ION EXCHANGE


past year, U. S. millers of domestically produced cane and beet sugar have been looking favorably toward ion exchange technology. The growth of superc...
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ROBERT K U N l N

FRANCIS X.

ANNUAL REVIEW

MCGARVEY

ION EXCHANGE The Cuban sugar situation, the use of supercritical steam boilers, and interest in water desalination have all contributed to accelerated growth

change technology. He has also described the significance of ion exchange processes in biological systems. Dorfner (7A) has written, in German, a book on the properties and applications of ion exchangers. I n view of the recent interest in macroreticular ion exchange resins, the book of Satterfield and Sherwood ( 3 A ) on the role of diffusion in catalysis is most timely.

o f ion exchange applications Theory

t is of interest to note that, as in the field of other unit operations, certain ion exchange developments do not proceed in an orderly manner. Various nontechnical situations may have either adverse or favorable influences on the growth of ion exchange as a processing technique. The use of ion exchange resins in the United States for treating various sugar sirups and juices has been stimulated by the Cuban situation. During the past year, U. S. millers of domestically produced cane and beet sugar have been looking favorably toward ion exchange technology. The growth of supercritical boilers in the electrical power field has placed increasing demands on the performance of ion exchange resins in view of the ultrapure water quality demanded in the operation of the boilers and turbines. Experience has shown that some ion exchange resins can be used effectively and economically under conditions that were formerly considered as being deleterious to the ion exchange materials. The macroreticular ion exchange resins have been found quite useful in many areas of water treatment where aggressive conditions prevail and where water of extremely high purity is demanded. New ion exchange resins and techniques have been developed which extend the economic range of ion exchange into the brackish water field. Pertinent literature published during the period February 1,1963, to May 1, 1964, has been reviewed and included here.

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Reviews

Reichenberg (24) has written a review of the prevailing theories pertaining to ion exchange selectivity and some of the more recent developments in ion ex-

Effort continues on the development of a suitable theory to account for the selectivity of various ion exchange materials for exchanging ions of varying size, charge, and structure. Bonner and Overton (3B) have continued +heir studies on ion exchange selectivity using soluble polymeric sulfonic acids as models for sulfonic acid cation exchange resins. Diamond (9B) has proposed a new type of ion-pairing to explain the behavior of large univalent ions. Boyd, Vaslow, and Lindenbaum (4B) and Gaertner (75B)have measured some thermodynamic values for several ion exchange systems, the former for cation exchangers and the latter for anion exchangers. Athavale (7B) has studied the selectivities of a sulfonic acid cation exchange resin for several monovalent cations in the presence of watermiscible alcohols and has explained the results on the basis of increased ion association in the resin phase. Elovich and Sharapova (74B) have compared the Cs-H and Cs-Na exchange systems for phosphonous acid, phenolic, and sulfonic acid cation exchange resins and have applied Harried's rule for electrolytes as a means of explaining the behavior of the different ion exchangers. Nikol’skii, Vysokoostrovskaya, and Trofimov (30B) have completed a similar study on carboxylic, phosphoric, phosphonous, and sulfonic acid cation exchange resins for several divalent ion exchange systems. The selectivity and Donnan effect for carboxylic cation exchange resins were studied by Mikhanosha, Yudin, and Barboi (28B),Kunin and Fisher (25B), Chatterjee and Marinsky (6B),and Gustafson (77B). Studies on the various factors influencing the swelling of ion exchange resins were described by Dickel and Bunzl (70B) and Starobinets and Novitskaya (33B). Dresner and Kraus (73B) have developed a theoretical VOL. 5 6

