Introduction to Liquid Ion Exchangers

1
Introduction to Liquid Ion Exchangers

1.1 INTRODUCTION
Solvent extraction has become a very powerful method of separation for various reasons. One amongst them is, it is very simple, rapid, selective and sensitive. This method does not need any kind of sophisticated instrument excepting a separating funnel. The organic chemists have rendered yeomans service to analytical chemists by synthesizing an array of ligands with different functional groups containing varying donor atoms. The solvent extraction domain is dominated by the extraction by chelation or compound formation. It has received maximum attendation due to an array of reagents available for the purpose of separations in solvent extraction. Ion exchange is another method which is quite effective for the purpose of separations at macro and microgram concentrations. On account of discovery of plate theory one could easily predict and design the column from optimum conditions of sorption and carry out the separations. The efficiency of ion exchange separation could be easily improved by increasing column height or in other words increasing the number of theoritical plates (HETP) while in solvent extraction, efficency of separation could be accomplished by multiple extractions or counter current extractions. Liquid ion exchangers as the name implies combines the advantages of both solvent extraction as well as of ion exchange techniques. The greatest advantage of liquid ion exchanger is that one could regenerate the resin and use it again and again. Therefore the process becomes economical. This is one of the reasons why most of industrial processes for recovery of metals from minerals prefer the use of liquid cation exchanger like LIX 64 N or liquid anion exchangers like Alanine 336 or Amberlite LA-1.

1.2 HISTORICAL DEVELOPMENTS

The solvent extraction method has made great strides in last four decades. A number of monographs have been published15 dealing with various aspects of solvent extraction. Some of them put emphasis on the theory of chelats extraction25 while others have dwelt on rigorous treatment of extraction equilibria46 or on the mechanism of extraction. Few of

Solvent ExtractionSeparation of Elements with Liquid Ion Exchangers

them have ramification with aspect of solvent extraction12. The chemical engineering aspect pertaining to design and development have been covered by worthwhile monographs79. The handbook10 of solvent extraction is an excellent source of information on all aspects of the extraction. The modern chemistry of supramolecules in solvent extraction is very well covered in a recent research monograph11 by the author.

1.3 BASIC WORK

The first discovery of extraction method dates back to 1842 when Peligot12 discovered a novel method for the extraction of uranium(VI) with ethylacetate or diethyl ether. This was followed by intensive study1314 on the solvent extraction of iron (III) with diethyl ether from hydrochloric acid. Serious attempts15 were made to replace explosive diethyl ether with an equivalent solvent without much success. The solvent extraction methods were put on firm footing by Nernst16 by formulating an equation satisfying thermodynamic consideration of concentration as well as the activity coefficent of solute both in aqueous and the organic phase. When dithizone17, 18 was first discoverd by Fisher there was a great excitement as by just controlling pH of the solution one could extract as many as six metals with dithizone in chloroform or carbon tetrachloride as diluents. This was followed by the discovery of the cupferron19. It was an ideal reagent for both iron (III) and copper (II) at varying conditions of extractions. Since it was used for extraction of both copper as well as iron it was designated as cupferron. Sandell and his group20 discovered dimethyl-glyoxime which was a real landmark in the chemistry of organic ligands. In spite of development of sophisticated instruments for the analysis of metals, dimethyl glyoxime, continues to enjoy favoured place for the complexation of nickel, palladium and bismuth. Oxine was also an equally promising21 ligand.

1.4 EQUILIBRIA
An extensive account of extraction equilibria was given by many chemists2226. They presented a vivid picture of the extraction behaviour and enumerated various parameters which influenced the process of extraction. They attempted to classify various extraction systems. The significance of the KD or D in predicting stability of a complex was ascertained rigorously by equation22, 23, in overall extraction. The authoritative reviews2427 are a landmark in extraction chemistry which deal with various factors influencing the process of extraction and the possibility of using them in analytical chemistry2729 which was favoured by many workers. Quantitative interpretion of extraction equilibria and factors promoting separation were reviewed3031 in analytical chemistry.

