Review of Fundamental Developments in Analysis
Ion Exchange Robert Kunin and
F.
X . McGarvey, Rohrn & Haas Co., Philadelphia, Po.
widespread utilization of ion exchange techniques and principles in the various areas of analytical chemistry has necessitated a revision of the manner in which the topic of ion exchange is treated in these review. Ion exchange chromatography, for example, has been treated as a part of the general topic of chromatography and has been included in that section. This review covers the period November 1959 to November 1961. In addition, omission has been made of those articles which are in essence variations on a theme. HE
THEORY
Much of the theory pertaining to ion exchange and of interest to the analytical chemist is now being covered in Annual Reviews of Physical Chemistry. However, in view of the importance attached to ion exchanger uniformity by the analytical chemist, the recent work of Glueckauf and Watts ( S A ) and Freeman ( I A ) on the heterogeneity of ion exchange resin particles has been significant. In the previous review and in the Annual Rc views of Physical Chemistry for 1961, Kunin reviewed some of the problems associated with heterogeneity on a macroscopic scale; however, Glueckauf and Watts cite evidence for the nonuniformity present in the exchanger phase due to the inherent nature of the polymerization process itself during the synthesis of ion exchangers. It is most important that the chemist designing analytical procedures basfd upon ion exchange resins realizes that some nonuniformity must exist between batches and samples of a psrticular exchanger type, between particles of a single sample, and even within a single bead of an ion exchange resin. NEW ION EXCHANGE MATERIALS
The continued utilization of ion exchange techniques by the analytical chemist has increased the number of ion exchange materials available through laboratory supply houses. Resins of graded particle sizes and degrees of cross linking, ion exchange chromatographic papers, ion exchange modified celluloses, and liquid ion exchangers are now readily available. Of recent interest to those working in nonaqueous media is
the availability of macroreticular ion exchange resins described by Kunin, Neitzner, and Bortnick ( I B ) . These ion exchange resins possess a rigid pore structure and surface area similar to that of the inorganic sorbents such as the aluminas, silicas, and the carbons. The new inorganic exchangers such as the phosphomolybdates, p h o s p h o t u n g states, zirconium phosphates, etc., are also available.
various materials such as caustic, urine, bone, and water. Ion exchange procedures for the determination of beryllium were developed by Smythe and Whittem (,99D), Kocheva (17D), and Vetejska and Mazacek (S6D). Various procedures involving ion exchange for the analysis of steels were developed by Hall and Bryson (ISD),Duval, Ironside, and Russell (7D), Athavale, Xadkarni. and Venkateswarlu (SO), Warren, Hazel, and McNabb (58D), and Bilinska and CONCENTRATION OF DILUTE SOLUTIONS Terpilowski (SD). One of the major functions of the ion Various ion exchange procedures for exchanger in analytical chemistry is determining copper were developed by that of concentrating dilute solutions Kolonina (18D), Edge (go), Turse and of various ionic species. Various proRieman (S5D), Schrenk, Graber, and cedures have been developed by Canney Johnson (26D), and Forberg and Lundand Hawkins (SC), Golovatyi and and Imoto ( 1 4 0 ) employed a gren (9D), chelating resin for determining mangaKhemel’nits’ka (4C), Kocheva (6C), and Brooks ( I C ) , for concentrating nese in brines. trace metals present in water supplies Ion exchange procedures for determining trace amounts of radioisotopes prior to their estimation in the laboratory. Phosphotungstate precipitates were developed by Stronski and Rybakow (SLD), Ryabchikov and were found to be excellent ion exchangers by Sugihara (9C) and Krtil Terent’eva ( 2 5 0 ), Moore (SOD), and Petrow et al. (SSD). Procedures suib (7C) for the concentration of cesium and rubidium from sea water. Adsorption able for the determination of thorium and concentration of trace metals from in low grade ores were proposed by concentrated salt solutions were studied Strelow ( S I D ) and Petit and Lumbroso by Gartner and Penndorf (SC) and van ( S S D ) . Brooks and Ahrens ( 4 0 ) employed a strong base anion exchanger for Erkelens ( I N ) . Grant (5C) developed