Ion Exchange Robert Kunin and Richard I. Gusfafson, Rohm and Haas Company, Philadelphia, Pa.
A
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IS THE previous review, those topics that are specifically related to ion exchange chromatography have been excluded because they will be treated separately in another review. The past several years have seen ion exchange techniques employed in many areas of analytical chemistry throughout the academic, industrial, and iiistitutional laboratories of the world. -41though ion exchange is employed for a variety of analytical purposes, the technique is basically employed in order to (1) concentrate, ( 2 ) separate, and (3) purify various substances to be analyzed or to be employed in analytical procedures. A review of the literature of the past two years illustrates both “gainsJ’ and “losses” for the growth of ion exchange as an analytical procedure. New ion exchange materials have broadened the scope of this technique; however, techniques other than ion exchange have developed in recent years which compete with ion exchange for certain areas of analysis. For example, the recent developments in flame photometry and atomic absorption analysis now permit the analysis of traces of many metals without the need for concentration and separation of mixtures of traces of many metallic species. Gas chromatography is now beginning to compete with ion exchange for the analysis of mixtures of some amino acids. These “losses” have been compensated, however, by many gains. The development of the new macroreticular ion exchange resins and new ion exchangers based upon cellulosic aiid dextran derivatives has extended the utility of ion exchange in the analysis of materials dissolved in nonpolar media and in the analysis of biological materials. One limitation to the widespread use of ion exchange has been the slowness in the development of standardized procedures for the routine analyst in such areas as covered by the water, sugar, fertilizer, and metallurgical industries. Some progress may be noted by the inclusion of ion exchange procedures in the standard methods of A4.0.Ai.C., A.K.W.A., and AIS.T.lI, This progress, however, seems to lag far beyond the potential of ion exchange in analytical chemistry. The availability of many ion exchange materials of analytical quality from most laboratory supply houses should stimulate further development and acceptance of routine ion exchange analytical procedures.
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This review covers the period Eovember 1966 to November 1967. REVIEWS
A book devoted to the analytical applications of ion exchange has been written by Inczedy (24). It is a translation of an earlier ~iublicationwritten in Hungarian. The translation, however, is a considerably expanded version of the original book. The book, which covers many detailed ion exchange analytical procedures, is devoted entirely to the area of inorganic analysis. Kakihana and Kato (Sil) have reviewed recent developments in the use of ion exchange resins as spot test reagents. Although this technique has not found wide usage, the Japanese have developed the technique to a fine degree covering the qualitative analysis of most inorganic species. The technique supposedly increases the sensitivity of the conventional spot tests. A review of the principles involved in the ion exchange separation of biochemicals has been prepared by Dixon ( I A ) .
exchange selectivity data for the alkaloid cations mere studied by Starobinets and Koka (18B). Of considerable interest are the studies of RIathieson aiid Shet (ISB)on the dissociation and swelling of the cation exchange resins based upon the copolymers of methacrylic acid, methyl methacrylate, divinylbenzene, and ethylvinylbenzene. Boyd and Bunzl (SB) have presented data for anion and cation exchangers which they claim support the validity of the Donnan membrane equilibrium to the absorption of salts by these ion exchangers. Dranoff and his students ( I B , 2B, 4B) have applied the models of Helfferich for both film and particle diffusion to their kinetic studies on cation exchange. The approach of Dranoff has been confirmed by Petrova and Lifshits (ITB). The influence of ion exchange selectivity on film diffusion-controlled ion exchange has been studied by Copeland, Henderson, and Marchello (5B). The kinetics of ion exchange in a weak acid cation exchange resin mas determined by Hanley, Churms, and Leisegang (9B) to be particle-diffusion controlled.