Introduction to Liquid Ion Exchangers

Table 1.1
S. No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

International Solvent Extraction Conferences (ISEC)

Year 1965 1966 1968 1971 1974 1977 1980 1983 1986 1988 1990 1993 1996 1999 2002 2005 Place where held Harwell Gothenburg Jerusalem Hague Lyon Toronto Leigh Denver Munich Moscow Kyoto York Melbourne Barcelona Johannesberg Montreal Name of sponsoring country U.K. Sweden Israel Netherlands France Canada Belgium USA Germany Russia Japan U.K. Australia Spain South Africa Canada

1.5 SEPARATION METHODS

The separation science plays a significant role in analytical chemistry. In the past many methods have been developed using large number of sophisticated instruments. It facilitated quantitative analysis of metals from milligram (103) to ato level (1018). The methods were rapid and sensitive. They included absorption spectroscopy, fluorosence technique, plasma spectroscopy including atomic absorption method and numerous electroanalytical and radiochemical methods. However, inspite of these methods being so sensitive and selective, for the purpose of quantitative analysis the demand grew for analysis of extra pure materials specially those free from interfering components. Some methods could not furnish reliable results if in case nanogram (109) impurities were present. This led to search for reliable methods for the purpose of isolation and purification of compounds before one could undertake the task of instrumental quantitative analysis. Many separation methods are described in authoritative monographs3244. Each of them is important in a true sense. An account of various separation methods3236 like chromatography, reversed osmosis, electrophoresis, dialysis are available in the monographs3744. They indicate how an excellent instrumental method of analysis can be used if supplemented by an efficient separation technique. All colorimetric methods3742 need preliminary separation of impurities. In the presence of such impurities it would influence the process of analysis. Some books4344 present information on the specialised methods for the isolation and determination of rare metals or the radioactive isotopes. Only few methods were an exception to this rule of pre-separation as are atomic absorption spectroscopy or inductively

Solvent ExtractionSeparation of Elements with Liquid Ion Exchangers

coupled plasma atomic emission spectroscopy which generally do not need preliminary treatment of sample solution for separation. Amongst separation methods so far utilized, solvent extraction occupies the most favoured position.

1.6 CLASSIFICATION
The solvent or liquid-liquid extraction methods have been broadly classified on the basis of process of extraction. Based on this the four broad categories of extraction4 were given as extraction by chelation or compound followed by a method of extraction by solvation or ion pair formation and the blending of these two methods into synergic extraction.

1.7 CHELATION
The major share of success for the extraction procedure goes to extraction by chelation. As described earlier the discovery of dithizone, cupferron, dimethylglyoxime or 8hydroxyquinoline have permitted extractive separation of large number of elements. This group of extraction also includes acid alkylphosphoric acid derivatives (i.e. liquid cation exchangers). Unfortunately none of the chelation methods had applications in the industrial scale operation. However, for analytical chemists the methods were a blessing, as many chelating agents like say 2-thenoyltriflurocetone 1 or 8-hydroxy2quinoline permitted simultaneous extraction and direct photometric determinations in one single operation. Even with newly discovered thia or aza crown ethers11 the direct extraction and colorimetric determination of metals was the most popular mode of analysis.

1.8 SOLVATION
In nuclear energy programmes, the greatest contribution pertains to solvation system. The versatile solvating solvents like TBP, TBPO, TOPO or simple compounds like diethyl ether, ethyl acelate or MIBK which facilitated separations of various elements like uranium, thorium, plutonium or californium. The method of substochiometric extraction44 was quite satisfactory for analysis of various isotopes of elements. Even common transition metals like zirconium, hafnium, niobium and tantalum or series of transition elements or the elements like uranium or thorium were separated with solvating solvents like TBP. In such a system more the basic solvent it offered better the extraction. TBP>TBPO>TOPO (order of extractibilty). The last-named compound provided better extractions. Apart from basicity the electron density sorrounding the donor atom was of utmost significance. CH3CH2 O .. CH2 CH 3
..

diethyl ether (I) In the above example oxygen is the donor atom the electron density around it in compound (II) being large the repulsion increase to retard the process of extraction. Apart from this the presence of salting out agents also enhance extraction e.g. uranyl nitrate from nitric acid media containing lithium nitrate gave better extraction as the latter increased the anionic concentration viz. NO3.

