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    ION EXCHANGE Friedrich Helfferich ION EXCHANGE Friedrich Helfferich zs DOVER PUBLICATIONS, INC. New York Thais one O0Z8E-QSD-WDLP E Published in Canada by General Publishing Company, Ltd., 30 Lesmill Road, Don Mills, Toronto, Ontario. Published in the United Kingdom by Constable and Company, Ltd., 3 The Lanchesters, 162-164 Fulham Palace Road, London W6 9ER. Bibliographical Note This Dover edition, first published in 1995, is an unabridged and unaltered republication of the work first printed in English by McGraw- Hill Book Company, Ine., New York, 1962, as part of the McGraw-Hill Series in Advanced Chemistry. The original German edition was published by Verlag Chemie GmbH, Weinheim/Bergstrasse, Germany, in 1959, under the title Jonenaustauacher. Library of Congress Cataloging-in-Publication Data Helfferich, Friedrich G., 1922- [onenaustauscher, English] Ton exchange / Friedrich Helfferich. Pp. cm. Originally published (in English): New York : McGraw-Hill, 1962. (McGraw-Hill series in advanced chemistry). Includes bibliographical references and indexes. ISBN 0-486-68784-8 (pbk.) 1. Ion exchange. I. Title. QD562.163H4513 1995 541.3°723—de20 96-4971 Manufactured in the United States of America Dover Publications, Inc., 31 East 2nd Street, Mineola, N.Y. 11501 Contents Preface . cui dh Gi Wei SS EES Bias ee 1. Elementary Principles. $e Bo 2 2. Structure and Properties of lon Exchongers.. - ss sO 21, Mineral Jon Exchangers. on ei isi ld wis 10 22. Synthetic Inorganic Yon | Exchanger ; = a2 23. Ton-exchange Resing =e 14 24. Ton-exchange Coals. a 25. Other Materials with Jonesthange Properties . =e ee eS 26. Liquid Jon Exchangers... 2 Beh es te BD, 2-7, Survey and Comparison ee 20 Summary... z : 20 “References ee 21 & Preperation . 0. Sirsa eee gt et 3-1. Principles. . gaat sre gee 2 27 3-2. Cation Exchangers pes zi 2 F 320) 3-3. Anion Exchangers. z Se : 47 3-4. Amphoteric Ion Exchangers 58 35. Particle Shape and Size, Macroreticular Resins, and Soper Ton Exchangers 59 3-6. Ton-exchanger Membranes. a z 61 Summary. 4. Copacity . 72 4-2. Apparent Capacity and Its Dependence on Experimental Conditions 79 4-3. pH Titration. . 81 ‘4, Determination of pK Values 84 45. Ripaiietel Mabaie. z 90 ‘Summary. Es see 93 ee a re 94 Obras protagidas por direitos de autor vit ‘CONTENTS: 5-1, Theoretical Ano and Models . 96 5-2. Swelling. as oy . 100 5-3. Sorption of Solutes . 5 5 SSS 135 5-4, Ton-exchange Equilibria. sess itv DEB 5-5. Systems with More Than Two Counter-ion Species... 200 5-6. Ton-exchange Equilibria Involving Complexing Agents : 208 5-7. “Ligand Exchange”. ed ae 5-8. Reactions with Materials of Low Sob SS, 226 5-9. Experimental Methods. a area . 229 Summary... SS __ 239 6. Kinetics r 250 6-1, Mechanism of Jon Exchange... Ss ad _ 250 6-2. The Rate-determining Step. ee 852 6.3. Rate Laws of Ton Exchange g aes 257 6-4. Empirical and Simplified Rate Laws. === ae 65. Systems with More Than Two Counter-ion Speen jie . 88 6-6, Kinetics of Sorption and Swelling. z —s 289 6-7._Reactions with Materials of Low Solubility... ... 205 6-8. Diffusion Coefficients in Ton Exchangers. =e 299 69. Bapestsiostal Methods... = ee 309 Summary. Sie S25 we ee eo eB References. oe 319 7. Electrochemical Properties. tesco sac est sere se ere eee Se 7-1, Electric Conductivity . ics Bast 323 7-2. ‘Transference Numbers and Transport Numbers ; zs 326 7-3. Transference of Solvent; Convection Conductivity. coe . 827 7-4. Quantitative Relations. a eotas 328 7.5. Experimental Methods = == 333 Summary... : sat od at en i_ne 336 References. i _ _ 336 8. lon-exchonger Membranes. ss a 339 8-1. Characteristic Properties of Ion-exchanger Membranes 340 $2. Models and Theoretical Approaches... 5 342 8-3. Diffusion across Membranes... ——e . $4, Membrane Potentials . 368 85. General Integration of the Nernst-Planck Equations. ._ 385 &6,__Anomalous Osmosis 389 “8:7. Streaming Potential, Streaming Current, and Hlstolte Filtration 301 8-8, Transport of Electric Current across Membranes . . 397 8-9. Sorting Effects . , Se ue es 3 M8 ‘$10. Experimental Methods. | | |. coe 409 Summary. 2 eg Wis a ole 2 _ 414 References _ _ _ - _ 417 Q.lonexchonge Columns. 9-1, Ton Exchange in Columns. . ee _ 422 9-2. Conventional Column Operation... =. . . . ~ 428 Obras protegidas por direitos de autor CONTENTS ix 9-3, Two-stage, Multistage, and Mixed-bed Deionization 430 9-4, Ton Exclusion : a= 431 9-5, Ion Retardation. 