapid method for the determination of the alkaline components of ash from milk. Samuelson and Sjostrom (932)developed a n ion exchange procedure for this determination of alkali metals in the presence of alkaline earths. Rubidium and cesium (101C)were concentrated from Bea water by ion exchange. Similar separations were reviewed by Rieman ( 8 9 C ) . A variety of problems involving the determination of alkaline earths were solved using strongly acidic cation exchangers (1C, 13C, 16C, 19C, 22C, 69C, 7 l C , 7 7 C ) . Lerner and Rieman ( 6 8 C ) developed a quantitative separation procedure for the alkaline earths. A method for the separation of barium and strontium was developed by Bovy and Duyckaerts ( 1 4 C ) and Hahn and Straub ( 4 4 C ) . Bertrand and hlyers ( 1 O C ) separated ammonium and guanidine salts by cation exchange. Drterniination of ammonium, amide, a n d nitrate nitrogen in plant extracts \\-as described by Varner and others (117C). Rhodium and iridium separations were accomplished by ion exchange techniques ( S C , 23C). Separations of zinc from cadmium and magnesium were successfully carried out with the aid of ion exchangers (5C, 17C, 35C). Lead was concentrated (5%’) and dissolved ( 8 4 C ) hy means of cation exchange. T h e use of the high capacity ion exchange resins has become a n accepted procedure for concentrating extremely dilute solutions of electrolytes prior to their estimation. This technique has been employed in several hydrological and geochemical field studies. For example, rain water analysis has been facilitated by this technique ( I S C , 88C, I l S C ) , and Nydahl ( 8 2 C ) used similar techniques for the analysis of lake waters. Boiler scale analysis for total solids has been simplified by ion exchange methods (67C). Lane, Larson, and Paukey ( 6 4 C ) developed a convenient steam purity test. Gabrielson ( 3 1 C ) devised a n ion exchange procedure for determination of the total metal content in phosphating solutions. Tot,al anion concentrntion of uranyl solutions i\-as detemiicrd hy ion exchange by Day and others ( M C ) . X method for the separation of ferric iron and aluminum was developed (55C). Kadomtzeff ( 5 4 C ) studied the diffusion of nickel and cobalt ions in chromatographic separations. Ion exchange continues t,o play a n important role in the analytictil chemistry of transuranic elements, rare earths, and other elements of importance in atomic energy studies. Beryllium, a common element’in nuclear reactors, has been concentrated by ion esrhange prior t o itsdetermination (SOP, 115C). Scandiuni ( 5 1 0 \vas purified from rare earth contamination by cation exchange. Gabrielson ( 3 2 C ) removed interfering ions from plating bath solutions prior t o determining boric acid. Gallium, indium, and germanium ( 6 0 C ) were separated from other metals by ion exchange. T h e ion exchange separation of the rare earths was improved with the use of sequestering agents as the eluting reagents. Brooksbank and Leddicotte ( 1 6 C ) developed extremely sensitive tests for the rare earths in animal tissue. Wish, Freiling, a n d Bunney (118C) employed lact’icacid as a n eluent for trivalent actinides. Stewart, ( 1 1 1 C ) used ion exchange techniques for
731 determination of trace amounts of rare elements of the yttrium group. Similar studies on a macro scale were reported by Spedding and Powell (104C). Copper TYUS used as the retsining ion in the elution of rare earths rvith ammonium ethylenediamine tetraacetate (108C). Spedding and Powell ( 1 0 6 C ) di theory of these separations and their group (105C) elution of neodymium using citric acid-ammonium citrate solutions. T h e use of EDT.1 as a complexing agent for the elution of rare earths from cation exchangers has received consiJerable attention (7BC, 74CJ 107C). Thorium was determined in the 52C). Stevenson and others ( I f O C ) presence of rare earths (49C, described the separation of the platinum group metals on a cation exrhange resin. Zirconium and hafnium ( 7 C , 66C) were separated on a cation exchange resin using perchloric arid and nitric acid-citric acid solutions as the eluents. Antimony was determined in the presence of tin by means of an ion exchange procedure (5W). Ion exr-hange procedures have been utilized t o provide rnl)iti methods for the separation and determination of short-lived radioactive materials. These techniques are now standard for the evaluation of transcurium elements obtained by irradiation in nuclear reactors. Glass ( 3 7 C ) reported the separation of americium and curium using chelating agents as the eluents. Diamond, Street, and