ClCH2CH2 O .. CH2CH 2Cl - dichloro ether (II)

..

Introduction to Liquid Ion Exchangers

The addition of lithium nitrate decreased the dielectric constant of the aqueous phase thereby promoting extraction due to better association of ions and finally by removing the water molecules from the coordination sphere of the metal to give room for the solvent molecule. Many worthy separations have been carried out in the solvation system on pilot plant scale. The synergic extraction is a system dealing with combination of the two extractants e.g. uranyl nitrate was better extracted with mixture of TBP as well as HDEHP (bis-2 ethyl hexyl) phosphoric acid. This was because the stablisation factor increases due to joint action of process of solvation as well as chelation leading to the synergic extraction. Large number of systems could show synergic extraction. Unfortunately none of the synergic extraction systems have been used in industry for recovery of ion or purification of metals by such system on pilot plant scale.

1.9 ION PAIR FORMATION

Another way of classification of extraction process is largely based upon a kind of acidic or basic solvents used for extraction e.g. extraction with (H-DNNS) dinonylnapthenic sulphonic acid is an example of acidic extraction while extraction with high molecular weight amines (HMWA) is usually termed as basic extractions. In fact both systems viz. acidic or basic extractants have one thing in common namely the extraction proceeds by ion pair formation. An anionic species associates with suitable cation to form an uncharged species which readily undergoes quantitative extraction1, 2, 6. An authoritative review on solvent extraction by ion pair formation4550 have appeared outlining influence of various parameters influencing process of extraction. A review article by Smith46 and Coleman47 or by Green48 and Khopkar49 are real landmarks in the chemistry of extraction by ion pair formation. The other reviews49, 50 have brought out real examples of the solvent extraction with high molecular weight amines.

1.10 ALKYLPHOSPHORIC ACIDS

At this juncture, it is worthwhile to explain the significance of the words Liquid cation exchangers. Now, all acidic alkylphosphoric acids, napthenic acid, caporic acid or similar fatty acids are examples of liquid cation exchangers. This is because the extraction proceeds in same manner as one in solid cation exchange reaction in column. If orefers to organic phase, R = ligand and M is metal with valency n. [H2 R]0 + Mn+ (Mn R)0 + 2H+ In this example we note that a proton was replaced by metal ion Mn+ with the valency as n either in resin phase in cation exchange reaction in column or in solvent extraction in the organic phase. In view of the fact that the exchange proceeds with reference to cation and since extractants were mostly used in liquid form, we designate these process as liquid cation exchange reaction. All fatty acids have protons which were exchanged by metal ions.

Solvent ExtractionSeparation of Elements with Liquid Ion Exchangers

1.11 AMINES
As far as the significance of liquid anion exchanger was concerned, all high molecular weight amines (HMWA) were termed as liquid anion exchangers. These amines might be primary, secondary, tertiary or quaternary and depending upon the kind of extraction one, two, three or four hydrogen atoms are replaced by anionic species to form the complex e.g. if R3 NH+ was tertiary amine and underwent reaction with anion in the following manner
R3 N + H

+ Cl

(R NH Cl )
3 + 2

a uncharged complex was formed. Now this salt of amine when contacted with anionic chloro complex e.g. (PtCl62) we had

