ION EXCHANGE ROBERT KUNIN, F. X. McGARVEY, AND ANN FARREN Rohm & Haas Co., Philadelphia, Pa.
T
HI!: review of the developments in the field of ion exchange
during the past year has been interesting from sevelal viewpoints. First, promising and new applications for this unit operation are continuing to appear, sccond, established applications are proving their worth on a large scale; and third, improvements are being developed for these well-established applications. I n the realm of new applications, the rccovery of uranium by means of ion exchange on a large scalc ranks as one of the more interesting and spectacular applications of ion elchange. At the Geneva “International Confcrenre on the Peareful Uses of Atomic Energy,” it was revealed that ion exchange has a prominent role in the recovery of uranium from lo^ glade uranium ores. -4nother development that has proved itself on an industrial scale is the use of ion exchange in the preparation of liquid sugar siiups from cane sugar. Although ion exchange has been used in sugar refining, it has been only recently that resins having the piopcr physiral and chemical properties have s h o n~ theii economic importance in cane sugar refining. The past year also has revealed that deionization b j ion exchange resins is a well-established technique for preparing the high quality water required by thc new high pressurr systems of the electric power gericration field
REVIEW ARTICLES
The rapid growth of ion exchange technology has reached the point that all inclusive review articles cannot be written n ith any degree of success. Deuel (2,4) has written a comprehensive article on structural properties and applications of ion exchange resins. Hutcheon (5.4, 6 A ) covered the same material less intensively. Column chromatography was the subject of a review by Hesse ( 4 A ) , whereas the British Medical Society ( l 2 A ) has published an extensive review of chromatography in its application to biochemical and medical problems. Ion exchange matcrials as catalysts for chemical reactions are reviewed by Xachod (8d). The technology of ion exchange membranes is discussed by Wegelin ( 1 l A ) and hfelkersson ( 7 A ) . R a t e r treatnicnt in the food industry as applied t o ion exchange materials is reported b y Nordell (9.4) and Cihal (1.4). The use of ion exchange tcchniques in analytical chemistry is described in an elementary article by Pallaud ( 1 O A ) Glneckauf (3-4) summarizes problems in the atomic energy program. THEORY
The theory of ion exchange has progressed rapiclly following the pattern set in previous year?. The mass of experimental data on the basic aspects of ion exchange has increased, particularly with respect to osmotic pressures, and efforts have been made to estimate activity coefficients by analogy to linear polymeric systems. Grcgor’s theory of ion cwhange ( 1 6 B )has been applied in a number of cases satisfactorily. Recent investigators have em540
phdsid(d ion hydration as discusscd by HelfEerich ( I 7 B ) . Moralli ( S I B , 32B) suminarizes some early work from a structural standpoint. The thermodynamic relationships in ion exchange have received considerable attention. Duncan ( 8 B ) obtained energy balances for a vaiipty of systems, and Loebl and coworlters (27B) obtained similar data on cation exchangers having carboxylic groups. Rios and Ruiz ( S 4 B ) developed an equation from kinetic eonsidcrations, which has proved to be useful for predicting equilibria in inorganic ion exchange materials. The effcct of ion species on the heat of wetting of ion exchange material has been meawrcd by lliatsuura (SOB). The osmotic properties of both anion and cation exchange resins have been carefully studied by Soldano and associates (4IB-4323). These propel tics were found to be dependent upon the ionic radii, and the selectivities of anion exchange and cation exchange resins were correlated with the osmotic pressure of the system. Sobue and Tabata (SQB,40B) employed spectrophotometric methods for obtaining equilibrium values in films. Bonner ( 6 B ) examined the activity cocfficients for lithium, hydrogen, sodium, and potassium salts of p-toluenesulfonic acid and compared these values with his results on sulfonated cross-linked styrene divinylbenzene cation ewhangp resins. Anstcrweil(1 R ) developed a mathematical relationship for the calculation of activity coefficients for a resorcinol-formaldchyde exchanger. Studies wcre reported during the year for various exchange. equilibria. Saldadze and others (35B-37B) correlated data for the bariiim-magnesium, potassium-barium, and zinc-cadmium equilibria for a phenolformaldehyde sulfonic arid cation exchanger. Strocchi (44B)obtained comparable valucs using strong and wcak acidic cation exchangers, A complete study of the sodium chloride and potassium chloride equilibrium on a cation exchanger is reported by Whiteombe (46B). Hogfeltit (19B) made a careful study of the silver-hydrogen equilibrium. Seiyama and coworkers ( S B B ) developed equations relating the eqiiilihrium constant to the fraction of the ions on the ration cxchanger Diamond ( 7 B ) summariaes work on the equilibria of berj Ilium, calcium, strontium, barium, radium, sodium, rubidium, and cesium in concentrated hydrochloric acid solutions in
ROBERT KUNIN received his B.S. in 1939 and Ph.D. in 1942 from Rutgers University. H e is head of the laboratory for research and development of ion exchange resins for the R o b & Haas Co. Kunin spent two years as research chemist for TVA, a year a t Mellon Institute on the Petroleum Refining Fellowship, and two years during the war on the Manhattan Project a t Columbia University.
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 48, No. 3
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ION EXCHANGE
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contact a i t h cation emhangers. E'elecetta and others ( 9 B ) obtained cationic equilibrium results on ammonium ions in' the presence of a cation exchange resin. Gregor (15B) investigated the selectivity coefficients for quaternary base anion exchangr resins and employed an ion pair formation mechanjsm t o explain his results. Yamabe (47B, 4 8 R ) coilclated equilibrium values for anion and cation exchangers over a wide range of concentrations. Lurk (28R) evaluated the complex reactlons which accompany the exchange of silvrr thiosulfate on wt3akly basic anion exchange resins. Solid-solid reactions involving ion exchange betwern two independent ion exchange systems have been studied extenpively in India by Krishnamoorthy ( i ' f B ,22B), and the kinetics of such processes examined in considerable detail. Similarly Alanccke and others ( 2 9 B )examined the interaction of ion exchange particles by measurement of conductivity. The dependence of equivalent conductance of ions in the resin phase upon the hydrated ionic radius was again verifird. The kinetics of ion exchange procrsses have stimulated a considerable amount of interest. Bieber and others ( 4 B ) developed an ion exchange ratc mechanism for the silver-hydrogen cycle 11 hieh could be correlated well. The liquid phase mass transfer coefficient is reported t o vary as the 0.56 power of the velocity and inversely as thc particle diameter. Glueckauf ( 1 S R ) reevaluated the theoretical plate concept of chromatographic separations. Gapon and coworkers ( I d B ) report on the state of chromatographic theory in Russia. JAapidus (26B) obtained data on the sodium-hydrogen cycle which could be applied to cheek mathematical relationships for fixed bed operation a t high flow rates. Gradient elution of chromatographic columns has been applied in several studies. The theory of this operation has been developed by Preiling (10B);howevei his devrlopment applies only to systems phich operate under equilibrium conditions for materials giving linear isotherms. Baddour and associatrs ( 2 B )have examined the rlution of partially saturated beds in the sodiumhydrogen cycle using the equations developed by Goldstein [Proc. Roy. Sac. (London) A219, 151 (1953)l; an excellent relationship was found between experimental results and those that had been calculated. Hiester and others (18 B ) studied a countercurrent ion exchange system for continuous ion exchange processes. Tetenbaum ( 4 6 B ) obtained values for the self-diffusion of cations in a cation euehange rebin using the shallow bed technique t o obtain the diffusional constants. Similar data were obtained by Rachinskii ( S S B ) . Bikson ( 5 B ) applied the minimum bed concept to columna1 oprration. The effect of mixed solvents on ion exchange performance was examined by Gregor (14R). I n tbese studies swelling appeared to be determined largely by the dielectric constant of the sorbed solvent. Baker ( S B ) examined the effect of ion exrhange in catalytic studirs using different solvents. Kakihana (20B) determined the equilibiium constants for sodium hydrogen exchange in acetone-water mixtures and found that the selectivity of the sodium ions increased m ith the ncetone concentration of the
solution. The reciprocal of t h r logarithm of the equilibrium constant varied linearly with the dielectric constant of the mixed solution. The effect of "large ion" blocking on the exchange rate of cation eschange resins was obtained by Krzysztofowicz and Woycicki (23B-95B). Gabriel ( 1 1 R ) determined the adsorption isotherms of a homologous series of aliphatic acids for a nonionic resinous adqoi bent.
