UNIT 9 ION EXCHANGE

CHROMATOGRAPHY

Ion Exchange
Chromatography

Structure
9.1

Introduction
Objectives

9.2
9.3

Basic Features of Ion Exchange Mechanism

Classification of Ion Exchangers
Natural Ion Exchangers
Synthetic Ion Exchangers
Liquid Ion Exchangers

9.4

Synthesis of Ion Exchange Resins

Cation Exchangers
Anion Exchangers
Amphoteric Exchangers

9.5
9.6

Trade Names and Nomenclature

Resin Properties
Moisture Content
Particle Size
Cross Linkages
Capacity
Distribution Ratio
Equivalency of Exchange
Resin Selectivity

9.7

Operating Methods
Batch Operation
Column Operation
Moving Bed Operation

9.8 Ion Exchange in Mixed Aqueous - Organic Media

9.9 Specific Cation Exchangers
9.10 Synthetic Inorganic Ion Exchangers
Different Types and Their Characteristics
Special Properties and Applications

9.11 Applications
Separation of Metal Ions and Anions
Separation of Organics
Separation of Ionized from Nonionized
Separation of Actinide Elements
Miscellaneous Applications

9.12 Summary
9.13 Terminal Questions
9.14 Answers

9.1

INTRODUCTION

Amongst various separation techniques, ion exchange is the most popular name
because of its use for water softening. It is also unique in terms of its versatility and
historical developments. Besides the well-known use of ion exchangers in water
treatment, they find use in industry, nuclear fuel processing, hydrometallurgy,
agriculture and biology. The treatment of water by solid adsorbents is as old as
civilization. There are records available that in the time of Aristotle, sand filters were
used for purification of sea water. Moses used a tree branch for making bitter water
sweet. But the credit of recognizing the ion exchange phenomenon goes to two
agricultural chemists-Thompson and Way. They observed the exchange of ammonium
ions with calcium ions in soils. The realization of the fact that certain clay minerals
were responsible for the exchange, led to the attempts to use such materials for water
softening. It also prompted scientists to synthesize materials with similar properties.
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Methods-III

The first synthetic ion exchanger was prepared in 1903 by two German
chemists-Harm and Rumpler. Another German, Gans, worked on several pioneering
applications of permutits. But the permutits could not stand in the market because of
their poor reproducibility and chemical stability.
A real breakthrough in the subject came in 1935 when two English chemists, Adams,
and Holmes, observed that crushed phonograph record exhibited ion exchange
properties. This observation led to the synthesis of several organic ion exchangers
which had better properties. It was illustrated that stable and high capacity cation
exchangers could be prepared as sulphonic acid resins and polyamine type resins
exhibited anion exchange properties. The area of ion exchange blossomed at a very
fast rate. The versatility of ion exchange resins was readily recognized. Many attempts
have been made to modify and improve the existing materials. It is possible to tailor
make ion exchange resins for specific applications.
Ion exchange is firmly established as a unit operation. All over the world, numerous
plants are in operation accomplishing the tasks that range from the recovery of metals
from industrial wastes to the separation of rare earths and from catalysis of organic
reactions to the decontamination of cooling water of nuclear reactors. In the
laboratory, ion exchangers prove themselves as useful materials for accomplishing
analytical separations. The ion exchange membranes find quite a good use in
physiological chemistry and biophysics. Ion exchange separation played a major role
in the identification of trans-uranium elements by Glen T. Seaborg. The identify of
each element of 5f series was established beyond any doubt by the sequence of their
appearance a analogous to the appearance of the corresponding 4f elements
The above applications clearly indicate that a variety of ion exchangers are available
and these materials can be used for different applications. In view of this, it is
important to understand the basic ion exchange mechanism, and a broad classification
of ion exchangers. Ion exchange resins are synthesized by following different
chemical routes. An idea about it can be had by illustrating the synthesis of some wellknown ion exchange resins. The practical utility of an ion exchanger depends upon its
properties, both chemical and physical. Another point which is important in this
context is as to how the material is being operated. The discussion on ion exchangers
will not be complete if we do not talk about some special type of ion exchangers viz.
chelating resins and synthetic inorganic ion exchangers. Finally, a discussion on
various types of applications will be taken up. It may be noted that some of these uses
may not be directly based on separations.

