Ion Exchange

Rohm & Haas Co., Philadelphia, Pa. ALTHOUGH the application of ion exchange to analytical chemistry has received considerable attention during the pas...
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ION EXCHANGE ROBEKT KUNLN Rohrn &: Huas Co., Philudelphiu, P a ,


LTHOUGH the application of‘ ion exchange t o :~nalytical

and rarer c~lcint~iit,*.de:tiiorg and his co-worker.; ;X, i3) have separated rind iso1:it rcl hrrkelium, americium, and rurium using ion exchangc resin.:. I’roinethium has been separated from europium t>y Huffman and Oswalt ( 4 0 ) with t h e aid of a strong h:isr anion esr1i:tnge rcsin. T h e separation of hafnium and zirronium hy ion esr1i:ingr resins and silica gel has receivcd ronsitlerable attention. Hiiffman and Lilly (39) and Kraus antl Jloorc have Found so paration of the hafnium and zirconium using t he :inionic coi es of these elements on a strong hiisr :inion rsrhitngrr. Hon.cver, N a n w n and Gunnar (56)h a w had coniiider:il)le siicress in ;sr1):ir:itirig these elements on silica gel. T h e raw earth separ;itions on cation exchange resins h:~vercreivrd further attention from Spedding and his co-workers (75-77) and Jcng-Tsong ( $ 2 ) . At lel)erry, Larson, and 13oyd (sj hnvr studied t h c fission product Reparations on a precision-type ion exchange rxolunin :in(l h : i w reported particularly sue sults for the srparation 3f tlir halogens., Cobble and Adammi ( 8 )havr reported thcx ~epar:itionof the Ferrocyanide a n d frrrii,y:inidc complcs iotis on :in anion cschange resin. iiew

chemistry has rereived considerable attention during the past few years, much of‘ the effort has been directed torvard t,he establishment, of principles and techniques and not towird the drvelopnient of analytical procedures useful for the routine analyst. M a n y of the techniques t h a t have been developed reed analyst and e1abor:rte equipment. However, rements indicate a trend tov-ard the establishmr~ntof ion rschtinge proecdwrs t h ~ will t he generally useful t o tlir ivutine analyst. REVIEWS

Althougli not specificnlly written for the analytical chemist, the recent reviews of Xachod (65),Lundberg (50),and Rahck (63)on t h e general nature of ion exchange are of considera1)le interest. T h e w reviews and those described previously (47, $3) contain useful genei,nl information for those interested in t h r :tpplir:tt,ion of ion cxc*h:itiget o :in:ilytical chemistry. THEORY

Of interest to those analytical chemists studying tlie throry ( I ( ion eschtingc are the contributions on t h e equilibria of ion eschange processes. Elirdahl, Hogfeldt, and Sillen (21, 37. 38) have applied the Gil)l) ion t o several equilibria for a sulfonic w i d cation r assuming thc cxchanger behaves as a solid solut s approach, these investigaactivities of the components tors have attempted t of the rwin ph:isc~. Other interesting theoretiral contributions have been in:itic. 1)y Dunrun and Lister ( 1 9 ) , Gregor (90, ,3f ), .\layer (5J), and T o p p and Pepper (8f), T h c considcr:rtions of Glueckauf (2.9), hniuntl~en( f ), and Gapon (27, 28) on thc tliror). ePt to those rniploying of chrotii:itogr:rphy arc of con ion eschange rhrorn:itograph T h e ion rxchanKc resin nic~nibranesprepared and rtutlitd 1)y J u d a and l l r l l a e (.C:7), I-llie a n d I’at,notir ( 8 6 )indicate t h a t such tncnilmnes may be of use to t h r :in:rlyticul chemist for vitrious activity measurements. b’urthrr rtutlics on the tlieorj, of ion cxrhtinge niemliranes have been r r p ~ r t e dliy Chatterjee and 3I:irshttll (6) and Eriksson ( 2 2 ) . .Jriiny! Sielsen, Coleman, :ind \J~illi:tnis($9) have studied the “suspensioii effrct” of ion eschange mntrri:ils on the glass electrode and ha\.(, attrihuted the effrct to that of n nienihrane potential. T h e contri1)utions of Grigorov and Tarshis (52) a n d \\-ikl:intler (86) on ion exchange sj-steins involving insoluble precipit:ttrs will be of intrrest. t o tlios(: studying gravimetric analysis.