FRANCIS X. MCGARVEY obtained his B.S. in 1941 and M.S. in 1943 from the University of Pennsylvania. He has been engaged for the past nine years in development of ion exchange processes for Rohm & Haas Co. During the war he served with the U. S. Army at Oak Ridge and Los Alamos. Prior to this, he spent three years with the Bureau of Ships on radar and ordnance installation.
ANN L. FARREN, a graduate of the University of Pennsylvania (A.B., 1948), has been B member of the ion exchange research staff of Rohm L Haas for the past two years. Before joining Rohm & Haas she spent four years doing biochemical research at Valley Forge Hospital and Jefferson Medical College and a year on colchicine chemistry for Smith, Kline and French.
March 1956
MEMBRANES
The use of ion permselective niembranrs for various industi i d applications continues to be of coniidwable interest. Some iniportant conti ibutions to the theory of membranes have alqo appeared. Schlogl (19C, SOC) exteiided Tenrill's equation for mono-monovalent processes involving ion exchange membranes. Graydon and S t e a w t ( 7 C ) have prepared membranes by bnlk copolymenmtion of the propyl ester of p-styrene sulfonic acid. They discuss the propertles of these membranes from a structural standpoint. Hills and others ( 8 C ) performed a similar study using poly-a-methacrylic acid cross linked with ethylene glycoldimethacrylate. Tajima ( 2 2 C ) preparrd and evaluated membranes using finely divided ion exchange iesin disprrsed in poly(vinyl chloride). In India, Xrishnaswamy (14C) prepared membranes by molding plastic and exchanger fines in a molding dtvice. Similar niateiials were prepared by Kosalra ( I S C ). Kasper ( I O C ) prepared cation exchange membranes from the condensation products of sulfonated phenol and formaldehyde Similarity between synthetic and natui ally occurring memhi ancs is noted in papei s by Carr ( 4 C ) and Altamirano (1C ) . Bramer ( 3 2 )and Kunin and coworkers ( I 5 C ) have developed permselective membrane procrsses for the recovery of sulfuric acid from spent iron pickle solutions. Economic analysis of this application indicates that a pi actical solution to this serious waste problem may be achieved by a mcmbrane process. IIunter (9C) exaniinrd an adsorption clialj sis technique for recovei y of amino acids. R'ingerd and Block (24C) applied a siinilar technique to thr deionization of n h q r . Tajima (21C) used a membrane in an electrolytic bath used for the electrodeposition and iefining of silver sulfamate. Bergin and Heyn (SC) used ion exchange membranes a8 elec trotlcs in studies involving liquid ammonia. Similarly Carson and associates (66")found that salt bridges plugged with ion exchange disks a ere superior to the conventional potassium chloride salt biidge. The greatest emphasis in the application of ion exchange menibranes has been dirccted toward the problem of brackish water deioniiation. A comprrhensive study of this problem is reported by Ringrr and others (23C)n ho usrd a 50-component cell to test relationships involving energy requirements and flow capacity, Apparatuq for the removal of electrolyte from solutions were developed by Rosenberg ( I N ' ) and Katz ( I l C ) . Eliassen ( 6 C ) reviews t h r cconornics of these processes. Kosaka ( 1 2 C ) employed a continuous process nsing membranes and electrical energy to regrnrrate the exchangers. Pattle (17C) and RianecAc (1") used the multicomponent cell to create electrical current.
INDUSTRIAL AND ENG INEERING CHEMISTRY
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UNIT OPERATIONS REVIEW
. . . Low grade uranium ores now processed on commercial scale by means of ion exchange These cells were of very low etfciency and did not appear practical. Future developments rest on the perfection of new and more practical cell designs.
a method for the chromatography of amino acids which employed volatile acids for elution. Campbell and others ( 3 F ) studied amino acid fractionation from the standpoint of ion exchange resin hydration. A special publication from the British Medical
WATER SOFTENING
Society contained several excellent papers on peptide and protein fractionation (dF, 6 F , IOF, l l F , 13F, l 4 F ) . Chromatography of serum protein ( B F ) and neutral proteins (IF)was accomplished using anion exchange resins. Blood chemistry procedure8 involving ion exchange techniques have been developed by Szold (178’) and Vanatta (18F). A gradient elution procedure for thc separation of urinary ketosteroids has been developed by Lakghmanan ( 9 F ) . Strocchi fractionated amino acids from natural products (16F). Chondroitin, a new micropolysaccharide, was fractionated by Davidson ( 6 F ) , using a quaternary ammonium anion exchange resin. Neomycin ( 1 9 F ) and the antibiotic, polymyxin ( 7 F ) , were recovered by ion exchange techniques. Severa ( 1 5 F ) describes an antibiotic processing plant in Czechoslovakia that employs cation exchangers. The hydrolysis of proteins and dipeptides was achieved by ion exchange techniques (20F). Blood was desalted by a mixture of ion exchange resins prior to pasteurization (12F). Pharmacological studies on deionized water were evaluated by Zinnitz (21F) from a biochemical standpoint.