a concentration procedure for deterthe spectroscopic detection of noble mining yttrium in biological materials. metals in silicate rocks. Paper impregnated with ion exchange The growth of the fluorocarbon indusresins was employed by Lewandowski try and increased fluoridization of water (8C) for the concentration of various supplies have resulted in the developionic species. ment of various techniques for determining fluorine. Ion exchange procedures, primarily designed for the INORGANIC ANALYSIS removal of interfering substances prior to the estimation of fluorine, n-ere Concern over radioactive fallout has stimulated the search for methods for developed by Fresen, van Gogh, and van Pinxteren ( I I D ) , Talvitie and analyzing water and foods for various radioactive isotopes. Ion exchange Brewer ( S 4 D ) , and Hensley and Barney methods have been developed by Jean( I S D ) for use in water analysis. Related maire and Michon (160) and Porter procedures were developed by Shapiro (240) for determining the concentration ( S s D ) , Schroder and Waurick (S7D), of strontium-90 in milk and milk prodand Sporek (SOD) for the determination ucts. Knapstein (16D) and Agg, Eden, of fluorine in phosphate rocks, polymers, and Melbourne ( I D ) have developed and uranium salts. similar procedures for determining Ion exchange procedures for the strontium-90 in water supplies. determination of boron in steels were devised by Parker and Barnes ( S I D ) Various ion exchange techniques have and Danielsson ( 6 D ) . Anion exchange been developed by Kade and Seim (S7D), Carpenter ( 5 D ) , Foss (IOD), procedures were suggested by LagerTakagi and Imoto ( S S D ) , and Weiss and strom and Samuelson ( I 9 D ) for the Lai (39D) for the determination of determination of chlorides in sulfite calcium and other alkaline earths in waste liquors. VOL. 34, NO. 5, APRIL 1962
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ORGANIC ANALYSIS
As in the case of the use of ion exchange in inorganic analysis, ion exchange has proved useful in many areas of organic analysis. Lewandowski and Jarczewski (4E), Carruthers, Oldfield, and Teague (IE), Takimoto and Yatsuo (IZE),and Hrdy and Lochmanova (SE) have employed cation exchange resins for the concentration and separation of various amines prior to their estimation. Wiseman, Mallack, and Jacobson ( l 4 E ) and Bose and Gupta (1E) have developed ion exchange procedures for the analysis of sugar juices and products. Various ion exchange procedures have been investigated for the analysis of food products. Storherr and Burke (IOE)have employed a cation exchanger for determining the presence of 3-amino1,2,4triazole in vegetable crops. Murata and Suzuki (5E) have determined carbonyl compounds in brandy and wine with the aid of exchangers. Vanilla extracts have been analyzed by ion exchange procedures by Prill et al. (7E)and by Sullivan, Voelker, and Stahl (11E). Phifer and Bell (6E) have determined xanthate sulfur in viscose by a batch anion exchange procedure. Similar anion exchange procedures were developed for the analysis of acids and iodine in biological materials by Tompsett (1SE)and Sterling and Tabachnik (9E). Tandem strips of cation and anion exchange papers have been used by Smille (8E) for the deionization of solutions prior to the estimation of various nonionic organic compounds. MICROANALYSIS
With the availability of stable, uniform, light colored, and translucent ion exchange resin beads, a notable amount of research has been devoted to the use of ion exchange resins in microanalysis, particularly as a reaction media for spot tests. The Japanese have pioneered in this area of activity. Fujimoto (4F6 F ) , Kakihana, Mori, and Watanabe ( Y F ) , and Kat0 and Kakihana (8F)have developed many procedures utilizing ion exchange resins as reaction media for microdetection spot tests and report an order of magnitude increase in sensitivity over conventional spot tests. Similar studies have been reported by West (IIF), Koblyanskii (9F),Boase and Foreman ( I F ) ,Eastoe ( S F ) , Legradi ( I O F ) , and Malissa ( I I F ) . Alimarin and Petrikova ( I F ) in a review of ultramicroanalysis describe the use of microscopy with the above techniques. MISCELLANEOUS PROCEDURES A N D TECHNIQUES
As the analytical chemist becomes familar with the basic phenomena of ion exchange and the characteristics of various ion exchange materials, it is not 102 it
ANALYTICAL CHEMISTRY