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model based upon the Poisson-Boltzmann equation for predicting the “salt-filtering” behavior of porous ion exchange materials. Various attempts have been made by Dinius and Choppin ( I I B , 72B), Devilliers and Parrish (8B), and Reichenberg and Lawrenson (32B) to interpret the water structure of hydrated ion exchange resins by means of nuclear magnetic resonance. Various diffusion-controlled kinetic models for ion exchange resins have been studied by Glaski and Dranoff (76B), Hering and Bliss (IQB),Rao and David (37B), and Helfferich (78B) in an attempt to predict the performance of ion exchange resins in packed beds. Libinson (26B) has measured the diffusion coefficients of several organic cations in a sulfonic acid cation exchange resin. Millar et al. (29B) have examined the kinetics of exchange for several inorganic and organic cations in a series of solvent modified sulfonated styrene-divinylbenzene copolymers. Kressman et al. (27B-24B) have summarized in four papers their studies on the transference numbers of counter-ions and water through a cation-selective ion exchange membrane. Block and Spiegler (ZB), DeKorosy and Szekely (7B), and Caramazza (5B) have described similar studies on anion-selective ion exchange membranes. Matsuda and Ishino (27B) have measured the electrical conductivity in air at various relative humidities of a series of cation exchange membranes previously equilibrated in various electrolyte solutions. Of particular interest to those engaged in the hydraulics of ion exchange beds are the studies of Hershey and Peebles (2OB) on the kinetic friction data of an ion exchange resin in compacted and noncompacted beds.

described by Araten and Schachter (ID)and Kunin ( 7 0 ) . Procedures for separating rare earths, thorium, and trans-uranic elements were detailed by Mottel and Proctor (72D), Bhatki, Gopinathan, and Rane (30), Asher et al. (ZO), and Marchello and Davis (IOD). A method for purifying zinc as zinc sulfate was developed by Leclercq and Duyckaerts (9D) and a method for recovering gold from waste solutions was presented by Kutil and Stamberg ( 8 0 ) . A countercurrent procedure for recovering bromine from industrial brines by an anion exchange technique has been proposed by Schoenbeck ( 1 3 0 ) . Meeker, Dunlop, and Luten ( I 7 D ) have removed organic acid impurities present in hydrogen peroxide with an anion exchange resin in the salt form. A method for separating mixtures of strong acids and their salts by means of an anion exchange resin in the common ion form has been demonstrated by Hatch and Dillon ( 4 0 ) . Kenworthy (6D)has purified impure TiOz suspensions using both anion and cation exchange resins. Organic Chemistry

Data for the exchange of several organic and inorganic cations in dioxane and alcohol solutions have been described by Gordon (3E) and Fessler and Strobe1 (ZE). Skoroknod and Tavulo (5E) have studied the sorption of phenol and organic acids from aqueous solutions, organic solvents, and from the gas phase on the hydrogen form of sulfonic acid cation exchange resins. A strong base anion exchange resin has been used for removing acids from styrene monomer ( I E ) . Ring (4E) has described a petroleum sweetening treatment which utilizes the hydroxide form of a strong base anion exchange resin. Food Technology

Water Conditioning

Duff and Levendusky ( I C ) and Grant et al. (2C) have described the use of finely divided ion exchange resins as a filter pre-coat for the polishing of condensate in a power plant. The technique combines ion exchange with filtration and results in water of high purity. Holt, Lux, and Valberg (3C) have combined distillation and ion exchange to produce water for trace metal analysis. Kunin (4C, 5C) has described two new deionization techniques employing weak electrolyte ion exchange resins. An ion exchange method for removing NaCl from sea water employing lime as a regenerant has been described by Popper, Bouthilet, and Slamecka (6C). Design data for removing boric acid from water by means of a strong base anion exchange resin have been reported by Szentgyorgyi (8C). Several designs for the continuous operation of ion exchange systems have been described by Turner and Church (9C), Zsigmond and Gryllus (IOC), and Rudelick (7C). Inorganic Chemistry and Hydrometallurgy

The conversion of salt to dilute NaOH by cation exchange using lime as a source of alkalinity was demonstrated by Herwig, Swinton, and Weiss (5D). Ion exchange processes for converting NaCl into NaHC03 were 54