Traditionally water softening has been the most familiar application of exchange. A popular treatise by Tyler (101)) reviews the subject for the general public. A variety of methods for water softening has been developed by Baunian (ID), Blight ( 3 D ) , and Rantebeen (6D). Calmon and Simon (40) investigated changes in alkalinity which ocrur when water is softened by ion exchange. Reduction in pH and alkalinity was observed in waters treated by exchangers which contained weakly acidic groups. Monofunctional sulfonic acid cation exchangers did not show this effect. Davision (90) developcd a method for removal of ammonia from waters which are softened. An anionic “softening” process has been developed which removes certain objectionable anions in a manner analogous to softening ( 7 0 ) . Industrial experience with large scale softeners has been summarized by Cummings (60) and Schmidt (80). The economics of water softening is discussed by Berry ( 2 D ) . An automatic softener for domestic use is desrribed by Waugh (111)). DEIONIZATION
Deionization is the most extensive industrial application of ion exchange technology. The past year has indicated a considerable expansion in this application. Applebaum ( I E ) ,Bouchard ($E), and Miller (f S E ) have sumniarbed modern practice in the field. Kunin and McGarvey ( 1 0 8 ) developed a process for regeneration of a column containing a mixture of resins. Waters which are deionized b y the mixed bed principle were found suitable for feed water to nuclear reactors (27E). Deionized water was considered acceptable for pharmaceutical use according to Buchi (4E) and Saunders (16E). Steam purity testing (12E) and scale removal (18E) were accomplished by deionization methods. The advantages of deionization in the textile field are reviewed ( 7 E ) . Latex washing was aided by deionization according to Burwell and Nordell ( 6 E ) . Studies in Italy indicated that waters contaminated during warfare may be purified by ion exchange procedures ( 1 1 E ) . A variety of field experiences in large scale treatment of water has heen reported by O’Reilly (16E),Morrow ( f 4 E ) , Gurney (9E),and Finnegan (BE). These authors report considerable savings by use of ion exchange deionization. Finnegan reported a 44 cent per gallon saving over a similar installation employing notes the effect of organic matter on evaporation. Bogers (,%‘E) the performance of deionization units. His study indicates that sodium chloride rinses aid in correction of these difficulties. I n other cases, oxidants must be employed to remove irreversible fouling from the bed. Adequate pretreatment is recommended as the best solution. The extensive sale of small portabic deionization units for home use has continued (6E). BIOCHEMICAL SEPARATIONS
Ion exchangc techniques for the chromatographic separation, purification, and concentration of biochemically active materials have become BO widespread in scope that a complete review of this field is beyond the scope of this section. The following papers summarize some of the more pertinent contributions from an ion exchange viewpoint. Hirs and associates ( 8 F ) developed
542
RECOVERY, PURIFICATION, PREPARATION, AND NEW RESINS
The role of ion exchange in recovery, concentration, and preparation of various interesting and valuable materiels continues a t an acceleratcd pace. New exchangers have been developed for special applications. Soloway (342) describcs an electron exchanger prepared from formaldehyde and naphthazarin. Parrish prepared exchangers with chelation properties (SOG). An oxidation-reduction resin was prepared from poly-p-thiolstyrene by Lebovits (29G) and evaluated in detail by Gregor (SG, I N ) . An amphoteric resin was prepared by Hojo (17G) from hexamethylenetetramine-furfural condensation. Anion exchangers prepared from quaternarized acrylamido compounds are also reported ( 1G ) . Continued efforts to develop processes employing ion exchange resins a t their maximum selectivity have held the interest of many research groups. The program a t Chemical Research Laboratory in Teddington has been directed along these lines (8G, 25G). Lillin (22G) and Glass (12G) devcloped and applied methods for the selective elution of heavy metals from ion exchange beds. Americium and curium were separated on a cation exchanger when eluted in the presence of chelating agents. Special specificity was observed for anion exchange processes in concentrated solutions of hydrochloric acid (24G, 26G, BTG). Wesly (SoG) showed retention of iron complexes under unusual conditions. Dizdar (8G) used a reversible column technique t o reproduce the effect of a countercurrent technique for the chromatographic elution of cesium, cobalt, uranium, manganese, and europium. Kadomtaeff (19G) studied the variable8 of separation of transition elements using the nickel and cobalt system as a model. Ion exchange continues to be employed in numerous analytical procedures. Some of these have been reviewed by Pollard (310), Rieman ( J g G ) , and Berntsson (2G). The “Bikini Ashes” were analyzed using exchanger techniques (gOG). The newly synthesized elements 99, 100, and 101 were isolated from reactor targets using rapid ion exchange elution techniques (ZIG, 96G).
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 48, No. 3
ION EXCHANGE Okamoto (88G) developed an automatic extraction unit for alkaloids which used a carboxylic cation exchanger to concentrate the alkaloid. Quantitative methods for the scparation and evaluation of morphine and other alkaloids have been developed (14G, 18G, Y7G). Lobo (23G) and Dvorakova (QG) studied methods for concentrating alkaloids. Many natural products were purified arid stabilized by ion exchange methods. Kiseman (4OG), Villforth ( S g G ) , and GarinoCanina (10G) used exchangers to treat wine. Milk was processed (S6G), vitamin A palmit a t e was purified (SG), aconitic acid was recovered from blackstrap molasses (5G), and mineral oil-vegetable oil mixtures werc separated (16G) by means of resins. Levi (21G) removed impurities from nonaqueous solvents. T h e oxidation products of phenanthrene (4C) were s e p a r a t e d b y c h r o m a t o g r a p h y o n strongly basic exrhangers. Racemic miutures were studied (16G) and acetylenic hydrocarbons (41G) were prepared by action of ion exchange substances. Indicator compounds in conjunction with ion exchange resins were developed as indicators for acid concentration in gastric juices (SSG).