surprising to find publications relating to a variety of tricks of the trade. Mixtures of surface-active agents are now analyzed routinely after fractionation of the mixture into the cationic, anionic, and the nonionic components by ion exchange resins. Rosen (IOG) and Kwata and Inone (7G) have developed such procedures. Cabbell, Orr, and Hayes (IG) have applied such a procedure using a mixed bed of a sulfonic acid cation exchanger and a weakly basic anion exchanger to the determination of germanium. Kniestedt and Wahle (6G)have developed a rapid method for determining CaS04 in gypsum products which involves the reaction between the solid sample and a slurry of a sulfonic acid resin folloa-ed by a subsequent titration of the filtrate with standard NaOH. Various procedures have been developed by Kemula et al. (5G), Ziegler (ISG),and V7ynne, Burdick, and Fine (IZG) for the determination of lead, iron, manganese, etc., in which the anion exchanger serves as a precipitant for either the sulfates or hydrous oxides of these metals. Collin (SG),van Kiekerk and de Wet ( I I G ) , and Mosen, Schmitt, and Vasilevskis (8G) have combined ion exchange with x-ray fluorescence and neutron activation in trace analysis by first concentrating the trace constituents into various solid or liquid ion exchange materials and then directly irradiating the exchanger in the x-ray spectrograph. Ion exchange is still widely employed for the determination of the total concentration of ions present in solutions and the assay of various solid electrolytes by converting the salts to their respective acids or bases followed by an acid-base titration. The technique has been applied by Ceausescu (IG) to the microdetermination of sodium by titration of the liberated acid following the passage of the dissolved triple acetate through a cation exchange in the acid form. Richardson (9G)has modified the technique for the assay of citrates and tartrates by the use of nonaqueous titrimetry. Galakhovskaya (4G)has employed the technique for the analysis of salt waters and brines. PREPARATION OF REAGENTS
Although ion exchange materials are in themselves analytical reagents, they are also employed for the preparation of other reagents. The well known use of ion exchange resins for the preparation of deionized water for analytical purposes needs little discussion. However, it should be emphasized that, for certain analytical studies, the use of deionized water prepared in a conventional manner may not be suitable. Some water supplies contain sufficient quantities of nonionic surfactants that will
pass through an ion exchange resin deionizer without being adsorbed. In cases such as these, ion exchange is usually combined with distillation for the preparation of water where difficulties due to the presence of traces of nonionics can occur. Hanselman and Rogers (WH)have generated various reagents coulometrically with the aid of ion exchange membranes for the preparation of reagents that normally could not be prepared by conventional coulometric techniques. Serjeant ( S H ) has prepared pure standard metallic perchlorate solutions and Blaedel and Olsen ( I H ) an unusual oxidizing reagent by means of ion exchange. ACKNOWLEDGMENT
The authors acknowledge the assistance of Erich Meitzner and Helen Tucker and the library staff of the Rohm & Haas Co. Without this assistance, it would have been impossible to review the many articles that appeared during the past year. LITERATURE CITED
Theory (1A) Freeman, D. H., J . Phys. Chem. 64, 1048 (1960). (2A) Glueckauf, E., Watts, R. E., Nature 191, 904 (1961). New Ion Exchange Materials (1B) Kunin, R., Meitzner, E., Bortnick, N., J . Am. Chem. SOC.84,305 (1962). Concentration of Dilute Solutions (1C) Brooks, R. R., Analyst 85, 745 (1960). (2C) Canney, F. C., Hawkins, D. B.,
U.S.Geol. Survey, Profess. Papers h’o. 400-B,89 (1960). (3C) Gartner, K., Penndorf, H., Chem. Tech. (Berlin) 12, 29 (1960). (4C) Golovatyi, R. K.,Khemel’nits’ka, S. LI., Nauk. Zapiski, L’wivs’. Derzhav. Unav. am I . Franka Khim. Zbirnik 5 ,
141 (1958). (5C) Grant, C. L., AXAL. CHEM. 33, 401 (1961). (6C) Kocheva, L. L., Fiz.-Mat. Fak. 52, 97 (1959). (7C) Krtil, J., J . Inorg. & Suclear Chem. 19,298 (1961). (8C) Lewandowski, A., Chem. Anal. ( W a r saw) 4, 545 (1959). (9C) Sugihara, T. T., Progress report for year ending Jan. 31, 1961 (Clark University, Worcester, Mass.). (lac)van Erkelens, P. C.. Anal. Cham. Acta 25,42 (1961).