THEORY
The development of new analytical procedures depends materially upon an adequate understanding of the theoretical principles involved. In this respect, studies on the various aspects of ion exchange theory have kept pace with the development of new ion exchange analytical prodedures. Various thermodynamic studies on the heats of ion exchange have been conducted by Vaslow and Boyd (dOB), Xancollas and Paterson (15B), and Flett and Meares (6B, 7 B ) . -4critical thermodynamic approach to ion exchange selectivity has been presented by Marillsky ( I I B ) . Anion exchange selectivity data have been obtained by Strelow and Bothma ( f 9 B ) for 52 elements in sulfuric acid media. Marple (12B) has developed some anion selectivity data for cadmium in chloride media and Molnar, Horvath, aiid Khalkin (14B)have obtained anion exchange selectivity data for the light rare earths in methanol solutions of ammonium nitrates. Cation exchange selectivity data for the alkali elements have been presented by Ghate, Gupta, and Shankar (8B) and Xovitskaya and Starobinets ( I 6 B ) . Similar data were obtained by Iirylova (10B) for the alkaline earths. Ion
INORGANIC ANALYSIS
Various studies pertaining to the analysis of the alkali elements have been presented by Hourquin, Scheidecker, and Hereiiguel ( I C ) , Polakovic and Polakovicova (34C), Yarovenko, Komarova, and Kreshkova 14IC) and Jankowska (21C). -inion exchange procedure for determining small amounts of silver was developed by Kashlinskaya, Strel’nikova, and Prelovskaya ( 2 3 2 ) . Procedures for the analysis of lead have been described by Hamza and Headridge (16C) and Rosenburg (36C). Various procedures for the analysis of the alkaline earths have been investigated by Kemula, Brajter, and Bogdanska (26C), Ibbett (20C), Blake, Oldham, and Sumpter (5C), Gregory (14C), Hantabal, Fojtik, Rusek, and Trnovec ( I TC), and Pavlotskaya and Levina ( 3 3 2 ) . The analysis of iron and other transition elenleiits by ion exchange has beeii noted by Fardy (I%’), De and Sen (9C), Campbell, Spano, aiid Green (TC), Korkisch and Gross (29C) , Grossmann, Doege, and Grosse-Ruyken (15C), Korkisch (27C), Babachev and Raeva-Sikolova (dC), Danielsson and Ekstrom ( 8 0 ,Babachev (SC), Jurcsik ($E), deGelis ( I O C ) , Aizeiiberg ( I C ) , and Kawabuchi and
Kiriyama (25C). Procedures for the analysis of thorium have been described by Toribara and Koval (4OC) and Alimarin and Medvedeva (WC). Strelow (39C) and Shimizu ( S X ) have employed anion exchange resins for the analysis of rare earths. Other miscellaneous ion exchange procedures have been described by Korkisch and Feik (2SC) for rhenium and molybdenum, Bottei and Trusk (SC) for tungsten, Lovasi and Szuecs (SOC) for niobium, and Simek (38C) foi telluriuni and selenium. The use of ion exchange materials in neutron activation and X-ray fluorescence analysis has been reported by Eisner et a l . ( I l C ) , Hayden (18C), and Campbell, Spano, aiid Green i?'C). llicrochemical qualitative spot tests based upon ion exchange resins have been proposed by Fukui, Oshima, and Yoshiiio ( I S C ) , Qureshi and Qureshi (35C), Murase, Kakihana, and Kato (32C),Murase and Kakihana ( S I C ), and Kato, Ichikawa, and Kakihana (Z4C). O R G A N I C ANALYSIS
The use of macroreticular ioii exchange resins for the analysis of petroleum products has been studied i i i detail by Webster, Wilsoii, and Franks ( 4 0 ) . Other procedures for use in organic analysis have been described by Leivalidowski and Kojcicka i3D), Kreshkov and Tumoi-skii (ID), dkimov, Smiriiov, and Eniel'yanova ( I D ) , aiid \I-est. Qureshi, and Qureshi (50). PHARMACEUTICAL A N D BIOLOGICAL ANALYSIS