INDUSTRIAL A N D ENGINEERING CHEMISTRY

Continued experience with ion exchange and the expansion of domestic sugar production in the U. S.have stimulated further interest on the part of the sugar refiner in ion exchange techniques. Furukawa and Iizuka (527) have made an economic analysis of the cost of decolorizing sugar sirups with anion exchange resins. Other sugar decolorization studies using anion exchange resins have been summarized by Lespagnol ( 8 F ) , Moebes (IOF), and Plato and Schopf (72F). The nature of the color bodies present in sugar juices and sirups was studied by Prey, Hammer, and Braunsteiner (73F) and Carruthers, Dutton, and Oldfield ( 2 F ) by means of ion exchange techniques. Extensive field data have been presented by Paparelle ( 7 IF) on the use of sulfonic acid cation exchange resins for softening sugar juices. Data for deionizing various sugar juices and sirups have been reviewed by Dickinson ( 4 F ) , Iwashina and Asami (6F), and Smith et al. (7527). Since glutamic acid recovery is practiced by various beet sugar producers, the ion exAUTHOR Robert Kunin is Research Associate, Research Laboratories, Rohm @ Haas Co. Francis X . McGarvey is a specialist in the development of ion exchange processes for the same company. The authors grateful& acknowledge the assistance of Dr. Erich Meitzner and the library staff of the Rohm €8 Haas Co.

change procedure described by Magyar, Hersiczky, and Simonyi (9F) for recovering this amino acid will be of interest to the sugar chemist. Miscellaneous ion exchange techniques for separating sugars were developed by Dahlberg and Samuelson (3F),Adachi and Sugawara ( I F ) ,and Kunugi (7F). An ion exchange procedure useful for clarifying wines has been studied by Rankine and Emerson (74F). Biochemistry

Although much of the ion exchange work in the field of biochemistry is of analytical interest, there has been a steady growth in the use of ion exchange technology in the industrial production of biochemicals. I n this connection, the studies of Feitelson (2G) on amino acids, Schroeder, Jones, Cormick, and McCalla (3G) on proteins and peptides, Weil, Hebding, and Ebel (6G) on ribonucleic acids, and Vancraenenbroeck (5G) on flavonoids are of interest. The problem of growing food under unusual conditions in connection with the various space programs lends practical importance to the work of Skogley and Dawson (4G) on the use of ion exchange resin salts as substrates for plant nutrition. Zvyaginstev (7G) has studied the sorption of microorganisms on ion exchange resins by microscopic techniques. The use of mixtures of anion and cation exchange resins to assist in pharmaceutical tablet disintegration has been proposed by Coletta and Warfield (7G). Catalysis

Kunin, Meitzner, and Bortnick (4H) have described the catalytic properties of a macroreticular cation exchange resin. The catalytic activity of this same cation exchange resin for the direct hydration of propylene was studied by Kaiser (3H). Fulmer ( 2 H ) has compared the catalytic activities of sulfonic, phosphonic, and carboxylic cation exchange resins for the cyanoethylation of fatty amines. The alkylation of isoparaffins with olefins using a sulfonic acid cation exchange resin as the catalyst was reported by Van Dyke (8H).Strong base anion exchange resins have been used by Shimo and Wakamatsu ( 6 H ) as catalysts for the synthesis of malonic esters and related compounds. Conte and Ape1 ( I H ) have converted phenol esters to ketones using a sulfonic acid cation exchange resin. The chromic salts of cation exchange resins have been employed by Sirota and Paramonkov ( 7 H )as catalysts for the preparation of low molecular weight polyethylene. Leum et d.(5H) have used anion and cation exchange resins for purifying slurries of inorganic catalysts. Membranes

To a considerable degree, the development of the electrodialysis technique for the treatment of brackish waters has been seriously retarded because of the difficulties experienced as a result of the irreversible fouling of the anion exchange membrane. Efforts to overcome this difficulty are now in progress in several research labhave reoratories. Solt, Wegelin, and Chapman (4.J) viewed both the theoretical and practical aspects of

electrodialysis as a unit operation. Improvements in the design of electrodialysis units have been described by Jasionowski and Gaysowski (2J) and Roberts and Rogers ( 3 . 4 . Chrysikopoulos ( 7 4 has evaluated several cation exchange membranes for use in chlor-alkali cells. New Ion Exchange Materials