Edison Co., New York City WASTE TREATMENT
I n addition to the ion exchange treatment of metallic a-astes which have been studied for several years, the problem of radioactive waste disposal has received considerable attention. Paulson and Mindler (1b H ), Black (%”), and Arden (1H) reviewed the field of metallic waste disposal. Ion exchange techniques are being applied extensively in the plating and allied industries as indicated by the many papers in the metal finishing journals (4HJ811). Fraetkin ( 6 f I )describes a procedure for the rejuvenation of spent sulfuric acid liquors using a cation exchanger to remove metallic impurities. Chromic acid rejuvenation and chromate waste recovery continue t o be used widely according to Brink (Y3H) and Ledford (9H).Cupric ammonium liquors from rayon wastes have been treated in Germany ( 6 H ) and Japan (11H). Carboxylic cation exchange resins have been used t o recover copper from mine drainage waters (1S H ) . Hydrochloric acid solutions have been freed from iron by contact with an anion exchange resin (14H). Spent sulfite liquors containing ammonia have been treated with a cation exchanger to concentrate and recover the ammonia (IOH). Radioactive wristcs may be disposed of in a variety of waste techniques which require ion exchange. Swope and Anderson (16H) used a cation bed to reduce radioactivity in water. Precipitation and adsorption methods were used by Ginell (7H) and the Corps of Engineers (I7 H ) . Multiple cell ion exchange membrane techniques were also used by Walters ( 1 6 H ) to concentrate radioactive wastes. CATALYSIS
Although industrial use of ion exchange resins as catalysts for various organic reactions has not materialized, interest in this field remains high. Considerable interest has developed in the use of sulfonic acid cation exchange resins as catalysts in epoxidation reactions with hydrogen peroxide. A t the September 1955 meeting in Philadelphia of the Association of Oil and Paint Chemists, several papers were presented on the use of ion exchange catalysts in such reactions. The convenience of solid ion exchange resins as catalysts has been demonstrated repeatedly in the literature. Helfferieh (61) has developed a quantitative
March 1956
interpretation of these catalysts by treating the ion exchange phase as a homogeneous system. &lowery (101) examined the selectivity of catalytic action for the hydrolysis of D-galactose when strongly acidic cation exchangers of varying degrees of cross linking are used. The rate of reaction was found to vary inversely as the degree of cross linking of the resin. Increased mobility in the resin phase is believed to account for selectivity in these systems. Zafiriadis and coworkers (141) found weakly basic exchangers were effective catalysts for the dehalogenation of aliphatic dihalogen compounds. A cation exchanger was found to be an effective catalyst for the hydration of ethynylcarbinols to acetylcarbinols (51). Several esterification reactions (11, 81) and rcactions involving condensations of aldehydes and ketones were studied ($1,SI, 91). Paulson and Deatherage (121) employed strongly acidic cation exchangers for the hydrolysis of proteins; alcohols were dehydrated (1S I ) , and acetylation of thiophene and alkyl-substituted thiophenes was accomplished with cation exchange resins (111). These exchangers were also promoters for the polymerization of epoxy compounds such as diglycidyl ethers of dihydric phenols (?‘I). Bafna and associates (41) summarize the literature on catalytic action of ion exchange materials. MEDICINAL
Activity in medicinal applications of ion exchange materials has been stimulated by the appearance of a comprehensive book by Martin ( I J ) . The use of exchangers as bulking laxatives has been considered (bJ) and since nervous disturbances are involved with electrolyte inbalance in the body, some success has been reported through the fecding of cation exchange resins in casea of epilepsy (3J). A critical evaluation of cation exchange resins for cases of sodium edema has been m i t t e n by Spencer and LloydThomas (6J). Effects of colitis and other intestinal irritants were counteracted with polyamide anion exchange resin in conjunction with polymyxin ( 6 J ) . The quinine form of a carboxylic cation exchanger was used to evaluate the concentration of acidity in gastric juices ( 4 4 .
INDUSTRIAL AND ENGINEERING CHEMISTRY
5-43
UNIT OPERATIONS REVIEW APPARATUS, PROCESSES, AND MISCELLANEOUS APPLICATIONS
As in previous years, continuous ion exchange processes received considerable attcntion. The research groups a t Stanford Research Institute report on several interesting aspects of this technique. I-Iiester and others (14K, .?OK) summariae such operations and present an interesting economic survcy which appears very favorable for moving bed techniques. TIiggins and Roberts ( I 6 K ) a t Oak Ridge describe a new continuous countercurrent process called a “jerk” bed. The application of a spinner column for continuous processes is reported by O h and coworkers (29K). A continuous ion exchange process based on the movement of an endless belt has been described by Muendel (d8K). Interest in these processes has also been expressed in Europe (39K). Collier ( 4 K ) developed a continuous process based on vibrating screens. New techniques for the evaluation of exchangers have been summarized by Fisher and Kunin ( 7 K ) . Stoch ( S T K ) developed similar procedures in Germany. A small ion exchange unit for testing ion exchange applications in the field has becn described (26K). The problems of titration studies as a method for characterizing exchangers have been revicwed by Strobe1 (38K). The evaluation of a strongly basic anion exchanger prepar ed in Czechoslovakia has been rcported in considerable detail (34K). Information on the void volume of packed coluinns has been correlated in two papers (16K, 22K). Procedures for the operation of ion exchange installations have been reported from a variety of sources. Mindick ( Z 6 K ) discusses the various fvctors involved with capacity and leakage values. Juneno and Ruiz ( 1 9 K ) developed a procedure for the calculation of critical bcd depths in softeners. Klumb ( d l R ) , Whcaton (,$OK), and Gill ( 8 K ) describe methods for operation of ion exchange systems. Reents and Stromquist ( 3 1 K ) describe deeigns for mixing ion exchangers in units. Skold and Wilkes (JJK) report on the design and operation of an industrial mixed bed unit. The use of mixtures of sulfuric and sulfurous acids to regenerate cation exchangers in the hydrogen cycle is the subject of a recent patent (36K). Gilwood ( Y K ) and LeClerc ( Z J K ) studied the stability of anion exchange rcsins and discussed inethods for the restoration of fouled materials. The efforts to increase