Inorganic Analysis (1D) Agg, A. R., Eden, G. E., Aielbourne, K. V., Proc. SOC.Water Trealment Exam. 6, 142 (1957). (2D) Athavale, V. T., Nadkarni, M. S., Tenkateswarlu, C. H., Anal. Chim. Acta 23, 438 (1960). (3D) Bilinska, W.,Terpilowski, J., Chem. Anal. (Warsaw)5,17 (1960). (4D) Brooks, R. R., Ahrens, L. H., Spectrochim. Acta 16, 783 (1960). (5D) Carpenter, J. H., Limnol. Oceanog. 2, 271 (1957). (6D) Danielsson, L., Talanta 3, 203 (1959).
(7D) Duval, G. R., Ironside, R., Russell, D. S., Anal. Chim. Acta 25, 51 (1961). (8D) Edge, R. A.,Ibid., 24,143(1961). (9D) Forberg, S., Lundgren, S., ANAL. CHEM.32,1202 (1960). (10D) Foss, 0. P., Scand. J . Clin. & Lab. Invest. 11. 211 11959’1. --, (11D) Fresen, J: A., ‘vanvan Gogh, H., van Pinxteren, J. A. C., Pharm. Weekblad os. 22 (1960). iinfini 95,33 (12D)-: (12D) Hall, G. M., Bryson, A,, Anal. Chim. Acta Acia 24, 138 (1961). . (13D) Hensley, A. L., Barney, J. E., AKAL.CHEM.32,828 (1960). Imoto, H.. (14D) Imoto. H., JJapan m a n Analyst 10, 124 (1961). ( 1 5 ~ ) nmaire, L., Michon, G., Lait 39,369 (:1959). (16D) Kn.apstein, H., 2. anal. Chem. 175, 255 (1960). ( l i D ) KOI zheva. L. L.. Fiz.-iMat. Fak 52,’97 (1959).’ (18D) Kolonina, X. P., Zhur. Priklad. Khim. 33,2475 (1960). (19Dj Lagerstrom, O., Samuelson, O., Svensk Pappers, tidn. 62,679 (1959). (20D) Moore, F. L., ANAL.CHEM.33, 748 (1961). (21D) Parker, C. A., Barnes, W. J., Analyst 85,828 (1960). (22D) Petit, J., Lumbroso, R.. Compt. rend 250, 2568 (1960). (23D) Petrow, H. G., iillen, R. J., Lindstrom, R., Sohn, B., U S. Atomic Energ Comni. Rept. TID-6870 (Part 111),I pn l 1961. (24D) Porter, c., ~ A L CHEV. . 33, 1306 (1961). (25D) Rynbchikov, D. I., Terent’eva, E. A., Cspelzhi Khim. 29,1285 (1960). (26D) Schrenk, W. G., Graber, K., Johnson, R., ANAL. CHw. 33, 106 (1961). (27D) Schroder, E., Raurick, U.,Plaste u. Kautschuk 7, 9 (1960). (28D) Shapiro, L., -&SAL. CHEM. 32, 569 11960). (29D) ‘Smythe, L. E., Whittem, R. K., Analyst 86,83 (1961). (30D) Sporek, K. F., Chem. in Can. 11, 66 (1909). (31D) Strelow. F. K.E.. AXAL.CHEY. 33, 1648 (1961). (32Dj Stronski, I., Rybakow, W. K., Chem. Anal. (Warsaw)4 , 8 i i (1959). (33D) Takagi, T., Imoto, H., Japan Analyst 8,782 (1959). (34D) Talvitie, N. A., Brewer, L. W., Am. Ind. Hyg. $ssoc. 21, 287 (1960). \
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(35D) Turse, R., Rieman, W., 111, Anal. Chim. Acta 24,202 (1961). (36D) Vetejska, K., Mazacek, J., Collection Czechoslov. Chem. Communs. 25, 2245 (1960). (37D) Wade, M. A., Seim, H. J., ASAL. CHEM.33,793 (1961). (38D) Warren, R. J., Hazel, J. F., McNabb, W. M., Anal. Chim. Acta 21, 224 (1959). (39D) Weiss, H. W., Lai, M. G., ANAL. CHEM.33,39 (1961).