R NH+ PtCl + Cl 6 2 0 3 + So we have an ion pair with cation as (R3NH ) with uncharged anion as (PtCl62) forming ion which is a paired complex. Such extraction is common in purex process for recovery of uranium e.g. the sulphate complex during extraction with HMWA. Since we use amine in liquid form and since the reaction proceeds with the exchange of anion, the whole product was called liquid anion exchangers. There are many amines as TOA, TIOA, TLA, MDOA, etc. Further we have synthetic amines like Primene JM-T (primary), Amberlite LA-2 (tertiary) or Aliquat 336 (quaternary) amine. Higher the basic amine, better was the process of extraction. On these assumptions the extractability varies with rise in extraction from primary> secondary> tertiary> quaternary amines.
+ 3 0

(R NH Cl )

+ ( PtCl6 )

1.12 NEW FACETS

Before undertaking extensive discussion on the applications of liquid ion exchangers in analytical chemistry it is worthwhile to undertake description of some recent work on important facets of solvent extractions with liquid ion exchangers5165 which were noted in the last few years during extraction studies. An interesting review on extractions involving organophosphorous compounds or sulphur containing alkyl sulphoxides, high molecular weight amines and quinoline compounds51 was published. An attempt was made to draw an analogy52 between amine extractions of metals and their anion exchange sorption on the solid anion exchange resin in column. A useful chart was prepared53 listing the extraction of many elements with quaternary amines from all mineral acid solutions mostly based on the value of the distribution constants along with investigations on the mechanism of extraction. An exhaustive account54 on extraction of selected metals with alkyl amine or their corresponding salts as well as extractions with alkyl organophosphorous compounds was carried out. The extraction of anionic chloro complexes of iron, cobalt, indium and gallium were extracted with quaternary ammonium compounds in aromatic hydrocarbons. This revealed that the process represents anion exchange phenomena55 as was seen in columnar work. Another review appeared almost the same time in 1964 on extraction of metals with high molecular weight amines. A similar authoritative review appeared on extractions with quaternary ammonium compounds of the transition elements56, 57 as well as inner transition elements58. A typical example cited was the synergistic extractions involving two extractants viz. chelating agent and aliphatic or aromatic amine59. The role

Introduction to Liquid Ion Exchangers

of organic polymers as ion exchanger was stressed in another review 60. A paper chromatographic studies61 were carried out using with Amberlite SA-2 and SB-2 paper strips and mixtures of chelating extractants like 2-thenoyltrifluoro acetone (TTA) to separate several multi-component mixture of the metals. A general review on extractions in analytical chemistry62 comprised of the inorganic compounds and organometallic complexes by water immiscible solvents. Another review63 was presented on extractions in chemistry in the past three years (19591961). A large number of papers presented in Conference on Separation Science and Technology included several high molecular weight amines64. A specfic reference merits mention of liquid cation exchangers like LIX 65N (2hydroxyl 5-nonyl benzophenone oxime) from the viewpoint of extraction equilibria and stripping in process of extraction.