Seaborg (28C) examined the exchange properties of the actinides by means of a n ion exchange process. Our knowledge of the chemistry of americium-241 and -243 W R S extended by purification of this elements on a cation exchanger (R7C, 45C). Elements 99, 100, and 101 were isolated and their existence verified by ion exchange (SC, 29C, 33C, 34C, I 1 3 C ) . Studies on uranium chemistry Tvere facilitated by these techniques (53C, 35C). Japanese analysts (b8C) developed a complete ion exchange procedure for the radiochemical analysis of “Bikini ashes” which fell on the ship, Fukuryn Ilfaru. Several workers employed ion exchange for a variety of other radiochemical problems (S9C, 96C). Contributions were made in the field of chromatographic separations of inorganic elemerits by Pollard ( 8 6 C ) , Hiester and others (48C), and Carleeon (2OC). Trace metals in petroleum were determined by Sherwood and Chapman ( H C ) , and Baticle ( 6 C )followed chromatographic separations by means of condurtometric methods. Physical variation in ion exchange systems, such as sn-elling and shrinkage, have been used for analytical purposes (86C). S e w materials have been prepared which will aid in the evaluation of oxidation-reduction reactions (doc, 103C). Reactions involving ion exchange resins in liquid ammonia have been examined as possible separation systems (57C). Techniques for rapid analysis of iron were reported by Kojima and Kakihana (61C). Lillin (7OC) reviewed the synthesis of exchange resins which contain groupe having selectivity for heavy metals. Metalamine ciomplexes were studied by Shaw and Bordeaux (97C) and Stokes and Walton ( 1 1 2 C ) . Membranes containing ion exchange properties were used in several inorganic systems and their properties measured. Kyllie and Iiannan (119C, 12OC) reported the basic properties of such materinls. Spiegler and Coryell ( 1 0 9 C ) and Schlogl (Y.$C) obtained data on their elect,rical properties. Bergin and IIeyn ( 3 C ) employed such membranes in liquid ammonia systems. Ion exchange resin membranes were also used as electrodes for the determination of ion activity in solwtion (99C, 1OOC). Salt bridges were constructed using these membranes and these bridges were reported t o he superior to conventional salt bridges (21C). Anion exchange resins were studied further for the concentration and separation of numerous metallic anionic complexes. T h e ahilit’y of certain metals to form anionic complexes when in hydrochloric acid solutions has been used to advant:tge t)y a number of investigators. Kraus, Selson, and Smith (62C, 6.92, 79C, 80C, 81C) examined these reactions for the separation of a
ANALYTICAL CHEMISTRY
732 large variety of metallic anions including gold, titanium, vanadium, scandium, indium, gallium, thallium, palladium, and platinum. Similar methods were developed by Hague and others ( J l C , 42C) and applied to the analysis of alloys. Miller and Hunter (76'2) used such procedures for the determination of zinc in brasses. Hahn, Backer, and Backer ( 4 3 C ) and Beukenkamp, Rieman, and Lindenbaum ( 1 l C ) used strongly basic anion exchangers for the separation of phosphates and condensed phosphates. Hall and Johns ( 4 6 C ) employed strongly basic anion exchange resins for the separation of technetium from molybdenum, cobalt, and silver, An analytical separation was developed by Meloche and Preuss ( 7 5 C )for the accurate determination of rhenium after a n ion exchange separation of t h a t element from molybdenum. Russian workers summarized their studies of a similar problem (91C). Sulfate determinations were accomplished by a n ion exchange procedure using a barium precipitation (JOC). Chlorides in detergents were measured after an ion exchange concentration step (87C). Langvad ( 6 5 C ) attempted to separate chloride isotopes by adsorption on deep beds of strongly basic anion exchange resins. A chromatographic separation of the halides was reported by DeGeiso (26C). The platinum group metals were fractionated using anion exchange techniques ( 4 C , 12C, 73C). The use of complexinp agents has proved valuable in a variety of separations. Gillis and others (S6C) separated niobium and tantalum, using oxalic acid. Similarly, Kakihana ( 5 6 C ) detected trace amounts of germanium by adsorption of a germanium hematoxylic complex on a strongly basic porous exchanger. Tin, antimony, and tellurium were separated chromatographically on a strong base anion exchanger using oxalic acid to develop the chromatogram (102C). A theory of complex formation was reported by Coryell and Marcus (S4C). Nelson ( 7 8 C )studied the separation of alkali metals as their E D T A complexes on anion exchangers. Herber and Irvine (47C) completed extensive studies on the separation of cobalt, copper, zinc, and gallium using hydrobromic acid as the complexing agent. Citric acid and its salts were also found to be convenient complexing agents for a variety of separations (SOC, 92C). ORGANIC SEPARATIONS