.1method for the measurement of the ionizable calcium and magnesium in plasma has been described by Frizel, lIalleson, and llarkq ( 4 E ) . The analysis of amino acid. in blood has been described in detail by Reid et al. ( 8 E ) . Klotz and Rehfeld (6E) have employed a cation exchange resin for the determinatioii of lactic acid in infusion solutions. Various procetluies for the sellaratioii and analysis 07 the alkaloids and related compounds have been developed by Fang and Huo M E ) , Diiiic ( I E ) , 1Ianikowski and Xiezgodzki (6E), Fleming et al. ( 3 E ) , and llontgomery and Weinsn ig (YE). NEW I O N EXCHANGE MATERIALS
Although there are many, many ion exchange materials available to the analytical chemist, there is a constant search for new ion exchangers exhibiting unusual selectivities and functionalities. Kew studiei 011 phosphonic acid cation exchange resins have been presented i n publicatioiii by llarhol aiid Chmelicek ( 1 1 F ) and Leikin, Davaiikov, and Korshak ( S F ) . Several studies on chelatiiig ioii exchange resins have been made by Gustrow (ZV), Hering and
Haupt ( S F ), Hering, Trenne, and Neske ( 4 F ) , Hering ( 6 F ) , Koster aiid Schmuckler ( S F ) , and Veruovic ( 1 4 F ) . The properties of amphoteric ion exchange resins basic upon copolymers of 2-methyl-j-vinylpyi idine and fumaric or maleic acids have been described by Vasil'eva and Gavuriiia ( I S ) . Various redox copolymers with and nithout ion exchange characteristics have been described by Manecke and Eourrvieg ( I O F ) and Kuii (?F,S F ) . The exchange characteristics of ammonium hexacyanocobalt ferrate have been determined by Petrow and Levine ( 1 2 F ) and the properties of ferrocyanide molybdate have been described by Eaetsle, Huys, and van Deyck (117). ACKNOWLEDGMENT
The authors acknowledge the assistance of Dolores Sosnowska, Erich hIeitzner, and the library staff of the Rohm aiid Haas Company. Without this assistance, this review would not have been possible. LITERATURE CITED
Reviews (1A) Dixon, H. B. F., C s p . Biol. Khinz. 8, 278 (1967). (2.4) Inczedy, J., "Analytical Applications of Ion Exchangers," Pergamon Press. S . Y.. 1966. (3A) Kakihana, H. and Kato, K., Bunseki Kagaku 15, 199 (1966). Theory (1B) Blickenstaff, I?. A., FVagner, J. D., and Dranoff, J. S., J . Phys. Chem. 71,
1665 (1967). (2B) Zbid., p. 1670. (3B) Bovd, G. E. and Bnnzl. K.. J . Amer. Chem."Soc. 89, 1776 (1967j. ' (4B) Colwell, C. J. and Dranoff, J. S., A.I.Ch.E. 12, 304 (1966). (5B) Copeland, J. P., Henderson, C. I., and Naichello, J. lI., Ibzd. 13, 449 (1967). (6B) Flett, D. S. and Meares, P., Trans. Faraday Soc. 62, 1469 (1066). (7B) Flett, D. S. and Meares, P., J . Phys. Chem. 70, 1841 (1!166). (8B) Ghate, 11. It., Gupta, A. R., and Shankar, J., Indian J . Cheni. 4, 333 (1966). (9B).Hanley, 11. B., Chrirms, S. C., and Leisegang, E. C., Chem. Commun. 1967, 78. (10B) Krylova, A. A., et al., Russ. J . Phys. Chem. 40,233 (1966). (11B) JIarinsky, J. A., J . Phys. Cheni. 71, 1372 (1967). (12B) JIarple, L. FT., J . Inorg. S u c l . Chem. 28, 1319 (1066). (13B) Mathieson, A. It. aiid Shet, It. T., J . Polymer Sc?.,Pt. A-1 4, 2943 (1966). (14B) AIolnar, F., Horvath, A , , and Khalkin, V. A., J . Chrornatog. 26, 215 ( 1967). (l5B) Nancollas, G. H. and Paterson, R., J . Inorg. ,Vucl. Chem. 29, 363 (1967). (16B) Novitskaya, L. V. and Starobinets, G. L., Dokl. d k a d . S a u k Belorussk. S S R 10, 7 5 5 (1966). (17B) Petrova, L. Ya. and Lifshits, P. Z., Zh. Fzz. Khzm. 40, 2947 (1966).