433 9-6. Separation by Selective Displacement. 434 9-7. Principles of Ion-exchange Chromatography. 436 9.8. “Ligand Exchange” and Other Techniques Based on Chemical Reactions 445, 9-9. Quantitative Treatment. z 447 9-10. Hydrodynamic and Thermochemical Effects. 485 9-11. Electrochemical Properties. 489 9-12, Experimental Methods. 493 Summary 495 References 499 10, Behavior in Nonaqueous and Mixed Solvents 507 10-1, Ton Exchange in env fetes 508 10-2. Swelling. 2.5 309 10-3. Capacity : : 312 10-4. Ton-exchange and Sorption Equilibria .. 5B 10-5. Kinetics = 515, 10-6. Electrochemical Properties. 516 Summary 57 References. 517 1. Catalysis by lon Exchangers. me st nee a 11-1, Resetions of Gases and Vapors ffs Sa _ 519 11-2, Reactions of Liquids and Solutes . : _ 822 11:3. Kinetics ee ae ge ee 524 11-4. Experimental Methods . ——— Summary é es @ Bid #@ el hs 48 References. = =i ee) 12. Electron Exchangers and Redox lon Exchangers. . . . . » . ) ss 551 12.1. Preparation E 552 12-2. Reactions and Applications : = 556 123. Physicochemical Properties Sms a8 7. 689 12-4, Experimental Methods. Se Summary. | ae # ew a ~ OT References $e a & 367 Symbols, Abbreviations, and Units... 569 ‘Commercial Ion Exchangers. . Fog a aes ‘74 Tables of Mathematical Functions 0.4... Nome Indep 0 Subject Index. 85.8 82 i Be bos Soi ee Obras protegidas por direitos de autor Introduction “Corpora non agunt nisi fluida sive soluta’”—substances do not react unless in a liquid or dissolved state. This ancient empirical rule is not universal. One of the noteworthy exceptions ision exchange. Here, a solid reacts with a solution. Ions can be exchanged and electrolytes and even precipitates can be removed by treating the solution with a solid ion exchanger. These reactions are by no means a recent discovery. Nature makes extensive use of them and has done so long before man attempted to eluci- date and apply its principles and to copy and surpass its performance. Ion exchange occurs in inanimate soils, sands, and rocks, and in living organisms. At first, these processes remained unnoticed by chemists, geologists, and biologists. Later, when ion exchange in soils was dis- covered, it was considered as an exceptional phenomenon, a “miracle,” in which other than purely natural causes were supposed to have their part. To show that here, too, the well-established rules of nature hold remained the task of scientists in the second half of the nineteenth century. Still later, about two decades ago, organic chemists succeeded in synthesizing ion exchangers which proved to be far superior to the natural materials, Jon exchange in living organisms is indispensable for most vital functions, but its significance remained obscure until recent times. Only in our day has progress been made in understanding this phenomenon. Ton exchange has an interesting history. Thorough investigators have shunned no efforts to discover ancient references. The earliest of these, it seems, is found in the Holy Bible. In establishing Moses’ priority it reads They could not drink of the waters of Marah, for they were bitter. ... And he cried unto Jehovah; and Jehovah showed him a tree, and he cast it into the waters, and the waters were made sweet. Exodus 15: 23-25 2 INTRODUCTION ‘Thus Moses succeeded in preparing drinking water from brackish water, undoubtedly by an ion-exchange technique which he developed on an industrial scale. About a thousand years later, Aristotle stated that sea water loses part of its salt content when percolating through certain sands [2]. Subsequent to this time, only scarce references are found until, in 1850, Thompson [8] and Way [9], two English chemists, rediscovered “base exchange” (cation exchange) in soils. The materials which are responsible for these phenomena were identified chiefly by Lemberg [7] and later by Wiegner [10] as clays, glauconites, zeolites, and humic acids. These discoveries led to attempts to use such materials in plant operations for water softening and other purposes and to synthesize products with similar properties. The first synthetic industrial ion exchanger was pre- pared in 1903 by Harm and Riimpler [4], two German chemists. Gans (3), also a German and perhaps the most colorful pioneer of ion exchange, had far-reaching applications in mind even at that