Ion exchange techniques have become standards for the separation of many important biological substances. The analysis of amino acids has reached the point where their separation by cation or anion exchangers has become the accepted procedure throughout the world ( 9 D , I I D , 1 2 0 , 4 1 0 , 4220, 440, 48D, 5 9 0 ) . Perhaps the most interesting recent development in this field has been the use of volatile acids as the eluting agents (630). Strongly basic anion exchangers have been used extensively for the analysis of sugars from various natural sources ( l D , 1 5 0 , 340). Complex condensed ring systems, such as ketosteroids (SOD), have been separated. The chromatographic separations of peptides (IOD), nucleotides ( 3 5 D ) , and proteins (36D, 5 6 0 ) have been reviewed. Porter ( 4 5 0 ) reported his findings on the chromatography of proteins on a carboxylic cation exchanger. Grubhofer and Schleith ( 1 8 0 ) concentrated proteins on a carboxylic cation exchanger. Takemoto ( 6 1 D ) isolated type A influenza virus by an ion exchange technique. Various organic acids were reported on weakly and strongly basic anion exchange resins. Derungs and Deuel ( 1 4 0 ) developed a n ion exchange separation of the mono-, di-, tri-, and tetragalacturonic acids. L-Pipecolic acid was isolated from green beans ( 7 l D ) and the chlorogenic acid content of coffee beans was determined (68D). A standard ion exchange procedure was developed for the determination of uric acid in fruit ( 6 5 D ) . Alginic acid was determined after conversion to its free acid form by ion exchange ( 5 8 0 ) . Schenker and Rieman ( 4 9 0 ) established conditions for the chromatographic separation of malic, tartaric, and citric acids. Berntsson and Samuelson ( 5 D ) studied the
elution of various organic acids of low molecular weight from both strong and weak base exchangers. Organic acids from grass extracts were separated chromatographically on anion exchange resins (130). Ketones and aldehydes were adsorbed on strong base exchangers ( 5 5 0 ) . Considerable interest has been expressed in the use of ion exchange resins in the analysis of materials of interest to the medical field. Semimicromethods T7ei-e developed by Achor and Geiling ( 2 0 ) for the determination of morphine. Grant and Hilty ( l 7 D ) separated morphine and codeine using a porous strongly basic anion exchanger. Various alkaloids were isolated and assayed after elution from a carboxylic cation exchanger ( 7 D ) . A report was presented giving details of a comprehensive study of the quantitative elution of morphine from cation exchangers of varying degrees of cross linking ( 6 7 D ) . Antihistaminics (Z7D) were determined in pharmaceutical preparations and similar analyses of medicinals have been reported in Europe ( 6 4 0 , 65D, ?'OD). Clinicians have found ion exchange resins to be valuable for certain diagnostic tests. Sobotka and Gregor ( 5 7 D ) reviewed this subject, and Martin ( S 7 D ) presented an extensive evaluation of the use of ion exchange in medicine. Segal ( J Z D ) and Sharp, Hazlet, and Shankman ( 6 5 0 ) described the technique by which a carboxylic exchanger in the quinine form is used to evaluate the acidity of the stomach. Various other indicators have been used in place of the quinine ( 5 1 D ) . Hofgaard ( 2 4 0 ) reported the clinical results of this resin technique. Total serum base (5OD, 66D) and the composition of blood plasma ( 2 8 0 ) have been measured rapidly by ion exchange procedures. Ion exchange resins have been found useful for a variety of miscellaneous separations and procedures which are of general interest. Ion exchange reactions have been performed in solvents other than water. Bodamer and Kunin ( 6 D ) carried out studies in ethanol, acetone, benzene, petroleum ether, and mineral oil. Sansoni ( 4 7 D ) , Gemant ( 1 6 D ) , and Levi ( 3 1 D ) reported on results in similar systems. Changes in rate of exchange and volume of exchangers are the variables of considerable interest in nonaqueous systems. Soaps and detergents ( 1 9 D ) were examined for fatty acid content after a n ion exchange conversion. Ion exchange membranes were employed for studies in milk ( S D ) and various organic electrolytes ( 2 6 0 , SdD). Acid and alkaline values of ash from food were measured after an ion (290) exchange conversion of the salts to the corresponding free acids. Flavins ( 6 9 D ) were purified and concentrated with exchangers. Hormones from the pituitary glands of beef and hogs were fractionated on a carbovylic cation exchanger ( 6 2 0 ) . Nicotinic acid and nicotinamide (4SDl6OD)were quantitatively separated. A method for the estimation of choline esters has been developed using a carboxylic cation exchanger ( 5 4 0 ) . A resin has been proposed for the selective retention of sulfhydryl compounds ( S 8 D ) . Work was continued on the use of ion exchangers for concentration and purification of cytochrome C ( 5 3 0 ) . Antibodies were purified by means of ion exchange resins which have been linked with antigens ( 2 5 0 ) . Angiotonin ( 8 D ) , a chemical essential for blood formation, has been studied after purification with a carboxylic cation exchanger. Hirs ( 2 2 0 ) conducted an investigation of chymotrypsinogen using a weakly acidic cation exchanger. The specific catalytic activity of ion exchange resins has proved to be of considerable interest in organic chemistry; in many instances, their use aids in the separation of relatively pure products from the reaction mixture. Bernhard, Hammett ( 4 D ) , and Helfferich (goo, Z l D ) reviewed the theory of such catalytic activity. Sugars were hydrolyzed from plant extracts using cation exchange resins ( 4 0 0 ) . >lowery ( 3 9 D ) studied the effect of such catalysts on glycoside formation but reported little selectivity when compared as a function of cross linking in the exchanger structure. Riesz and Hammett ( 4 6 D ) showed t h a t
V O L U M E 2 8 , NO, 4, A P R I L 1 9 5 6 the catalytic hydrolysis of esters may be accelerated when quaternary ammonium ions are introduced into the reaction mixture. ION EXCHANGE RESIN ANALYSES AND TECHNIQUES
T h e routine evaluation of ion exchange resins is important in any analytical process which involves ion exchange resins. Fisher and Kunin ( 3 E ) have prepared a complete set of test procedures for the capacity determination of all types of ion exchange resins n hich are available commercially. Austerweil ( 1 E )developed a method for estimating the activityofexchangers. Stoch discussed the general evaluation of ion exchangers for water-conditioning applications (15E). Rapid methods for the determination of residual capacity were reported by Fuchs and Wagner (4E). The use of a titration procedure for the evaluation of resin capacity and basicity was reported by Strobe1 and Gable ( 1 6 E ) . Wet combustion has been proposed as a convenient procedure in analysis of residues on the exchanger ( 9 E ) . Several techniques for elution have been reported and are applicable t o the evaluation of certain exchange processes ( 5 E , 6E, 10E, 14E). Apparatus was described ( d E )for simultaneously measuring ultraviolet absorption and the radioactivity of substances being eluted from a n ion exchanger. Methods were developed for the determination of residual capacity by tracer techniques ( 8 E ) . Gregor, Belle, and Marcus ( 7 E )and Pepper, Paisley, and Young (11E) described methods for the determination of structural variables in exchange polymers. The effect of p H on capacity was examined for some special cases (12E). Radding, Phillips, and Hiester (13E) developed analytical methods for use in the evaluation of continuous countercurrent ion exchange processes. MISCELLANEOUS ANALYTICAL APPLICATIONS OF ION EXCHAIYGE
Chromatographic separations were reviewed and described in detail by Lederer and Lederer ( 7 F ) . Lister constructed a n automatic fraction collector for chromatographic separations ( 8 F ) . A special ion exchange column has been developed for ion exchange laboratory use ( I F ) . Some new resins have been synthesized which may be of interest in future work. Sulfonium groups have been introduced into exchange polymers ( 4 F ) . Ferris ( 6 F ) prepared exchangers with carboxylic and sulfonic groups. A chelating exchanger has been synthesized and may be of interest for inorganic separations ( 9 F ) . Permselective films having anion and cation exchange properties have been described by Bodamer ( 2 F ) . Bray and Reiser ( S F ) developed a method for recycling complexing agents. T h e manufacture of a strongly basic anion exchanger was reported from Czechoslovakia ( 1OF). Amphoteric exchange resins were prepared in Japan ( 6 F ) . LITER4TURE CITED REVIEW
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733 THEORY
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