selectivity of ion exchange operations have resulted in considerable interest in chelation reactions. Bray and Reiser ( d K ) devcloped a mocedure for recycling solutions containing complcxing agents through the ion exchange unit. Jcntxsch ( 1 8 K ) examined the selective separation of cobalt on exchangers which had been treated with l-nitroso-2naphthol. Spencer ( % K ) studied the exchange reactions of cobalt in conventional ion exchange. Hagdahl ( 1 S K ) found that sharper chromatograms could he obtained if the operation was carried out in a threc-stop process using columns of progressively dccreasing diameter. Coryell and RIarcus ( 6 K ) developed a theory on complex formation which may be useful. Gregor and others (IOK) provided some information for the magnesiunipotassium exchange. Gregor and coworkers also obtained considerable thermodynamic data for the formation of chelates ( I 1K , IWK) in polymethacrylic and polyacrylic acid-copper systems. The use of ion exchange to purify gas streams has been studied in some recent work (17K). Phenols have been removed from waste streams by anion exchange resins a t least in part by an adsorption mechanism ( I K ) . Exchange reactions in aqueous ethyl alcohol solutions were studied in Russia ( 2 4 K ) . Xatcholsky and Zwick (dOK) used the swelling brhavior of cross-linked polymethacrylic acids to produce niechanical energy. Hydroponics was investigated in India using ion exchange resin salts ~b the source of plant nutrients ( S d K ) . Changes in glucose ( 3 K ) by ion evchangc treatment are reported by Buhler and associates. Color stability in apple juice ( 6 K ) resulted from the treatment of these juices with cation exchangers. 544
The status of the ion exchange field may be estimated from sales volume presented by Mindler and Paulson (d7K). Their cstimates for total sales volume are as follows: Softening Deionization M ithout silica reduction Deionization with silica reduction Mixed bed deionization Split strcain dealkalization Dealkalization
$18,000,000per 6,000,000 per 5,000,000 per 3,000,000 per 2,000,000 per 1,000,000per
year year year year year year
In concluding this ywr’s review of ion exchange, the contiiiued growth of this unit operation is reassured. Continued cffort on the part of resin manufacturers t o develop new products and to improve the rstablished resins, economic evaluations of the many establishpd applications, continued development of new methods and techniqurs for using ion exchange resins, and further srarches into new fields of applications are excellent signs of a hralthy development
Bibliography REVIEW ARTICLES
(1-4)Cihal, K., Selix, PI.,Prumysl Potratin 3, 144-50 (1952) (2.4) Deuel, H., Mitt. Lebensm. N g g . 46, 12-36 (1955). (3-4) Glueckauf, E., Endeavour 14, KO.54, 83-9 (1955). (4.4) Hesse, G., Angew. Chenr. 67, 9-13 (Jan. 7, 1955). (5A) Hutcheon, J., Chem. & Process Eng. 35, 379-83 (Doc. 1954). (6A) Ibid., 36, 5-9 (Jan. 1955). (iA) Melkersson, Karl-Aerel, T e k . Z’idskr. 84, 865 (1954). (8-4)Xachod, F. C., Research Council of Israel, Spec. Pub1 S o . 1 (L. Farkas Meni. Vol.), pp. 188-92, 1952. (99) Kordell, E., Food Eng. 27, 89-99 (April 1955). (10.4) Pallaud, R., Chim. anaE. 37, 16-19 (1955). (1lA) Wegelin. E., Bull. centre belge e‘tude et document e a t u ( M g e ) , No. 21, 182 (1953); Abst., J . Am. V a t e r Works Assoe. 47, 80 (June 1955). (12.4) Williamq, R. J. P., B i t . Med. Bull. 10, 165-9 (1954). THEORY
Austerweil, G., Industrie plastiqi(e8 mod. (Paris) 5 , 32-3 (1953). Baddour, R., Goldstein, D., Epstein, P., IND. ENG. CHEM. 46, 2192-5 (1954). Baker, J. W., Neale, A. J., Y a t u r e 172, 583 (1953). Bieber, H., Steidler, P., Selko, W., Chem. Eng. Progr. Symposium Ser., No. 14, 17-21 (1954). Bikson, Ya. &I., Zhur. F i t . Khim. 27, 1530-8 (1953). Bonner, O., Easterling, G., Weit, D Holland, V., J . Am. Chem. Soc. 77, 242-4 (1955). Diamond, R. &Ibid., I.,77, 2978-83 (1955). Duncan, J. F., Australian J . Chem. 8 , 1-20 (1955). E’elecetta, V.. Markham, A., hIcCarthy. J., T a p p i 37, 431-6 (Oct. 1954). Freiling, E., J . Am. C h e w SOC.77, 2067-71 (1955). Gabriel, II., Cooley, R. J., IND.EEL CHEM.47, 1236-9 (1955). Gapon, E., Gapon, T., Zhupakhina, E., A k a d . N a v k 8.S S R. Otdel. Khim. N a u k 1950, 5-29 (1952). Glueckauf, E., Trans. Faraday Soc. 51, 34-44 (1955). Gregor, H., Nobel, D., Gottlief, 11..J . Phys. Chem. 59 10-13 (1955). Gregor, €1. P., Belle, J., llarcus, R . A,, J . Ana. Chem. SOC.77 2713-19 (1955). Gregor, II., U. S. Dept. Commerce, Washington, D. C., OTS, P B 116546, March 29, 1949. Helfferich, F., Angew. Chem. 67, 13-16 (Jan. 7, 1953). Hicster, N., Phillips, R., Cohen, It., Chcm. Eng. Progr. Symposium Sei-., No. 14, 57-72 (1954). Hogfeldt, Erik, A r k i v . Kemi 7, 561-4 (1954). Kakihana, Hidetakc, Sekiguchi, Keji, J . Pharm. SOC.J a p a n 75, 111-12 (1955). Krishnamoorthy, C., Desai, A , Soil S c i . 79, 159-66 (1955). Ibid.,pp. 216-20. Krzysztofowicz, AI., Woycicki, W., Hull. acad. polon. sci. Classe I11 2,237 9 (1954). Ibid.,pp. 241-2. Ibid., pp 243 4. Lapidiiu, I,., Rosen. J , Chern. Eng. Progr. Syinposium Ser., NO. 14,97-102 (1954).
INDUSTRIAL AND ENGINEERING CHEMISTRY
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Vol. 48, No. 3
ION EXCHANGE ( 2 7 8 ) Loebl, E. M., Luttinger, L. B.. Gregor, 13. P., J . Phys. Chon.
59,559-60 (1955). (28B) Lur6, Yu., Peremyslova, E. S., Zhiir. Priklad. Khirn. 27, 1207-12 -~ 11954). (29B) Manecke, G., Otto-Laupenmuhlen, E., 2. physik. Chem. 2, NO.5/6,336-52 (1954). (30B) Matsuura, Tatsuo, Bull. Chem. Soc. J a p a n 27, 281-7 (1954). (31B) Moralli, G. J., J . Recherches centre natl. recherche sci., Labs. Bellevue (Paris) 1954, S o . 26, 265-76. (32B) Ibid.,pp. 277-89. (33B) Karhinskii. V. V..Z h w . P/iklad.K h i m . 27. 831-12 (1954). (34Bj Rios, E. G., Ruia, J. C., Anales edafol. y f i s w l . vegetal ( M a d ,id) 13,791-841 (1954). (35B) Saldadae, K. SI.,Kolloid z h w . 16, 79-81 (1954). (36B) Xbid., pp. 284-7. (37B) Saldadae, K. Ll., Bozhevol'nov, E. A., Ibid., 16, 371-3 (1954). (3813) Seiyama. T., Sagamatsu, LI., Sakai, W., J . Electvochem. Soc. ( J a p a n ) 21,393.4 (1953). (39B) Sobue, IIiroshi, Tabata, Yoneho, J . Chem. Soc. J a p a n , I n d . Chem. Sect. 57,469-71 (1954). (40B) Ibid., pp. 779-8 1. (41Bj Soldano, B., Chesnut, D., J . Am. SOC.77, 1334-9 (1955). (42B) Soldano, B., Larson, Q., Ibid.,77, 1331-4 (1955). (43B) Soldano, B., Larson, Q., Myers, O., Ibid., 77, 1339-44 (1955). (44B)Strocchi, P. >I., A n n . c h i m (Rome) 44, 147-61 (1954). (45B) Tctenbaum, h l . , Gregor, H., J . Phys. C h e w 58, 1156-63 (1954). (46B) Whitcornbe, J., Banchero, J., White, R., Chem. Eng. Progr. Symposium Ser., No. 14, 73---85(1954). (47R) Yamabe, Takeo, b. Chem. Soc. J a p a n , I n d . C h e m Sect. 56, 645-6 (1953). (48B) Ibid., 57,701-3 (1954).