time, for example, the recovery of gold from sea water. However, the “permutits” then available proved to be inadequate for such ambitious plans. A spectacular evolution began in 1935 with the discovery by two English chemists, Adams and Holmes, that crushed phonograph records exhibit ion-exchange properties. The study of this remarkable effect led the inventors to the synthesis of organic ion-exchange resins which had much better properties than any of the previous products [1]. These new resins were developed and improved by the former I. G. Farbenindustrie in Ger- many, and after World War II chiefly by companies in the United States and England. Nearly all current industrial and laboratory applications of ion exchange are based on such resins. At the same time, the synthesis of organic resins made it possible to vary the properties of ion exchangers in a systematic manner. A large part of our present theoretical knowledge is due to this latter fact. It is an outstanding achievement of organic chemistry to have surpassed the performance of nature which, in this case, makes use of inorganie substances. Today, ion exchange is firmly established as a unit operation and is an extremely valuable supplement to other procedures such as filtration, distillation, and adsorption. All over the world, numerous plants are in operation, accomplishing tasks that range from the recovery of metals from industrial wastes to the separation of rare earths, and from catalysis of organic reactions to decontamination of water in cooling systems of nuclear reactors. In the laboratory, ion exchangers are used as an aid in analytical and preparative chemistry. The aims of scientific research with ion-exchanger membranes extend far into physiological chemistry and biophysics. However, the most important application is still the purifica- tion and demineralization of water, a perennial challenge since Moses and Aristotle, and a task which the growth of population and industries has made more pressing than ever. INTRODUCTION 3 The development of ion-exchange resins and their applications progressed so rapidly that the theory lagged behind. For a considerable time ion exchangers were used on a purely empirical basis and without the possibil- ity of predicting efficiency and optimum operating conditions. The only exception is the most recent product, the ion-exchanger membrane. When synthesized in 1950 [5,6] the ion-exchanger membrane fitted nicely into the essentially complete theoretical framework which had been worked out for physiological, collodion, and other membranes. Ton-exchanger membranes have not only opened up new technological possibilities but, in addition, Number of publications oc 1946 1950 1955 Yeor Fra. 1. Number of scientific publications on ion exchange as a function of time. From R. Kunin and PF. X. McGarvey, Ind. Eng. Chem., 47, 565 (1955). have contributed to a better understanding of the electrochemical and kinetic phenomena in ion exchange. This, in turn, proved to be of great value to the general theory of ion-exchange materials. After a period characterized by predominantly empirical approaches, research efforts in the last fifteen years have led to a comprehensive and consistent picture of the relevant factors in ion exchange. This picture may be considered as qualitatively and quantitatively sound, though a few questions remain unanswered and the solution of certain equations poses mathematical difficulties. At the same time, the scientific literature on ion exchange has grown to such an extent that it has become virtually 4 INTRODUCTION impossible for a single individual to keep track of every detail. The constant increase in the number of publications (see Fig. 1) may be taken as the best evidence for the spreading interest in ion exchange and for the hopes and expectations that accompany its future development. REFERENCES . Adams, B. A., and E, L. Holmes, J. Soc. Chem. Ind. (London), 64, 1T (1935). . Aristotle, Works, vol. 7, p. 933b, about 330 3.c. (Clarendon Press, London, 1927). . Gans, R., Jahrb. preuss. geol. Landesanstalt (Berlin), 26, 179 (1905), and 27, 63 (1906); Zentr, Mineral. Geol., 22, 699, 728 (1913); Ger. Patent 174,097 and 197,111, 1906, Harm, F., and A. Riimpler, 5th Intern. Congr. Pure Appl. Chem., 1908, 59. Juda, W., and W. A. McRae, J. Am. Chem. Soc., 72, 1044 (1950); U.S. Patent 2,636,851-52, 