.\lthough niucsh of t,hc \vorli ricscril)ed above under tlie tw:i(ling of Separations has involved chroruatographic principlea, thv nature of the stuc1ic.s n-a:: preparative and not analytical. From i i n analytical point, of v i m , ion exchange chrornatography has :tlro heroine important. (’ohn anti his ro-workers (10-12) have loutid the technique useful in nurlcic acid analyses. Consden :ind Gordon (1-7, 16), J’:irtritlgc and his co-workers ( 6 7 , 6 2 ) , and dchranim and I’riniosigh ( 6 6 )Iitive employed ion exchange chromatography in :-rinino:irid analysts. .\ most interesting ion rschange chromatographic procrdure has l m ? n proposed and invrstigatecl Iiy Beukenkamp and Rirni:in (.7) For the determination of potassium and sodium in silicatrs. T h e procedure involvw the :irlsorpt.ion of t h r cations of the tlccoinposcd silicate on a column of :I finely tlividrd or colloitl:il niirlc:ir sulfonic acid eschangrr.. T h e c A m ~ is n then tlcvelopetl n i t h dilutr hydrochloric acid. Beukenkamp and Ilicinan h : t w st:iiidardizrd the procedure so th:it t h c sodium and potassium cinrrgc from the column completrly separated and eollertcd :in(I evaporated in individual beakers. T h e rhloride residues in cnch 1)caker are then titrat,ed with silver nitrate. These invrstigators h:rw heen thorough and have shown various pitF:tlls that may 1)r encountered-in pitrticulnr, hatch vwiation in resin samples. I ) F ~ E H \ I I V 4 T I O S OF TOTAL CONCENTRATION


Although ion eyeh;lngc has l)cen useful in determination or total cleetrolytr concentration, investigations by Erler (23, 2‘4 j, Tollichy, Thonip~on,antl Foreman (2.5, SO), and Lee ( 4 9 ) h a v r shown that erroneous results may be obtained due to the adsorption of the 1iher:itr.d arid on wrtain phenol sulfonic arid exchangers. I t non- :ippc~arsth:it tho nonphenolic, sulfonated styrene-type exchangers are to \)(? prefcrred. Hilfiger ( 8 6 )has found the method satisfartory for dctermining t h e total concentration of natural waters. The saniple is p:rssed through the hydrogen form of a sulfonic a r i t l exchanger and titrated. .\lk;iIiriity is rompcii~:itcdfor 113. titi:iting :in riliqunt of the original tlirrctly.

The use 01‘ ion exchange for the separation of ionic- epr(*iwcontinues to I)e of considor:ible interest t o the analytical clieinist. hlthough much of t h e n.orlc on ion exchange separations has 1)rcn for preparative purposes, the results of these inv5stigations :ire of considera1)lc interest. Partridge arid his co-workers (57-62 I . Cleavor and Cassicly (?), and others (54, 75, 84)have invcistigatetl furthckr thc use of ion rxchangc techniques for separating variou? amino arids. Colin nnd his co-workers (10, 12-14) have rontinued their rescnrchcs on t,he use of ion eschange resins for t h r separrrtion of the ribonucleotides. T h e separation of the adenosin? polyphosphates has becn st,udied hy Cohn and Carter (;jj I.?, 1 4 ) . .Istrong base anion e-ichanger has been used by Cohen :inti .\IcKtiir-Srott ( 9 ) for separating pentose phosphate from A-phosphogluconate. Sood:ik et al. (‘74)have separated cytoxitir :inti uracil w i n g a siiiceous exchanger. In the rcalm of inorganic clieniistry, ion exchange contiiiurs to lilay a n iinportant iolc i n the purification anti scpar:ition oi tllc,


Odciicran t z ii ntl 1i irma n (.i6) have developed a qua ntititt ive analytical procedurr f o v t h r rcinoval of iron and copper in the determination of :ii~srniri n iiirrct,icides. By passing the solution through a sulronic :rcitl cxrh:ingnr, the arwnic can he dctcrminetl




iodonietrjcally without dirtillation. Other procedures for renioving interfering ions have been developed by Edelshtein and PetatrkiI ($0)for water analysis, Lure and Filippova (51) for the removal of nickel and copper in the analysis of sulfur in alloys, and Usatenko and Datsenko (86)for the determination of molybdenum in alloys. Bonner and Wasserman (4)have employed a rarboxylic exchanger for the removal of excess alkali in the deterinination of niacin. Doery, Mason, and Weiss ( 1 8 ) have employed a carboxylic eschanger for removing the streptomycin trom interfering elemcnts prior to the analysis of the antibiotic. Fujiwara and Shimizu ( 2 6 ) have employed a similar technique lor the microdetermination of riboflavin. PHYSICAL CIIWIlCAL MEASUREMENTS

Ion exchange is being investigated further for various physical chemical measurements. Samuelson (64) has used these in his htudy on t h e nature of Graham’s salt. Schubert and his coworkers (67-71) have utilized the ion exchange techuiques on the -tudy of the nature of qoine oolloid systems and for the measurement of equilibrium, activity, and diwociation conctiintq Further studies on the use of ion exchange in the study ot chionriuiii complexes have heen reported by Gugtavson (33,3 $ ) MISCELLANEOUS