(9D) Thompson-Kennicot, Ltd., Brit. Patent 730,313 (May 18, 1955). (10D) Tyler, C. A., Water Conditioning Research Committee Report, 1955. (11D) Waugh, H. C., G. S. Patent 2,689,218 (Sept. 14, 1954). DEIONIZATION
'
(1E) Applebaum, S., McKeown, AI., Power Eng. 58, 76-7 (June 1954). (2E:) Rogers, P., Water (Holland) 38, 299--302 (1954). (3E) Bouchard, J., Chimie & industrie 72, 422-5 (1954). (4E) Buchi, J., Soliva, hl., Phnrm. Acta Helv. 29, 221-31 (1954). (5E) Burwell, J., Nordell, E., Power 99, 1 0 3 4 (Jan. 1955). (6E) Chena. Week 76,56 (April 30, 1955). (7E) Fibres (London) Natural & Synthetic 15, 328-30 (Oct. 1954). (8E) Finnegan, T., Miller, D., E'lec. Light and Power 32, KO.12, 117-22 11954). ~, (9E) Gurney, W., Stewart, C., Southern Power and l n d . 72, X o . 11, 58--63,78-80 (1954). (10E) Kunin, R., McGarvey, F., U. S. Patent 2,692,244 (Oct. 19, 1954). (1132) Lalli, G., Minerva .Wed. 1954, 11. 1372-8. (12E) Lane, R., Larson, T., Paukey, J . , ISD. ENG.CHEX 47, 47-50 (1955). (13E) Miller, Durando, Power 99, 73 -7 (July 1955). (14E) Morrow, E., Gehle, F., Power Eng. 58, S o . 7, 86-92 (1954). (15E) O'Reilly, L., Sukumar, A , , Faddan, W.,Power 99, 96-9 (Jan. 1955). (16E:) Saunders, L., J. Pharm. and Phainmcol. 6, 1014-22 (1954). ( l i E ) Sevita, M.,Scheibelhut, C., IND.ENG.CHEW 47, 1020-2 (1955). (18E) Webb, T. 1,. R., U. S. Patent 2,656,128 (Oct. 1953).
MEMBRANES
Altamirano, M., Schleyer, W.L., others, Biochim. et B ' i o p h ~ s . Acta 16, 268--82 (Feb. 1955). Bergin, M. J., Heyn, A. H. A., J . Am. C'hem. Soc. 76, 4765-9 (1954). ENC.CHEM.47, 67-70 (1955). Bramer, H., Coull, J., IXD. Carr. C. W., Woods, K. K., Arch. Biochem. and Riophus. 55, 1-8 (March 1955). Carson, W., Michelson, C., Koyama, K., A n a l . C'hem. 27, 472-3 (1955). Eliassen, It., Civ. Eng. 24, 366 (1954). Graydon, W., Stewart, R., J. Phys. Chem. 59, 86-9 (1955). Hills, G., Xitchner, J., Ovenden, P., Trans. Paradag Soc. 51, 719-28 (1955). Hunter, I. It., Houston, D. F., Kestcr, E. B., A n d . Chein. 27, 965-8 (1955). Kasper, A., U. S. Patent 2,702,272 (Feb. 15, 1955). Kata, W., Rosenberg, N., Ibid., 2,694,680 (Nov. 16, 1954). Kosaka, Y., Sato, A., .I. Chem. Soc. J a p a n , I n d . Chem. Sect. 55, 628 (1952). Kosaka, Y., Sato, A., Tajima, S., Ibid., 56, 279-81 (1953). Krishnaswamy. N.. J. Sci. I n d . Research ( I n d i a ) 13B, 722--6 (1954). Kunin, R.,IIorner, C . , others, IND.ENC.C H E x . 47, 1121-9 (1955). Nanerke, G., U. 8.Patent 2,700,063 (Jan. 18. 1955). Pattie, R. K., Nature 174, 660 (1954). Kosenberg, PI'. W.,E.S. Patent 2,708,658 (May 17. 1955). Schlogl, R., 2. Elektiochena. 58, 672-3 (Nov. 1954). Schlogl, R., 2. physik. C h e m 1, 305-9 (1954). Tajima, Sakae, Hiratsuka, Yutaka, others, J . Electroclieiri. S o c . J a p a n 22, 211 (1954). Tajima, Sakae, Ibid., 22, 67 (1954). Bodamer, G., others, IND.ENG.CHEX.47, 3 - 6 0 Winger, h., (1955). Wingerd, W. H., Block, R. J., J. Dairu Sci. 27, 932.; (1954). WATER SOFTENING
(1F) Boardman, N. K., Partridge, S. lI,,Biochrrit. J . 59, 543-52 (April 1955). (2F) Boman, Hans G., Nature 175, 898-9 (1955). (3F) Campbell, P., Jacobs, S., others, Chemistry & Industry 1955, h-0.5, 117-18. (4F) Campbell P. N , Work, T. S., B i t . M e d . Bull. 10, 196-201 (1954). (5F) Chibnall, A. C., Ibid., 10, 183-6 (1954). (6F) Davidson, E. A. Meyer, K., J . Biol. Chem. 211, 605-11 (Dec. 1954). (7F) Diamond, J., Can. Patent 507,162 (Xov. 9, 1954). (8F) Hirs, C., Moore, S., Stein, W.. J . Am. Chem. Sac. 76, 6063-5 (1954). (9F) Lakshmanan, T., Lieberman, S., Arch. Biochern. and Bwphys. 53, 258 -81 (Nov. 1954). (10F) Markham, It., Brit. Med. Bull. 10,214-17 (1954). (11F) Martin, A. J. P., Ibid. 10, 161-2 (1954). (1239 Kitschmann, H., Kistler, P., Helv. Chim. Acta. 37, 1767-78 (Oct. 1954). (13P) Partridge, S. M., Brit. .Wed. Bull. 10,241-6 (1954). (14F) Porter. R. It.. Ibid.. 10.237-41 (19541. (15F) Severa, Zdenek, Pecik, Vaciav, 'Hoffrnann. Josef, Chem. P r u m ~ ~ ENO. 4 , 29,223-9 (1954). (16F) Strocchi, P., Gliozzi, E., A n n . Chinr. (Rome) 43, 602-10 (1953). (17F) Saold, E., Vajna. S.,Acta X e d . Acad. Sci. Hung. 6 , 419-32 (1954). (18F) Vanatta, J. C., Cox, C . C., J . B i d . Chern. 210, 719-32 (Oct. 1954). (19F) Wehrmeieter, H., U. S.Patent 2,698,821 (Jan. 4, 1955). (20F) Whitaker, J . R., Deatherage, F. E., J . Am. Chem. Soc. 77, 3360-5 (1955). (21F) Zinnitz, F., Med. Monatsschr. 9, 18-25 (1955). RECOVERY, PURIFICATION, PREPARATION, AND NEW RESINS
(1D) Baunian, W., U. 5. Patent 2,702,275 (Fcb. 15, 1955). (2D) Berry, A., Eng. and Contract Record 67, 124-31, 169 (1954). (3D) Blight, F., Akeroyd, 1.. Sard, B., Brit. Patent 724,003 (Feb 16, 1955). (4D) Calmon, C., Simon, G., IND.EXC.CHEM.46, 2404-6 (1954). (5D) Cummings, W. S., Smith, C. L., T a p p i 37,133-b4-4 (-kx1954) (6D) Kantebeen, L. J., Norm. Patent 78,252 (1952). (7D) Kunin, K., McGarvey, F., IND. ENQ. CHEM 47, 1230-5 (1955). (8D) Schmidt, P.,Offic.Bull. N. Dakota Water & Sewage Works 20, No. 4,lO-12,1952.