1953. Kressman, T. R. E., Nature, 166, 568 (1950). Lemberg, J., Z. deut. geol. Ge 22, 355 (1870); 28, 519 (1876). ‘Thompson, H. S., J. Roy. Agr. Soc. Engl., 11, 68 (1850). Way, J.T., J. Roy. Agr. Soc. Engl., 11, 313 (1850); 18, 123 (1852). ). Wiegner, G., J. Landwirtsch., 60, 111,197 (1912). ee oe Beane 1 Elementary Principles Ion exchangers, by common definition, are insoluble solid materials which carry exchangeable cations or anions. These ions can be exchanged for a stoichiometrically equivalent amount of other ions of the same sign when the ion exchanger is in contact with an electrolyte solution. Carriers of exchangeable cations are called cation exchangers, and carriers of exchange- able anions, anion exchangers. Certain materials are capable of both cation and anion exchange. These are called amphoteric ion exchangers. A typical cation exchange is 2NaX + CaCla(ag) = CaX: + 2NaCl(ag) (1-1) and a typical anion exchange is 2XCl + Na:SO«(ag) = Xs80. + 2NaCl(ag) (1-2) X represents a structural unit of the ion exchanger; solid phases are underlined; aq indicates that the electrolyte is in aqueous solution. The process (1-1) occurs, for example, in water softening by ion exchange. A solut’ »n containing dissolved CaCl: (hard water) is treated with a solid ion exchanger NaX containing exchangeable Na*ions. The ion exchanger removes the Ca*+ ions from the solution and replaces them by Nat ions. An ion exchanger containing, say, exchangeable Na* ions is said to be in Na+ form. In the process (1-1) the cation exchanger, originally in Na* form, is “converted” to the Ca*+ form. Complete conversion to, say, Ca** form can be achieved by treating the ion exchanger with a suffi- cient excess of a solution of a calcium salt. Ion exchange is, with very few exceptions, a reversible process. In water softening, for example, a cation exchanger which has lost all its Na+ ions and thus has become “exhausted,” can be “regenerated” with a 5 6 ELEMENTARY PRINCIPLES: (Chop. 1 solution of a sodium salt such as NaCl. In regeneration the process (1-1) is reversed, and the ion exchanger is reconverted to the Nat form. Ton exchange resembles sorption in that, in both eases, a dissolved species is taken up by a solid. The characteristic difference between the two phenomena is that ion exchange, in contrast to sorption, is a stoichiometric process. Every ion which is removed from the solution is replaced by an equivalent amount of another ionic species of the same sign. In sorption, on the other hand, a solute (an electrolyte or non- electrolyte) is taken up without being replaced by another species. This Initial stote Equilibrium LP wotrix with fixed charges @ @ Counter ions © Co-ions Fic. 1-1. Ton exchange with a solution (schematic). A cation exchanger containing counter ions A is placed in a solution containing counter ions B (eff). The counter ions are redistributed by diffusion until equilibrium is attained (right) distinction seems clear-cut. However, it is sometimes difficult to apply it in practice since nearly every ion-exchange process is accompanied by electrolyte sorption or desorption, and most of the common sorbents such as alumina and activated carbon can act, in turn, as ion exchangers. Ton exchangers owe their characteristic properties to a peculiar feature of their structure. They consist of a framework which is held together by chemical bonds or lattice energy. This framework carries a positive or negative electric surplus charge which is compensated by ions of opposite sign, the so-called counter ions. The counter ions are free to move within the framework and can be replaced by other ions of the same sign. The framework of a cation exchanger may be regarded as a macromolecular or crystalline polyanion, that of an anion exchanger as a polycation. To give a very simple picture, the ion exchanger may be compared to @ sponge with counter ions floating in the pores. When the sponge is immersed in a solution, the counter ions can leave the pores and float Chap. 1] ELEMENTARY PRINCIPLES: 7 out. However, electroneutrality must be preserved, ie., the electric sur- plus charge of the sponge must be compensated at any time by a stoichio- metrically equivalent number of counter ions within the pores. Hence a counter ion can leave the sponge only when, simultaneously, another counter ion enters and takes over the task of contributing its share to the