Much of the effort in the development of new ion exchange materials is being devoted to the synthesis of exchangers that are capable of reversibly sorbing organic matter present in surface waters, sugar juices, and sirups. Bachmann (3K), Hisayama and Utsunomiya ( 7 K ) , Millar ( I I K ) , and Seifert, Corte, and Netz (13K) have described new techniques for preparing sulfonic acid cation exchange resins. Bachmann ( I K , 2K) has synthesized new anion exchange resins of reported improved mechanical stability. Detailed procedures for producing anion and cation exchange resins based upon styrenedivinylbenzene copolymers have been outlined by Guccione (SK). Amphoteric ion exchange resins supposedly selective for copper have been prepared by Manecke and Heller (IOK). A chelating ion exchange resin based upon hydrazide has been described by Blasius and Laser (4K) and a germanium selective resin based upon a fluorone derivative has been synthesized by Seidl (12K) Hopkins and Scudder (8K)disclose procedures for preparing open-cell ion exchange foams. Kamogawa and Cassidy ( 9 K ) have described the copolymerization behavior of vinylhydroquinone dibenzoate monomer with styrene to form redox polymers. Cerrai and Testa ( 5 K ) have prepared a redox column by impregnating Kel-F powder with tetrachloro-hydroquinone.

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Analytical Methods

Since many anion exchange resins are of mixed functionality initially or degrade to such a state, Polyanskii and Shaburov (3L) have developed a method for distinguishing between strongly and weakly basic groups present in anion exchange resins. Pollio (2L) has adapted the Karl Fischer method to the determination of moisture in hydrated and partially hydrated ion exchange resins. Saxby (4L) has demonstrated the presence of several fluorescent compounds in several commercial ion exchange resins by means of a n alcohol extraction followed by chromatography in acetic acid. DeKorosy (7L) has applied electronmicroscopy to the study of ion exchange membranes. Vassiliou and Kunin (5L) have developed a continuous procedure for the fractionation of fine particle-sized ion exchange resins. Stability of Ion Exchange Materials

The thermal stability of a cation exchange resin was investigated by Evlanov and Saf'yanova ( 7 M ) at temperatures to 500' C. The radiation stability of anion exchange resins was investigated by Hall and Streat ( 2 M ) and Kiseleva, Chmutov, and Krupnova ( 3 M ) . liquid Ion Exchangers

A spectrophotometric study of the extraction of the transition metal halo-complexes by amine extractants was described by Lindenbaum and Boyd ( 3 N ) . Liquid anion exchangers have been employed by Bennett and VOL. 5 6

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Marshall ( I N ) to extract dichromate from sulfuric acid solutions. Orme- Johnson and Skinner (4N) have separated amino acids by means of a liquid anion exchanger. Clingman and Parrish (Zit’) have studied the liquid anion exchange properties of water-insoluble derivatives of complexing agents dissolved in organic solvents. REFERENCES Reviews (1A) Dorfner, K., “Ionen Austauscher,” Walter Der Gruyter 8z Co., Berlin, 1963. 12A) Reichenbere. D.. Endeavour 22. 123 (1963). , , (3A) Satterfield, C. N., Sherwood, T. K., “The Role of Diffusion in Catalysis,” Addison-Wesley Publ. Co., Reading, Mass., 1963. “l