March 1956
BIOCHEMICAL SEPARATIONS
(1G) Anthes, J. A., Can. Patent 512,669 (May 10, 1955). (2G) Berntsson, S.,Samuelson, Olof. Acta, Chemica Scand. 9, 277-82 (1955). (3G) Beutel, R II,, U. s. patent2,712,515 ( ~5, lg55). ~ 1 ~ (4G) Brooks, J. D., J A p p l . Chem. (London) 5, 250-60 (June 1955). (5G) Bryce, II., U. S. Patent 2,697,725 (Dec. 21, 1954). (6G) Chem. Eng. S e w s 33,3165-6 (1955). (7G) Chemistry & I n d u s t r y 1955, No. 22,622. (8G) Diadar, J., Bull. Inst. Nuclear Sci. 4 , 31-54 (1954). (QG) Dvorakova, B., Tomko, J., Chem. Zvesta 8 , 193-200 (1954). (10G) Garino-Canina, Ettore, Ann. accad. agr. Torino 92, 13-26 (1949-50).
INDUSTRIAL A N D ENGINEERING CHEMISTRY
545
UNIT OPERATIONS REVIEW ~
(11G) Ghiorso, A., Harvey, B., others, Phys. Rev. 98, 1518-19 (June 1, 1955). (12G) Glass, R., J. Am. Chem. SOC.77,807-9 (1955). (13G) Gregor, II. P., Dolar, D., Hoeschele, G. K., Ibid., 77, 3675 (1955). (14G) Hamlow, E., DeKay, G., Ramstad, E., J . Am. Pharm. Aasoc. Sci. E d . 43,460-4 (1954). (15G) Harker, R. P., Chemistry & Industry 1954, No. 21, 592. (16G) Hellberg, H., J . Pharm. and Pharmacol. 7, 191-7 (1955). (17G) Hojo, H.. Kotera.. M... J . Chem. SOC.J a v a n . I n d . Chem. Sect. 55. ?92-4 (1952). Jindra, A., Motl, O., Ceskosloaenska Farmaeie 2, 190-1 (1953). Kadorntzeff, Irene, J . chim. phys. 51,197-200 (1954). Kimura, K., others, J a p a n Analyst 3, 335-48 (1954). Levi, L., Chatten, L., Pomarowski, M., J . Am. Pharm. Asaoc. 44,61 (1955). Lillin, H. V., Angew. Chem. 66,649 (Oct. 20, 1954). Lobo, J. Ma., Viguera, Botella, others, Andes real soc. espail. p s . y quim. ( M a d r i d ) 50B, 477-88 (1954). McGarvey, F., U. S.,Patent 2,695,875 (Nov. 30, 1954). Nature 174,817 (1954). Nelson. F., Kraus, K., J . Am. Chem. SOC.76, 5916-20 (1954). Ibid., 77,329-31 (1955). Okamoto, T., Tani, H., others, J . Phurm. Soc. J a p a n 74, 1405-7 (1954). 77, 3675-6 Overberger, C. G., Lebovits, .4.,J . Am. Chem. SOC. (1955). Parrish, J. R., Chemistry & I n d u s t r y 1955, KO.14, 356-7. Pollard, F. H., Brit. M e d . Bull. 10, 187--92 (1954). Rieman, W., Record Chem. Proy.. 15, 85-101 (1954). Security Trust Co. of Rochester, Brit. Patent 728,383 (April 20, 1955). Soloway, S., Schwartz, L., Science 121, 730-2 ( h h y 20, 1955). Stimpson, E. G., Riggs, L. K., U. S.Patent 2,708,633 (May 17, 1955). Thompson, S.,Harvey, B., others, J . Am. Chem. SOC.76, 6229-36 (1954). Van Elten, C. H., Anal. Chem. 27, 954-7 (1955). Villforth, F., M i t t . Klosterneubwg, Sey. A , Rebe u. W e i n 4, 212-24 (1954). Wesly, W., Mitt. Ver. Grosskesselbesitzer 1954, KO.30, 253-5. Wiseman, W. A., Brit. Patent 732,543 (June 29, 1955). Zafiriadis, Z.,Mastagli, P., Pierre, 0. R., Acad. Sei.Paris 240, 438-40 (1955). WASTE TREATMENT
(1H) Arden, T. V., Metal I n d . (London) 85, 513-16 (1954). (2FT) Black. H. H.. S e w m e and I n d . Wastes 26.’ 300-9 (1954). (3H) Brink, R. J , Ibid., i6,197-202 (1951). (4H) Electroplating and Metal Finishing 6, 121-30 (1953). (5H) Fraetkin, A., Tooper, E., IND.ENG.CHEM.47, 87-90 (1955). (6H) Gerstner, F., Cheni.-Ing.-Tech. 26, 264-9 (1954). (711) Ginell, W., Martin, L., Hatch, L., Nucleonics 12, 14-18 (Dec. 1954). @I€) Keating, R. J., Metal Finishing 52, No. 12, 52-5 (1954). (9H) Ledford, R., Hesler, J., IND.ENG.CHEM.47, 83-6 (1955). (10H) hlarkham, A. E., RlcCarthy, J. L., T a p p i 37, 355-63 (1954). (11H) Meinekata, Eiji, Ku, Nakano, others, U. S.Patent 2,707,671 (1955). (12H) Paulson, C., Mindler, A, Chein. Eng. Progr. Symposium Ser., No. 14, pp. 93 -6, 1954. (13H) Quarm, T. A . A,, Bull. Inst. &finingMet. 64, 109-17 (1954). (14H) Reents, A., Kahler, F., ISD. ENG.CHEW 47, 75-7 (1955). (15H) Swope, H., Anderson, E., Ibid., 47, 78-83 (1955). (16H) Wslters, W., Weiser, D., Marek, L., Ibid., 47, 61-7 (1955). (17H) Water & Sewage Works 102,285 (July 1955). \---I
.