1.13 APPLICATIONS OF AMINES IN SEPARATIONS

The high molecular weight amines or liquid anion exchangers facilitated several separations; the important being separation of uranium and transuranium elements. The most interesting factor of these extractions was that not only they facilitated separation of the chemically similar elements like zirconium and hafnium87 or niobium and tantalum or gallium, indium and thallium but they also provided selective methods for their separations specially of elements in two different oxidation states. For instance it provided the best tool for the separation of U(IV) from U(VI) or Tl(I) from Tl (III) in the organic acid solutions. An endeavour is made at this point to highlight some of the important separations so easily accomplished by use of liquid anion exchanger. The separation of cadmium and zinc66 was effected by Amberlite LA-2. The bromo or iodo complexes at pH~3.0 showed promising separations. Large number of liquid anion exchangers like MDOA66 i.e. methyldodecyl octyl amine or TOA was used for the extractive separation of cobalt in hydrochloric acid or thiocyanate media with Amberlite LA-168 facilitating the clean-cut separation of nickel. The separation of chromium in two oxidation states viz. Cr (VI) and Cr (III) was facilitated by use of MDOA, TBA (tributyl amine) or Aliquat 336S (a quaternary amine)6972 in chloroform. The method permitted direct photometric determinate of blue perchloric acid at 525 nm. The most challenging task was to separate zinconium from hafnium7374. This was carried out by use of TOA from 8M hydrochloric acid with xylene as diluent by process of multistage counter current extraction73. In comparison with liquid cation exchangers not much work has been carried out on extraction of lanthanides by amines or liquid anion exchangers. Only tetervalent lanthanides were extractable75 facilitating separations of lanthanides from actinides. Another landmark in the chemistry of liquid anion exchangers was separation of niobium and tantalum7678. The amines used were MDOA, or TIOA from 9M hydrochloric acid and only Nb95 was extracted but not Ta182, thus facilitating their separation with MDOA in xylene76. With TBA77 also, separation was possible from 9M hydrochloric acid when Nb was extracted and not Ta75. Oxalate species were best extracted in TBA77. Some of the extraction could be carried out with TOA78 in kerosene at pH~1.0 with tartaric or oxalic acids promoting formation of their anionic species. A large number of transuranic elements79, 8086, 9098 including uranium (VI) were seperated. The U (VI) separation was excellent in sulphate media80, 81 although good separation was also possible from nitrate81, chloride70 as well as acetate solutions70.

Solvent ExtractionSeparation of Elements with Liquid Ion Exchangers

The work in alkaline media84, 86 facilitated the separation of anionic carbonate complexes. Several examples could be cited to show usefulness of liquid anion exchangers in analytical chemistry.

1.14 SEPARATIONS WITH LIQUID CATION EXCHANGERS

Liquid cation exchangers consist of large number of extractants. They include alkyl phosphoric acids like HDEHP, derivatives of sulphonic acids like HDNNS (dinonyl napthelene) sulphonic acids or several fatty acids like caproic acids. The extractants behave almost like a chelating agent without formation of ring or cyclic structured compounds. Kimura89, 90 had done exhaustive work on extraction of several transition metals by extractions with H-DEHP as extractant. Maximum amount of work was done by Peppard et al.9193 on the extractive separation of lanthanides by HDEHP from hydrochloric acid. Uranium (VI) was best extracted from sulphuric acid with HDEHP in kerosene9496. The salting out agents promoted extraction97 while TBP, TOPO lead to synergestic extraction of uranium with HDEHP i.e., bis (2 ethylhexyl) phosphoric acid98. Other less common transuranic metals were also quantitatively extracted with bis 2-ethyl hexyl phosphoric acid. There were several examples involving extraction of copper with caproic acid90 or with napthnic or other fatty acids. The discussion on mechanism of extraction or extraction equilibria is given in subsequent chapters.

1.15 MERITS AND DEMERITS OF EXTRACTIONS

The most significant advantage was the possibility of separation of elements at microgram concentration. These methods facilitated the separation of the chemically similar metals. No other method in solvent extraction allows separation of elements in two different oxidation states. Further, the group separation of lanthanides or actinides was quite simplified by these extractants. The flexibility of adjustment of pH or controlling reagent concentration or choice of diluent or organic carboxylic acids facilitated the selective separations of large number of elements. On account of the advantage of regeneration of exchangers, the process became most economical. In several instances common solvents such as kerosene or aromatic hydrocarbons served the purpose of the diluent. Most of the extractants were commercially available in pure form, so further purification was not necessary. The extraction equilibria was attained in a few seconds. The stripping of the metals was possible with dilute mineral acids or water. The difference in stripping behaviour was fully exploited for metal separation. The only disadvantage was the formation of third phase during extraction. To mitigate this problem one had to use modifiers. Such modifiers consisted of decanol, or similar polyhydroxy alcohol. Third phase formation was specially a serious problem in industrial separations, which delayed separation. The phases were easily separated in the presence of the modifiers.