il8Bi Starobinets. G. L. and Koka. I. P.. Vestsi Akad. ,kavuk Belarusk.' SSR: Ser. Khim. I\'avuk 1966, 35. (19B) Strelow, F. W. E. and Bothma, C. J. C., ANAL. CHEM.39, 595 (1967). ' (20B) Vaslow, F. and Boyd, G. E., J . Phys. Chem. 70, 2507 (1966). Inorganic Analysis
(IC) Aizenberg, A. S . , Tr. Vses. Gos. Inst. Ll-auchn.-Issled. i Proektn. Rabot Ogneuporn. Proni. 37, 113 (1963). (2C) hlimarin, I. P. and Medvedeva, A. II.,Zh. Analit. Khim. 22, 436 (1967). (3C) Babachev, G. S . , Chim. Anal. ( P a r i s )48, 238 (1966). (4C) Babachev, G. S . and Itaeva-Nikolova, L. Al., Khim. i Znd. (SoJia) 38, 12 (1966). (5C) Blake, W.E., Oldham, G., and Sumpter, I)., .Yalure 203, 862 (1964). (6C) Bottei, It. S. and Trusk, A., Anal. Chim. ; I d a 37, 400 (1967). (7C) Campbell, W.J., Spano, E. F., and Green, T. E., Anal. Chem. 38, 987 ( 1966 ) .
( 8 C ) Danielsuon, L. and Ekstrom, T., Acta Chem. Scand. 20, 2415 (1066). (9C) De, A. K. and S e n , A. K.: Talanta 13, 1313 (1966). (10C) deGelis, P., Chim. Anal. (Paris) 49,
:in
(1967>.
(11C) -Ekner, U., Itott\chafer, J. AI., Beilandi, F. J., arid Mark, H. B.. Jr., .lnaZ. Chem. 39, 1466 (1967). (12C) Fardy, J. J., Australian At. Energy Comm., T R G R e p AAEC-E-152. (13'2) Fukiu, K., Ozhima, T., and Yoshirio, T., Kagaku To Kogyo (Osaka) 40,406 (1966). (14C) Gregory, L. P., Health Phys. 10, 485 (1964). (132) Grossmann, O., Iloege, H. G., and Grosse-Iliiykeri, H., Z . Anal. Chem. 219, 48 (1966). (16C) Ilamza, A. G. and Headridge, J. B., Analyst 91, 237 (1!166). (1iC) Ilautabal, E., Fojtik, 31., Riisek, Y.,and Trnovec, T., Chem. Zvestz 18, 20'3 (1964). (IhC) Havden, J. A., Talanta 14, 721 (1967).