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Theory (1B) Athavaie, V. T., Krishnan, C. V., Venkateswarlu, Ch., Inorg. Chem. 3, 533 (1964). (2B) Block, M., Spiegler, K., J . Electrockem. Soc. 110, 577 (1963). (3B) Bonner, 0. D., Overton, J. R., J . Phys. Chem. 67, 1035 (1963). (4B) Boyd, G. E., Vaslow, F., Lindenbaum, S., Ibid., 68, 590 (1964). (5B) Caramazza, R., Dorst, W., Hoeve, A . J. C., Staverman, J. A,, Trans. Faraday Soc. 59, 2415 (1963). (6B) Chatterjee, A,, Marinsky, J. A,, J . Phys. Chem. 67, 41 (1963). (7B) DeKorosy, F., Szekely, E., Israel J . Chem. 1, 272 (1963). (8B) Devillien, J. P., Parrish, J. R., J . Polymer Sci. AZ, 1331 (1964). (9B) Diamond, R . M., J . Phys. Ckem. 67, 2513 (1963). (10B) Dickel, G., Bund, K., Z . Pkys. Ckem. 39, 198 (1963). (11B) Dinius, R. H., Choppin, G. R., J . Phys. Chem. 68, 425 (1964). (12B) Dinius, R. H., Emerson, M . T., Choppin, G. R., Ibid., 67, 1178 (1963). (13B) Dresner, L., Kraus, K . A,, Ibid., p. 990. (14B) Elovich, S. Yu., Sharapova, 5 . P., Russ. J . Pkys. Chem., p. 409 (1962). (15B) Gaertner, K., Z. Phjrik. Chem. 223, 132 (1963). (16B) Glaski, F. A,, Dranoff, I. S., A.1.Ch.E. J . 9, 426 (1963). (17B) Gustafson, R . L., J . Phys. Chem. 6 7 , 2549 (1963). (18B) Helfferich, F., J . Chem. Phys. 38, 1688 (1963). (19B) Hering, B., Bliss, H., A.1.Ch.E. J . 9, 495 (1963). (20B) Henhey, D , Peebles, F. N., 2nd. Eng. Chem. Process Dpsign Deuelop. 3, l(1964). (21B) Kressman, T. R. E., Stanbridge, P. A , , Tye, F. L., Trans. Farudoy Soc. 59, 2129 (1963). (22B) Ibid,, p. 2139. (23B) Ibid., p. 2146. (24B) Kressman, T. R. E., Stanbridge, P. A,, Tye, F. L., Wilson, A . G., Ibid., p. 2133. (25B) Kunin, R., Fisher, S., J . Pkys. Ckem. 66, 2275 (1962). (26B) Libinson, G. S., Dokl. Akad. .&’auk SSSR 151, 127 (1963). (27B) Matsuda, Y., Ishino, T., Technol. Repi. Osuka Uniu. 13, 207 (1963). (28B) Mikhanosha, E , S . , Yudin, A. V.,Barboi, V. M., Izv. Vysshikh L‘chebn. Zauedenii, Tekhnol. Legkoi Prom., p. 34 (1963). (29B) .MilIar, J. R., Smith, D. G., hfarr, W.E., Kressman, T. R. E,, J . Chem. Sac. 1963, p. 2779. (30B) Nikoi’skii, B. P., Vysokoostrovskaya, A-. B., Trofimov, A. M., Radiokhimiya 4, 512 (1962). (31B) Rao, M. G., David, M. M., A.1.Ck.E. J . 10, 213 (1964). (32B) Reichenberg, D., Lawrenson, I. J., T r a m . Faraday Soc. 59, 141-(1963) (33B) Starobinets, G. L., Novitskaya, L. V., Kolloidn. Zh. 25, 689 (1963). Water Conditioning Duff, J. H., Levendusky, J. A , , Proc. Amer. Power Cotif. 24, 739 (1962). Grant, J. S., Novak, E. C., Levendusky, J. A,, Spillane, D. M., Ibid., 661 (1963). Holt, J. LM.,Lux, W-., Valberg, L. S . , Can. J . Biochem. Pkysiol.-41,’2029 (1963). (4C) Kunio, R., Belg. Parent 620,638 (January 1963). (5C) Kunin, R., U. S. Patent 3,111,485 (Nov. 19, 1963). (6C) Popper, K., Boutbilet, R., Slamecka, V., Science 141, 1038 (1963). (7C) Rudelick, J., U. S. Patent 3,073,674 (Jan. 15, 1963). (8C) Szentgyorgyi, P., Acad. Rep. Populare Romine, Studii Cercetari Fiz. 13, 965 (1962). (9C) Turner, J. C. R., Church, M. R., Trans. Inst. Chem. Enzr. 41, 283 (1963). (1OC) Zsigmond, A,, Gryllus, V., Elelm. Ipar 17, 169 (1963). (1C) (2C) 25, (3C)