Organic Analysis (1E) Bose, S., Gupta, K. C., Proc. Ann. Conv. Sugar Technologists Assoc. 88th Ann. Conv., India 88,1960. (2E) Carruthers, A., Oldfield, J. F. T., Teague, H. J., Analyst 85, 272 (1960). (3E) Hrdy, O., Lochmanova, S., Ceskoslov. Farm. 9, 335 (1960). (4E) Lewandowski, A., Jarczewski, A., Talanta 4,174 (1960). (5E) Murata, S., Suzuki, Y., J . Chem. SOC.Japan, Ind. Chem. Sect. 64, 174 (1961). (6E) Phifer, L. H., Bell, J. L., Tappi 43, 622 (1960). (7E) Prill, E. A., Porter, C. A., Staples, R. C., Burchfield, H. P., J . Assoc. Ofic. Agr. Chemists43,96 (1960). (8Ej Smille, R. M., J . Chromatog. 4, 494 (1960). (9E) Sterling, K., Tabachnik, N., J . Clin. Endocrinol. and Metabolism 21, 456 (1961). (10E’i Storherr. R. W.. Burke. J.. J . Assoc. O$c.Agr. Chemists 44, 19611961). (11E) Sullivan, J. H., Voelker, W. A., Stahl, W. H., Ibid., 43, 601 (1960). (12E) Takimoto. M.. Yatsuo. T.. J . Chem. . Soc. Japan, Ind. Chem. Sect.’63, 1938 (1960). (13E) Tompsett, S. L., Anal. Chim. Acta 24,438 (1961). (14E) Wiseman, H. G., Mallack, J. C.. Jacobson, W. C., J . Agr. Food Chem. 8 , 78 (1960). > -
Microanalysis (1F) Mimarin, I. P., Petrikova, h1. S., Talanta 8,333 (1961). (2F) Boase, D. G., Foreman, J. K., Ibid., 187 (1961). (3F) Eastoe, J. E., Biochem. J . 79, 652 (1961). (4F) Fujimoto, M., Bull. Chem. SOC. Japan 33,864 (1960).
(5F) Fujimoto, M., Chemist Analyst 49 4 (1960). (6F)‘ Fujimoto, M. Naturwissenschaften 47,252 (1960). (7F) Kakihana, H., Mori, Y., Watanabe, Y., Nivpon Kaaaku Zasshi 82. 594
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127 (1960). (12F) West, T. S., Chem. Age, p. 107 (July 16, 1960). Miscellaneous Procedures and Techniques (1G) Cabbell, T. R., Orr, A. A., Hayes, J . R., AXAL.CHEM.32,1602 (1960). (2Gj Ceausescu, D., 2. anal. Chem. 176, 1 (1960). ( 3 G ) Collin, R. L., ANAL. CHEM. 33, 605 (1961). (4G) Galakhovskaya, T. V., Trudy ~
Vsesoyuz. Nauch.-Issledovatel. Inst. Galuryii, Ministerstvo Khim. Prom. S.S.S.R.
36,404 (1959). (5G) Kemula, W.,Brajter, K., Cieslik, S., Lipinska-Kostrowicka, H., Chem. Anal. (Warsaw)5 , 229 (1960). (6G) Kniestedt, H., Wahle, J., Chem. Tech. (Berlin) 13, 110 (1961). ( i G j Kwata, M., Inone, S., J . Japan Oil Cheniists’ Soc. 6, 92 (1957). (8G) Mosen, A. W., Schmitt, R. A., T‘asilevskis. J.. Anal. Chim. Acta 25. 10 (1961). (9Gj Rirhardson, M. L., Ibid., 24, 46 (1961). (10G) Rosen, M. J., J . Ana. Oil Chemists’ SOC.38,218 (1961). (11G) van Niekerk. J. N.. de Wet. J. F.. Nuture 186, 380 (1960). (12G) Wynne, E. A., Burdick, R. D., Fine, L. €I., ANAL.CHEM. 33, 807 (1961). (13Gi Ziegler, RI., Z. anal. Chem. 180, l(1961). Preparation of Reagents (1H) Blaedel, R. J., Olsen, E. D., . ~ N A L . CHEM.33,531 (1961). (2H) Hanselman, R. B., Rogers, L. B., Ibid., 32, 1240 (1960). (3H) Serjeant, E. P., Suture 186, 963 (1960). ,
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