Of considerable interest are the studies of’ Idler (ii),Svarritt, &nger, and Ballje ( 6 b ) , and Il‘eiss (83) on the use of indicator dyed ion exchanger resins in following the course of ion escliangc. reactions. Jindra (44)has used an anion exchanger for converting the hydrochloride of air alkaloid to its free hase prior to the ulkaloid analysis. Segul, IIilIcr, and Morton ( 7 2 ) suggest the use of an ion exchange technique for studying g:riitric acidity. Djurfeldt and Samuelson ( I 7 ) have studied several vnriat)les that, are of interest to thosc emplolkig ion exchange techniques i n nnalytical chemistry. A new met’hod for determining the ion exchange capacity of ion eschniigers has been studied I,- 1I:irtirieg (66). LITERATURE CITED

(1) Amundsen, N., J . Phys. and Colloid Chem., 54, 812 (1950). (2) htteberry, R. W., Larson, Q. V., and Boyd, G. E., Division of Colloid Chemistry, 118th Meeting, AM. CHEWSOC., Chicago, Ill., 1950. (3) Beukenkamp, J., and Rieman, W., ANAL.CHEM.,22, 582 (1950). (4) Bonner, D., and Wasserman, E., J . Biol.Chem., 185, 69 (1950). (5) Carter, C. E., and Cohn, W.E., J . Am. Chrm. Soc., 72, 2604

(1950). (G) Chatterjee, B., and IIarshall, C. E., J . Phys. and Colloid Chenl., 54, 671 (1950). (7) Cleawr, C. S.,and Cassidy, H. G., J . Am. Chem. SOC.,72, 1147 (1950). (8) Cobble, J. W., and Adarnson, A. TT’., Ibid.,72, 2276 (1950). (9) Cohen, S.J., and McNair-Scott, B. B., Science, 111, 543 (1950). (10) Cohn, W. E., Division of Colloid Chemistry, 118th Meeting, AM. CHEY.Soc., Chicago, Ill., 1950. (11) Cohn, TV. E., J . Am. Chem. Soc., 72, 1471 (1950). (12) Ibid.,p. 2811. (13) Cohn, W. E., and Carter, C. E., Ihid., 72, 2606 (1950). (14) Ibid.,p. 4273. (15) Consden, R., and Gordon, A. H., Biochem. J . , 46, 8 (1950). (16) Consden, R., Gordon, A. H., and Martin, 8.S.P., Ihid., 44, 548 (1949). (17) Djurfeldt, R., and Samuelson, A., Acta Chem. Scand., 4, 165 (1950). (18) Doery, H., Mason, E., and Weiss, D., ANAL.CHEM.,22, 1038 (1950). (19) Duncan, J. F., and Lister, B. A. S., J . Chem. SOC.,1949, 3285. (20) Edelshtein, S., andPetatskiI, V., Zavodskaya Lab., 15,850 (1949). (21) Ekedahl, E., Hogfeldt, E., and Sillen, L., Acta Chem. Scand., 4, 556 (1950). (22) Eriksson, E., Kgl. L ~ n t b r i ~ k ~ - H O gAnn., ~ k ~ l16, 420 (1949). (23) Erler, K., 2. anal. Chem., 129, 209 (1949). (24) Ibid., 131, 106 (1950). (25) Foreman, G., Thompson, P. V., and Tolliday, J., J . Am. Leather Chemists’ Assoc., 45, 378 (1950). (26) Fujiwara, M., and Shimizu, H., ANAL.CHEY..21, 1009 (1949). (27) Gapon, T., and Gapon, E., Zhur. Anal. Khim., 4, 131 (1949).