(19C) Horirquiii, It., Scheidecker, AI,, and Herengriel, J., Chim. ilnal. (Parzs) 49, 28 (1967). (20C) Ibbett, It. D., ilnalyst 92, 417 (1067) ,- . - . ,. (21C) Jankowska, S., Intern. Dairy Congr., Proc. 17th, Jlunich, 1966, 2 , 253. (22C) Jiircsik, I., Ionenaustauscher, Ihre Anwendung, Vortr., S y m p . , Balatonsceplak, Hiing. 1963,203. ( 2 3 C ) Kashlinskaya, 8. E., Strel'nikova, h. P., and Prelovskaya, Z. Ya., ilnaliz. Blagorodn. Metal. A k a d . ,Yauk SSSR Inst. Ob.yhch. i Ayeorgan.Khim. 1965, 16. (24C) Kato, K., Ichikawa, T., and Kakihana, H., ,\-ippon Kagaku Zasshi 87, 718 (1966). (25C) Kawabiichi, K. and Kiriyama, T., Bunseki Kagaku 16, 128 (1866). (26C) Kemiila, R., Brajter, K., and Bogdanska, E., Chenz. -1nal. (Warsaw) 11, 123!) (lCJ66). ( 2 i C ) Korkisch, J., .Yature 210, 626 i106G). (2XC) Koikiych, J. and Feik, F , dnal. Chzm. Acta 37, 364 (1967) (t9C) Korkiach, J. and Gross, II., Separ. ,
Sri. 2 , 169 (1967) (30C) Lovaai, J. and Sziiecs, P., Kohasz. L a p o k . 98, 364 (1963). (31C) Aluraie, T. and Kakihana, I € , .Yzppon Kaaakzi Zasshz 87.721 11966). (32Cj 'Xnras& T., K a k i h k ~ ,~H.,and Kato, K., Ibid., 724 (1966). ( 3 X ) Pavlotskaya, F. I. and Levina, G. P., Zh. .Analit. Khim. 21, 553
(1966).
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(34C) Polakovic, J. and Polakovicova, J., Sb. Prac. Chem. Fak. SVST 1966, 87. (333) Qureshi, M. and Qureshi, S. Z., Anal. Chem. 38, 1936 (1966). (36C) Rosenburg, J. P., Rtw. B r a d . Quim. 60, 291 (1965). (37C) Shimizu, T., Anal. Chim. Acta 37, 75 (1967). (38C) Simek, M., Chem. Listy 60, 817 (1966). (39C) Strelow, F. W. E., Anal. Chem. 38.
Organic Analysis
(1D) Akimov, V. K., Smirnov, 0. K. and Emel'yanova, I. A., Zh. Analit Khim. 21,610 (1966). (2D) Kreshkov, A. P. and Tumovskii, L. A., J . Anal. Chem. USSR 21, 541 ( 1966). (3L)) Lewandowski, A. and Wojcicka, E., Poznan. Towarz. Przyjaciol Nauk,
New Ion Exchange Materials ( I F ) Baetsle, L. H., HLIYS,D., and van Deyck, D., J . Znorg. Nucl. Chem. 28, 2835 (1966). (2F) Gustrow, J . Prakt. Chem. 31, 320
Wydzial Mat. Przyrod. Prace Komisji
Mat. Przyrod. 12, 67 (1967). (4D) Webster, P. V., Wilson, J. N., and Franks. M. C.. Anal. Chim. Acta 38. 193 (1967). ' (5D). West, P. W., Qureshi, M., and Qureshi, S. Z., Zbid. 37,97 (1966).
(1966). \ - - - - ,
(3F) Hering, R. and Haupt, D., Z . Chem. 6, 192 (1966). (4F) Hering, Ii., Trenne, K., and Neske, P., J . Prakt. Chem. 32, 291 (1966). (5F) Hering, R., Ibid., 34, 69 (1966). (6F) Koster. G. and Schmuckler., G.. - , ' Anal. Chim. Acta 38, 179 (1967). (7F) Kun, K. A., J . Polymer Sci. AS, 1833 (1965). (8F) Kun, K. A., Ibid., A4. 847; 859 (1966). (9F) Leikin, Y. A., Davankov, A. B., and Korshak. V. Y.. Vusokomolekul. Soedin., A9, 619 (1967): " (10F) Manecke, G. and Bourwieg, G., Makromol. Chem. 99, 175 (1966). (11F) hlarhol, J. and Chmelicek, J., Collection Czech. Chem. Commim. 31, 3881 (1966). (12F) Petrow, H. G. and Levine, H., Anal. Chem. 39, 360 (1967). (13F) S'asil'eva, Ye. 11. and Gavurina, It. K., Polymer Sci. ( U S S R ) (English Transl.) 8, 781 (1966). (14F) Veruovic, B., Chem. Prumysl 17, 21 (1967).