1.16 INDUSTRIAL APPLICATIONS

No other extractant was so fruitfully used for the metal separation as was liquid ion exchangers. Although chelating extractants were numerous which facilitated excellent separations at tracer levels in laboratory, they were proved to be useless on industrial

Introduction to Liquid Ion Exchangers

scale in the pilot plant operation. Even the solvating solvents (with the exception of TBP and to some extent MIBK) were found to be worthless for large scale separations. However, liquid cation exchangers like LIX-64N, Versatic acid, SRS-100 had extensive applications for the separation of copper. The napthanic or caproic or nonyl sulphonic acids were used on a large scale. Similarly the separation of cobalt or nickel was accomplished on mass scale with Kelex-100 as the extractants. Not only liquid cation exchangers but also liquid anion exchangers were used in industry. The extraction of zinc, cadmium, platinum, vanadium, chromium, as well as zirconium and niobium was acheived by liquid ion exchangers. All over the world specially in South Africa, Europe, Canada, England and Australia there are big plants for recovery of metals. In comparison negligible progress was made for their use in asian countries like Japan, China and India. However, with knowledge of mechanism of the extraction equilibria and kinetics of extraction, one could develop selective methods for the separation of metals with these reagents. This is because all processes were economical and reproducible.

Conclusion
Solvent extraction is a most versatile tool of separation on account of its selectivity, sensitivity and speed of operation. The technique needs no sophisticated instrument excepting a simple pH meter or spectrophotometer. An evolution has occured since 1850 for the development of extractants for the purpose of separation. A large number of authoritive research monographs have appeared in the market. The history of development dates back to 1842 when procedure for extraction of uranium was developed. This was quickly followed by a selective method for solvent extraction of iron. Then new extractants like dithizone, cupferron, dimethylglyoxime and 8-hydroxyquinoline were synthesised. Some attempts were made to understand the mechanism of the extraction. At the same time, the subject of separation science grew well with the possibility of analysis from millito nanogram concentration of metal. A most suitable way of classification was based on process of extraction. It was widely accepted by analytical chemists although the one involving categorisation of acidic, neutral and basic extractants was also quite satisfactory. Enormous amount of work was carried out in the chemistry of chelating extractants. This was followed by use of solvating solvents permitting largescale separation. The synergic extraction system did not progress due to paucity of its application in industrial operations but extraction by ion pair formation involving basic extractants like high molecular weight amines or acidic extractants like alkyl phosphoric acid or fatty acids came to the forefront due to their applications in industrial separation. The alkyl phosphoric acid extraction mechanism was similar to chelation but did not form any cyclic structure. Amines or basic liquid anion exchangers had wide utility in chemistry. Some new facts of extractions encountered are briefly dealt with. Liquid anion exchangers have growing demand in separation chemistry on account of prepondrance of anionic complexes of mineral acids or organic carboxylic acids while liquid cation exchanger had wide applicability in chemistry of lanthanides for their separation. Many more liquid exchangers were listed with only one demerit of third phase formation in high molecular weight amines but it was circumvented with the use of modifiers. Numerous industrial applications were possible, more details of which will be provided in the last chapter of this monograph. In conclusion one can state that although these exchangers have very wide applicabilty and used in

10

Solvent ExtractionSeparation of Elements with Liquid Ion Exchangers

advanced countries like USA, UK, Canada, Europe, it has not become popular in most Asian countries excluding Japan. However, it is hoped that as the fundamental chemistry develops they would find very wide applicability in pilot plant operation in India.

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12 70. 71. 72. 73. 74. 75. 76. 77. 78. 79. 80. 81. 82. 83. 84. 85. 86. 87. 88. 89. 90. 91. 92. 93. 94. 95. 96. 97. 98. 99. 100.

Solvent ExtractionSeparation of Elements with Liquid Ion Exchangers

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