Gapon, E., and Gapon, T., Zhur. Obshchei Khim., 19, 1627 (1949). Glueckauf, E., J . Chem. SOC.,1949, 3280. Qregor, H. P., Division of Colloid Chemistry, 118th Meetlrrg, AM. CHEM.Soc., Chicago, Ill., 1950. Gregor, H. P., and Citarel, L.. 118th Meeting. .$M. CHEM.Sot-.. Chicago, Ill., 1950. Grigorov, 0. N., and Tarshis, d.,Kolloid Zhur., 11, 390 (1949). Gustavson, K., J . Am. Leather Chemists’ Assoc., 45, 536 (1950). Gustavson, K., J . SOC.Leather Trades’ Chemists, 34, 259 (1950). Hansen, R. S., and Gunnar, K., J . Am. Chem. Soc., 71, 4158 (1949). Hilfiger, .J. P., Chem. anal., 31, 326 (1949). Hogfeldt, B., Ekedahl, E., and Sillen, L., Actu Chrm. Scand., 4, 828 (1950). Ibid., p. 829. Huffman, E., and Lilly, R. C., J . Am. C l ~ e m .Soc., 71, 4147 (1949). Huffman, E., and Oswalt, R., Ibid., 72, 3323 (1950). Idler, D. R., Ihid., 71, 3854 (1949). Jeng-Tsong, Y., Anal. Chem. Actu, 4, 59 (1950). Jenny, H., Nielsen, T., Coleman, S . , and Williams, D., Sciencc. 112, 164 (1950). Jindra, A . , J . Pharm. Pharmacol., 1, 87 (1949). Juda, Walter, and McRae, W. A,, J . Am. Chem. SOC.,72, 1044 (1950). Kressman, T. R. E., Nature, 165, 568 (1950). Kunin, Robert, . 4 ~ . 4 t . CHEM.,21, 87 (1949). Ihid., 22, 64 (1950). Lee, H., J. Soc. Leather Trades’ Chemists, 34, 150 (1950). Lundberg, L., Dansk. Tid. Farm., 23, 227 (1949). Lure, Y., and Filippova, X. A,, Zavodskaya Lab., 15, 771 (1949). hfartineg, F., Inform. qulm. anal., 4, 1 (1950). Mayer, S.IT., J . Am. Chem. Soc., 72, 2292 (1950). hlunta, J. A , J . Biol. Chem., 182, 489 (1950). Kachod, F. C., Sci. Monthly, 70, 189 (1950). Odencrantz, J., and Rieman, IT., ANAL.CHEM.,22, 1066 (1950). Partridge, S.>I., Biochem. J . , 44, 521 (1949). Ihid., 45, 459 (1949). Partridge, S.hl., Chemistry Le. Indtislry, 20, 383 (1950). Partridge, S.&I.,and Brimley, R. C., Biochem. J . , 44, 513 (1949I . Partridge, 8. &I., Brimley, R. C., and Pepper, K., Ibid.,46, 334 (1950). Partridge, S.M., and Westall, R. G., Ibid.,44, 418 (1949). Kahek, T., Przemysl Chem., 27, 678 (1948). Samuelson, O., Scensk Kem. Tid., 61, 76 (1949). Scarritt, D. R., Senger, D. R., and Ballje, E. J., Division of Colloid Chemistry, 118th Meeting, AM. CHEM.SOC., Chicago. Ill., 1950. Schramm, G., and Primosigh, J., 2. phys. Chem., 282,271 (1947). Schubert, J., Division of Colloid Chemistry, 118th Meeting, AM. CHEX.SOC.. Chicago. Ill.. 1950. Schubert, J., Finkel, 11. P., White, >I. K.,and Hirch, G. AI., J . Biol. Chem., 182, 635 (1950). (69) Schubert, J., and Lindenbaum, A., Abstracts of Papers Presented at 118th Meeting, AM. CHEM.SOC., p. 7C, 1950. (70) Schubert, J . , and Richter, J., J . Colloid Sci., 5, 376 (1950). (71) Schubert, J., Russell, E , and Myers, L., J . Biol. Chem., 185, 387 (1950). (72) Sepal, H. L., Miller, L., and Morton, J., Proc. Soc. Ezptl. B i d . Med., 74, 218 (1950). (73) Sheehan, J. C., and Rolhofer. W. A , , J . Am. Chern. Soc., 72 2466 (1950). (74) Soodak, M.,Pircio, A., and Cerecedo. L. K , J . Biol. Chem., 181, 713 (1949). (75) Spedding, F., Fulmer, E., Butler, T., and Powell, S., J . A m Chem. SOC..72, 2349 (1950). (76) Spedding, F., Fulmer, E., Powell, J., and Butler, T., Ibid., 72, 2354 (1950). (77) Spedding, F., Fulmer, E., Powell, J., Butler, T., and Yaffe, I. S., Division of ColloidChemistry, 118th Meeting, AM.CHEM. Soc., Chicago, Ill., 1950. (75) Street, K., and Seaborg, G. T., J . Am. Chem. SOC.,72, 2700 (1950). (79) Thompson, S. G., Cunningham, B. B., and Seaborg, G. T., Ibid., 72, 2798 (1950). (80) Tolliday, J., Thompson, G., and Foreman, G., J . SOC.Leather Trades’ Chemists, 34, 221 (1950). (81) Topp, N. E., and Pepper, K. W., J . Chem. SOC.,1949, 3299. ( 8 2 ) Csatrnko. Y.. and Datsenko. O., Zasodskaya Lab., 15,779 (1999). (831 \Veiss. 1) E , S n t u r e . 166, 66 (1950). (84) Westall, R. G.. ,J. Sci. Food B g r . , 1, 191 (1950). (85) Wiklander, L.. Soil Sci., 69, 261 (1950). (86) Wyllie, M. R. J., and Patnode, H. W.,J . Phys. and Colloid Chem., 54, 204 (1950). RECEIVEDNovember 2. 1950.