I
CATALYSIS
(11) dstle, M. J., Schaeffer, B., Obenland, C. O., J. Am. Chena. SOC. 77, 3643-4 (1955). (21) Austerweil. G., Pallaud, R., Bull. SOC. chim. France 1954, 1164-7. (31) Austerweil, G. V., Pallaud, R., J . A p p l . Chem. (London) 5, 213-15 (May 1955). (41) Bafna, S. L., Bhale, V. M., Bhagwat, W. V., Paintindia 4, 36-7, 39 (1954). (51) Bilhmoria, J., NacLagan, N., J . Chem. Soc. 1954, 325762. (61) Hclfferich, I?., J . Am. Chem. SOC.76, 5567-8 (1954). (71) Koppers Co., Brit. Patent 721,150 (Dec. 29, 1954). (81) Losev, I., Trostyanskaya, E., Abad. hrauk. S.S.S.R. Otdel Khim. I f a u k 1950, 188-91 (1952). 546
(91) Mastagli, P., Durr, F., Bull. aoc. chim. France 1955, 26872. (101) Mowery, D., J . Am. Chem. Soc. 77, 1662-9 (1955). (111) Norten, T. R., U. S.Patent 2,711,414 (June 21. 1955). (121) Paulson, J., Deathorage, F., J . Am. Chem. SOC. 76, 6198-200 (1954). (131) Swistak, E., Mastagli, P., Compt. rend. 239, 709-11 (Sept. 20, 1954). (141) Zafiriadis, Z., Alastagli, P., Pierre, 0 , Ibid., 240, 43840 (Jan. 24. 1955). MEDICINAL
(15) Martin, G. J., “Ion Exchange and Adsorption Agents in
Medicine,” Little Brown, Boston, 1955. (25) Martin, G. J., Swayne, V. R., Beiler, J. A l . , Am. J . of Digest. Diseases 21, 293 (Oct. 1954). (35) Mertens, H. G., Gruttner, R., Ross, J., Klin. Wochschr. 33, 35-9 (1955). (45) Shay, H., Siplet, H., J . Am. Med. Assoc. 156, 224-7 (Sept. 18, 1954). (55) Spencer, A,, Lloyd-Thomas, 11, Brit. Med. J . 1954, I, 597603. (6J) Weiss, J., Am. J . Gastroenteiology 22, 64-72 (1954). APPARATUS, PROCESSES, A N D MISCELLANEOUS APPLICATIONS
(1K) Anderson, R., Hansen, R., IND.ENG.CREW47, 71-5 (1955). (2K) Bray, D., Reiser, C., U. S. Patent 2,694,681 (Nov. 16, 1954). (3K) Buhler, I>., Thomas, R., others, J . Am. Chem. Soc. 77, 481-2 (1955). (4K) Collier, D., U.S.Patent 2,697,724 (Dec. 21, 1954). (5K) Coryell, C., Marcus, Y., Bull. Research Council Israel 4, 90 (June 1954). (6K) Dryden, E. C., Buch, 11. L., Hills, C. II., Food Technol. 9, 264-8 (RIav 1955). (7K) Fisher, Sallie, Kunin, Robert, A n a l . Chem. 27, 1191-4 (1955). (8K) Gill, M. E., Self, J., U. S. Patent 2,703,313 (March 1, 1955). (9K) Gilwood, hl., Ibid., 2,702,795 (February 22, 1955). (10K) Gregor, H., Abolafia, O., Gottlief, AI., J . Phys. Chem. 58, 984-6 (1954). (11K) Gregor, H., Luttinger, L., Loebl, I:., Ibid., 59, 34-39 (1955). (12K) Ibid., pp. 366-8. (13K) Hagdahl, Lennart, Sczence Tools 1, 21-8 (1955). (14K) Iliestcr, N., Cohen, R . Phillips, R., Chem. Rng Progr. Syniposium Ser., No. 14, pp. 23 42, 1954. (15K) Higgins, I., Roberts, J., Ibad., pp. 57-92. (16K) Hirai, Is., Chem. Eng. ( J a p a n ) 18, 22-6 (1954). (17K) I N D . ENG.CHEY. 47, 14A ( l h y 1955). (18K) Jentzsch, D., Chem. Tech. (Berlin) 6, 339 (1954). (19K) Juneno, E., Ruiz, A., Anales real soc. espafi. fis y quim.(Madrid) 50B, 195-206 (1954). (20K) Katcholsky, A., Zwick, JI., J . Polymer Sci. 16, 221-34 (April 1955). (21K) Klumb, G., U. S.Patent 2,698,293 (Dec 28, 1954). (22K) Lambroso, R., Bull. soc. chim. France 1954, 1002-5. (23K) LeClerc, FL, Samuel, T., Bull. centre telge &tude et document. eaux (Libge) 1954, KO.26, 226-8. (24K) hlaterova, E. A., Vert, Zh. L., Grinberg, G. P., Zhur. Obshphel K h i m . 24, 953-65 (1954). (25K) J l f g . Chemist 26, 228 (May 1955). (26K) Jlindick, hi.,IND.EXG.CHEM.47, 96-101 (1955) (27K) Xindler, A., Paulson, C., Chem. Week 75, 43-56 (Doc. 18, 1954). (28K) Muendel, C., Selkc, W., Ibid., 47, 374-9 (1955). (29K) Olin, J., Koenig, W., others, Chem. Eng. Progr. Symposium Ser., No. 14, pp. 103-10, 1954. (30K) Radding, S. B., Phillips, R. C., Riester, N. K., Anal. Chim. Acta 11, 538-49 (1954). (31K) Reents, A., Stromquist, D., Can. Patent 513,143 (May 24. 1955). (32K) Sholto-Douglas, J. W. E. II., A’ature 175, 884-5 (1955). (33K) Skold, R., Wilkes, J., IND. ENG.C H m f . 47, 90-6 (1955). (34K) Smid, J., Radl, V., Chem. Pr&nzsyl 3, 179-82 (1953). (35K) Spencer, W., Gieseking, J., Soil Sci. 78, 267-76 (Oct. 1954). (36K) Standard Oil llevelopment Corp., Brit. Patent 715,877 (Sept. 22, 1954). (37K) Stoch, II., Angsw. Chem. 66, 571 (Sept. 7, 1954). (38K) Strobel, H., Gable, R., J . Am. Chem. SOC.76, 5911-16 (1954). (39K) Union des fabriques belges de tostiles artificiels “Fabelta,” Brit. Patent 714,665 (Sept. 1, 1955). (40K) Wheaton, R., Chem. Eng. Progr. Symposium Ser., No. 14, pp. 43-9, 1954.
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 48, No. 3