Inorganic Chemistry & Hydrometallurgy (1D) Araten, I . D., SchaEhter, O., Ind. Ckemirt 39,246 (1963). (2D) Asher, D. R., Hansen, R. D., Seamster, A. H., Small, H . , Wheaton, R. M., Ind. Eng.Chem. Process Des& Develop. 1, 52 (1963). (3D) Bhatki, K . , Gopinarhan, K., Rane, A , , J . Inorg. Nucl. Chem. 24, 215 (1962). (4D) Hatch, M. J., Diilon, J. A,, 2nd. Eng. Chem. Process Design Decelop. 2 , 253 (1963). (5D) Herwig, G. L., Swinton, E. A , , Weiss, D. E., Aust. J . App/. Sci. 14, 1 (1963). (6D) Kenworthy, L. A,, U. S. Patent 3,063,807 (Nov. 13, 1963) ENG.CHEW56, 35 (1964). (7D) Kunin, R., IND. (ED) Kutil, J., Stamberg, J., Ionenaustouscker Einreldarstell 1, 365 (1963). (9D) Leclercq, M., Duyckaerts, G., Anal. Chim. Acta 29, 139 (1963). ENG.CHEM.2, 27 (1963). (lOD) Marchello, J. M., Davis, M. W-., IND. (11D) Meeker, R. E., Dunlop, A. K., Luten, D . B., Jr., U.S. Patent 3,074,782 (Jan. 22, 1963). (12D) Mottel, W. J., Proctor, J. F., IKD.ENG.CHEM.55, 27 (1963). (13D) Schoenbeck, L. C., U. S. Patent 3,075,830 (Jan. 29, 1963).

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Organic Chemistry (1E) (2E) (3E) (4E) (5E)

Dow Chemical Co., Belg. Patent 626,438 (June 1963). Fessler, R. G., Strobe], H. A,, J. Pkys. Chem. 67, 2562 (1963). Gordon, J. E., J . Phys. Chem. 67, 16 (1963). Ring, S. B., U. S. Patent 3,108,948 (Oct. 29, 1963). Skoroknod, 0. P., Tavulo, M . L., Kolloidn. Zh. 25, 674 (1963).

Food Technology (1F) Adachi, S., Sugawara, H., Arch. Biochem. Biophys. 100, 468 (1963). (2F) Carruthers, A., Dutton, J. V., Oldfield, J. T. F., Intern. Sugar J . 65, 297 (1963). (3F) Dahlberg, J., Samuelson, O., Suensk. Kem. Tidskr. 75, 178 (1963). (4F) Dickinson, B. N., S q a r y Azucor 59, 61 (1964). T,Iizuka, T., Proc. Res. Soc. Japan Sugar Rejneries Technol. 11, (5F) Furukawa, i 63 (1962). (6F) Iwashina, S., Asami, T., Ibid., 12, 73 (1963). (7F) Kunugi, K., Chem. Pharm. Bull. 11, 922 (1963). (8F) Lespagnol, J., Sucr. Frunc. 104, 62 (1963). (9F) Magyar, E., Hersiczky, A,, Simonyi, J. M., Stnerke 15, 12 (1963). (10F) Moebes, E., U. S. Patent 3,090,707 (May 21, 1963). (11F) Paparelie, G. A., Muterie Plustiche 28, 923 (1962). (12F) Plato, W., Schopf, M., Zuckererzeugung 7, 36 (1963). (13F) Prey, V., Hammer, E., Braunsteiner, W., Z. Zuckerind. 13, 371 (1963). (14F) Rankine, B. C., Emerson, M‘. W., J . Sci. Food Agr. 14, 685 (1963). (15F) Smith, B. A,, Sugar Azucnr 58, 33 (1963). Biochemistry (1G) Coletta, V., Warfield, R. B., U. S. Patent 3,091,574 (hlay 28, 1963). (2G) Feitelson, J., J . Pkys. Chem. 67, 2544 (1963). (3G) Schroeder, W.A,, Jones, R. T., Cormick, J., McCalla, K., Anal. Chem. 34, 1570 (1962). (4G) Skoglev. - . . E. 0..Dawson., J. E... Nature 198. 1328 (1963). , , (5G) Vancraenenbroeck, R . , Robirst, A,, Lemaitre, H., Lontie, R., Bull. Soc. Ckim. Belg. 72, 619 (1963). (6G) Weil, J. H., Hebding, N., Ebel, J. P., Bull. Soc. Chhim. Bid. 45, 595 (1963). (7G) Zvyaginstev, D. G., Microbiology 31, 275 (1962) Catalysis (1H) Conte, L. B., Apel, F. N., Can. Patent 669,902 (Sept. 3, 1963). (2H) Fulmer, R . W., J . Org. Chem. 27, 4115 (1962). (3H) Kaiser, J. R., Beuther, H., Moore, L. D., Odioso, R . C., 2nd. Eng. Chem. Prod. Res. Deuelop. 1, 296 (1962). (4H) Kunin, R., Meitzner, E., Bortnick, A’., J. Am. Chem. Soc. 84, 305 (1962). (5H) Leum, L. h-.,Connor, J. E., Jr., Rothrock, J. J., Shipley, C. S . , U. S. Patent 3,073,675 (Jan. 15, 1963). (6H) Shimo, K., IVakamatsu, S., J . Org. Ckdm. 28, 504 (1963). (7H) Sirota, A. G.: Paramonkov, E. Y., U.S.S.R. Patent 154,403 (July 24, 1963). (8H) Van Dyke, R . E., U. S. Patent 3,116,346 (Dec. 31, 1963). Membranes (1J)