compen- sation of the framework charge. According to this simple model, the counter-ion content of the ion exchanger—the so-called ion-exchange capacity—is a constant which is given solely by the magnitude of the framework charge and is independent of the nature of the counter ion. The actual situation is somewhat more complex because electrolyte sorption may occur (see below and see Chap. 4). When an ion exchanger in A form (where A is an arbitrary counter ion) is placed in a solution of an electrolyte BY, counter ions A will migrate from the exchanger into the solution and counter ions B* from the solu- tion into the ion exchanger, i.e., an exchange of counter ions takes place, After a certain time, ion-exchange equilibrium is attained. Now, both the ion exchanger and the solution contain both counter-ion species A and B. The concentration ratio of the two counter ions, however, is not necessarily the same in both phases. As a rule, the pores are occupied not only by counter ions but also by solvent and solutes which can enter the pores when the ion exchanger is in contact with a solution. Uptake of solvent may result in swelling of the ion exchanger. Uptake of solutes is usually called sorption, though it is essen- tially a distribution of the solute between two liquid phases, namely, the pore liquid and the solution outside. Sorption of an electrolyte increases the counter-ion content of the ion exchanger. The sorbed counter ions, which are present in addition to those compensating the framework charge, are accompanied by an equiva- lent amount of so-called co-ions.* These are mobile ions with charges of the same sign as the framework charge. The counter-ion content of an ion exchanger thus depends not only on the magnitude of the framework charge but also on its co-ion content. The common definitions of ion- exchange capacities refer, for this reason, to ion exchangers which are free of co-ions. * Often the term “counter ion” is used exclusively for ions within the ion exchanger. According to this definition an ion becomes a counter ion only when entering the ex- changer. In this book, the notation will be used in a broader sense: whether in the exchanger or in the external solution, all ionic species with charge sign opposite to that of the exchanger framework will be called counter ions. Correspondingly, the notation co-ions will be used for all ionic species with the same charge sign as the exchanger framework. 8 ELEMENTARY PRINCIPLES [Chap. 1 In the discussion above and later in this book, the interstices in the framework are called “pores,” regardless of their actual geometric form. Often the term pore is used specifically for channels or capillaries of uniform cross section. Channels of this kind are present in only a few mineral ion exchangers. Most ion exchangers have an irregular, three-dimensional framework which resembles, in some respects, the crisscrossing steel struc- ture of a bridge or a television tower. Here, the “‘pores” are the void spaces between the girders. The simple model outlined above represents the most important properties of ion exchangers correctly. It shows at first sight why ion exchange is a stoichiometric process and why the capacity does not depend on the nature of the counter ion. The physical cause for both facts is the electroneutral- ity condition. In addition, the model shows that ion exchange is essentially a statistical redistribution of counter ions between the pore liquid and the external solution, a process in which neither the framework nor the co-ions take part. Therefore Eqs. (1-1) and (1-2) should be rewritten: 2Nat + Ca* = Ca + 2Nat (1-3) 2CF + S0}- = S0F + 2¢c1- (4) Quantities with bars refer to the inside of the ion exchanger. The model also describes ion-exchange kinetics correctly. Ion exchange is a diffusion process. Its rate depends on the mobilities of the counter ions. Thus ion-exchange kinetics has no resemblance to chemical reaction kinetics in the usual sense. However, the simple, well-known rate laws of diffusion hold only in exceptional cases. As a rule, electric forces affect the fluxes of the ions and cause deviations (see Chap. 6). Occasionally, ion exchange has been referred to as a ‘‘chemical’’ process, in contrast to adsorption as a “physical” process. This distinction, though plausible at first glance, is misleading. Usually, in ion exchange as a