Pharmaceutical and Biological Analysis
Anal. Chem. 37,692 (1963). ' (4E) Frizel, D. E., Malleson, A. G., and Marks, V., Clin. Chim. Acta 16, 45 (1967). (5E) Klotz, L. and Rehfeld, S., Pharm. Zentralhalle 106, 3 (1967). (6E) Manikowski, W. and Niezgodzki, L., Farm. Polska 21,657 (1965). (7E) Montgomery, K. 0. and Weinswig, bl.H., J . Pharm. Sci.55, 1141 (1966). (8E) Reid, R. H. P., Craft, M. C Roberts, E. G. G., and Wise, L., Technl: con Symp., 2nd iV. Y . London 1965, 671 (1966).
Inorganic Microchemical and Trace Analysis Philip W . West, Coafes Chemical laboratories, Louisiana State University, Baton Rouge, l a . Foymae K . West, Gulf South Research Institute, Baton Rouge, l a .
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and trends have taken place during the past two years which hold promise for significant advances in the field of inorganic microchemical and trace analysis. Membrane electrodes have been developed which show conclusively that electroanalytical methods are becoming available that are selective and even specific and have sufficient sensitivity and simplicity to make them competitive with other established methods. A%tomicabsorption spectroscopy which is inherently specific is now being improved by chemical adjuncts which improve the accuracy and provide means for very significant increases in sensitivity. The dramatic increase in interest in studying minute amounts of material and analyzing trace systems is leading to increasing interest in catalyzed and induced reactions. The electron microprobe is proving to be an invaluable tool in studying individual species of atoms concentrated on minute areas. The elegantly' simple ring oven method is proving useful for a wide number of diverse st'udies and is now established as a .valuable quantitative technique for microanalysis. Gas chromatography is E W DEVELOPMENTS
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now established as a tool in studying metals. This review, covering January 1, 1966 to December 31, 1967, is contiguous to the 1966 review of Inorganic -Microchemistry (226) although the scope and emphasis are slightly changed. Because of the voluminous literature which has appeared dealing with various aspects of microchemical and trace studies, it is no longer possible to attempt the recording of specific and detailed facts as was done in the past. I t is unfortunate that masking agents, isolated separations procedures, new organic reagents, and new gadgets for microcheniical manipulations can no longer be recorded for the convenience of the reader. Likewise, topics reviewed elsewhere will be nientioiied only when necessary to show applicatioiis in the development of significant new trends. ,4number of valuable and interesting reviews have appeared in the literature which serve to supplement and augment the present review. T. S. West (232) has reviewed inorganic trace analysis, hlinczewski (149) has reviewed methods of separation together with methods for determining trace impurities, and
Helbig has reviewed the status of ultramicro analytical techniques with special emphasis on electrochen~ical methods (94). In a review of developments in aiialytical chemistry, 13elcher (10) has discussed other techniques of interest in microchemical and trace studies. Various methods for concentrating elements for microchemical and trace studies has been reviewed (135)and individual techniques such as solvent extraction (84, the ring oven method (179), thin-layer chromatography (191), and the use of ion exchange beads as separation and reaction media (75) have all been discussed. Rechnitz has discussed the status of cation-sensitive glass electrodes (176, 177) as well as membrane electrodes applicable to anion studies (175). l'ungor, Havas, and Toth also reviewed the preparation and applications of membrane electrodes (167). Hanna and Siggia have reviewed kinetic methods of analysis (91), Walsh (217) has discussed recent major advances in atomic absorption spectroscopy, the use of laser-excited spectra for qualitative studies in geology and metallurgy has been summarized (150), and the principles and techniques of scanning