Chrysikopoulos, S., Tombalakina, A. S., Graydan, W. F., Can. J . Chem. En,?.

41, 91 (1963).

(25) Jasionowski, W. J., Gaysowski, J. J., U. S. Patent 3,074,863-5 (Jan. 22, 1963). (35) Roberts, W. J., Rogers, A. M’. F., U. S. Parent 3,073,774 (Jan. 15, 1963). (45) Solt, G. S., Wegelin, E., Chapman, C. V. G., Brit. Chem. Eng. 8, 485 (1963). New Ion Exchange Materials (1K) Bachmann, R., Krauss, U., Reuter, H . , Schwachula, G., Warnecke, D., Wolf, F., German Patent 1,153,906 (Sept. 5, 1963). (2K) Bachmann, R., Krauss, U., Schwachula, G., Warnecke, D., Wehlend, W . Wolf, F., German Patent 1,151,124 (July 4, 1963). (3K) Ibid., 1,155,603 (Oct. 10, 1963). (4K) Blasius, E., Laser, M., J . Chromatog. 11, 84 (1963). (5K) Cerrai, E., Testa, C., Anal. Chim.Acta 28, 205 (1963). (GK) Guccione, E., Ckem. Eng. 70, 138 (1963). (7K) Hisayama, H., Utsunomiya, Y.,Japan. Patent 10,343 (1963). (8K) Hopkins, R. P., Scudder, W. C., U. S. Patent 3,094,494 (June 18, 1963). (9K) Kamogawa, H., Cassidy, H . G , J . Poly. Sci. 1, 1971 (1963). (10K) Manecke, G., Heller, H., Mukromol. Chem. 59, 106 (1963). (11K) Millar, J. R., Smith, D. G., Marr, W. E., Kressman, T. R. E., J . Ciiem. SGC.1963, I). 218. (12K) Seidi, J., Stamberg, J., Hrbkova, E., J . Appl. Ckem. 12, 500 (1962). (13K) Seifert, H., Corte, H . , Netz, O., German Patent 1,151,120 (July 4, 1963). Methods (1L) DeKorosy, F., Israel J . Chem. 1, 269 (1963). (2L) Pollio, F. X., Anal. Ckem. 35, 2164 (1963). (3L) Polyanskii, S . G., Shaburov, 51.A,, J . Anal. Chem. USSR 18, 269 (1963) (4L) Saxby, M. J., Chem. Ind. No. 43, 1725 (1963). (5L) Vassiliou, B., Kunin, R., Anal. Chem. 35, 1328 (1963). Stability of Ion Exchange iMaterials (IM), Evlanov, G. A,, Saf’yanova, N. E., Izu. Vysshikh Uchibn. Zavedenii, Khim. Khrm. Tekhnol. 6 , 341 (1963). (2M) Hall, G. R., Streat, M., J . Chem. Sot. 1963, p. 5205. (3M) Kiseleva, E. D., Chmurov, K. V., Krupnova, V. N., Zh. Fiz. Khim. 37, 1626 (1963). Liquid Exchangers

(1s)Bennett, H., Marshall, K., Anaijst (2K) (3s) (4N)

88, 877 (1963). Clingman, A. L., Parrish, J. R., J . AppC. Chem. 13, 193 (1963). Lindenbaum, S., Boyd, G. E., J . Pkys. Ciiem. 67, 1238 (1963). Orme-Johnson, L\’, H., Skinner, C. G., J . Chromatog. 11, 549 (1963).