redis- tribution of ions by diffusion, chemical factors are less significant than in adsorption where the solute is held by the sorbent by forces which may not be purely clectrostatic. The absence of an actual chemical reaction also explains why the heat evolved in the course of ion-exchange processes is usually rather small (often less than 2 kcal/mole, unless ion exchange is followed by reactions such as neutralization, etc.). It has been mentioned above that, in ion-exchange equilibrium, the con- centration ratios of the competing counter-ion species in the ion exchanger and in the solution are not the same. As a rule, the ion exchanger pre- fers one species to the other. This shows that the redistribution of the counter ions is not purely statistical. The preference for one species may have several causes. The most important of these are: Chop. 1] ELEMENTARY PRINCIPLES: 9 1. The electrostatic interactions between the charged framework and the counter ions depend on the size and, in particular, on the valence of the counter ion. 2. In addition to the electrostatic forces, other interactions between the ions and their environment are effective. 3. Large counter ions may be sterically excluded from the narrow pores of the ion exchanger. All these effects depend on the nature of the counter ion and thus may lead to preferential uptake of a species by the ion exchanger (see Sec. 5-4). The ability of the ion exchanger to distinguish between various counter ion species is called selectivity. The selectivity is not adequately explained by the simple sponge model. The electrochemical properties of ion exchangers are readily interpreted in terms of the sponge model. Swollen ion exchangers have a high electric conductivity which is due to their high content of mobile ions (see Chap. 7). The model also shows that the ion exchanger must contain many more counter ions than co-ions. Many electrochemical phenomena in systems with ion-exchanger membranes can be explained with this fact (see Chap. 8). The model also gives an obvious explanation for the catalytic activity of ion exchangers. Reactions which are catalyzed by certain ions in solution can occur equally well in the pores of an ion exchanger which contains the catalytically active species as the counter ion (see Chap. 11). For a quantitative treatment, 2 model as simple as the charged sponge is, of course, insufficient. Nevertheless, this model is often useful in explain- ing the mechanisms of the processes. SUMMARY Ion exchangers consist of a framework carrying a positive or negative electric surplus charge which is compensated by mobile counter ions of opposite sign. Cation exchangers contain cations, and anion exchangers anions, as counter ions. The counter ions can be exchanged for other ions of the same sign. The exchange is stoichiometric and, as a rule, reversible. Ton exchange is essentially a diffusion process and has little, if any, relation to chemical reaction kinetics in the usual sense. Usually the ion exchanger is selective, i.e., it takes up certain counter ions in preference to others. Ton exchangers can also sorb solvent and solutes. A simple model for the ion exchanger is a sponge carrying an electric charge which must be compen- sated by charged particles within its pores. Many phenomena can be qualitatively explained with this model. 2 Structure and Properties of lon Exchangers Many different natural and synthetic products show ion-exchange prop- erties. The most important of these are ion-exchange resins, ion-exchange coals, mineral ion exchangers, and synthetic inorganic ion exchangers. Several other types of ion exchangers are historically interesting, but are now obsolete. Still others are used for special purposes. The general structural principle—a framework with electric surplus charge and mobile counter ions—is common to all ion exchangers. Never- theless, the various types of materials show marked differences in behavior. Characteristic features of the most important and interesting materials will be briefly discussed in this chapter. 2-1. MINERAL ION EXCHANGERS, Most natural ion-exchange minerals are crystalline alumosilicates with cation-exchange properties. Characteristic representatives of this group of materials are the zeolites which include, among others, the min- erals analcite, Na[SizAlO

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