Objectives
After studying this Unit, you should be able to

discuss basic ion exchange mechanism,

classify different types of ion exchangers,

describe the synthesis of ion exchange resins,

explain the properties which characterize an ion exchanger,

describe the operating methods for ion exchangers,

explain the behaviour of specific cation exchangers,

present a complete picture about the different types of synthetic inorganic ion
exchangers and their advantages alongwith applications, and

discuss different types of applications of ion exchangers.

9.2

BASIC FEATURES OF ION EXCHANGE

MECHANISM

Ion Exchange
Chromatography

The term ion exchange generally means exchange of ions of like sign between a
solution and a solid highly insoluble in it. The solid known as ion exchanger carries
exchangeable cations and anions. When the exchanger is in contact with an electrolyte,
these ions can be exchanged for a stoichiometrically equivalent amount of other ions
of same sign. Carriers of exchangeable cations are known as cation exchangers and
carriers of exchangeable anions as anion exchangers. Certain materials are capable of
both cation and anion exchange. These are known as amphoteric exchangers.
A typical cation exchange reaction is shown below:
2 NaX + CaCl2(aq)

CaX2 + 2 NaCl(aq)

Similarly, typical anion exchange reaction is as follows:

2 XCl + Na2SO4(aq)

X2SO4 + 2 NaCl(aq)

where, X represents a structural unit of the ion exchanger.

In the first process, a solution containing dissolved CaCl2, say something like hard
water, is treated with a solid exchanger, NaX, containing exchangeable Na+ ions. The
exchanger removes the Ca2+ ions from the solution and replaces them with Na+. Thus,
a cation exchanger in Na+ form is converted to Ca2+ form.
Ion exchange, with very few exceptions, is a reversible process. In water softening, a
cation exchanger has lost its Na+ ions and can be regenerated with a solution of a
sodium salt such as NaCl. Ion exchange resembles adsorption in that, in both cases, a
dissolved species is taken up by a solid. The characteristic difference between the two
is that the ion exchange in contrast to sorption, is a stoichiometric process. Every ion
removed from the solution is replaced by an equivalent amount of another ionic
species of the same sign. However, in the case of sorption a solute, an electrolyte or
non-electrolyte, may be taken up without any species being replaced.
Ion exchangers owe their characteristics to a particular feature of their structure. They
are built of a framework which is held together by chemical bonds or lattice energy.
The framework carries a positive or negative surplus charge which is compensated by
ions of opposite charge, called counter ions. The counter ions are free to move within
the framework and be replaced by other ions of same sign. The framework of cation
exchanger may be regarded as a macromolecule or a crystalline polyanion, that of an
anion exchanger as a polycation.
From the above discussion, it emerges out that a useful ion exchanger must have the
following requisites:
i)

It should have negligible solubility in the medium to be used.

ii)

It must contain sufficient number of accessible ion exchange groups and it must
be chemically stable.

iii)

It should be sufficiently hydrophilic to permit diffusion of ions through the

structure at a finite and usable rate.

iv)

The swollen exchanger must be denser than water.

SAQ 1
What is the basic difference between adsorption and ion exchange?
...

Chromatographic
Methods-III

SAQ 2
A sodium phosphate solution is passed through a column of an anion exchanger in the
chloride form. The PO43 ions are taken up by the ion exchanger. Write down the ion
exchange equilibria.
...
...
...
...

9.3

CLASSIFICATION OF ION EXCHANGERS

Many different natural and synthetic products show ion exchange properties. These
exchangers can be either cation or anion exchangers. Therefore, a simple broad
classification can be as
i)

Natural

ii)

Synthetic

However, within these two categories the material can be

i)

Organic

ii)

Inorganic

For the purposes of simple presentation, we will select the first classification i.e.,
natural and synthetic.

9.3.1 Natural Ion Exchangers

Most of the natural ion exchange materials are crystalline aluminosilicates with cation
exchange properties. The typical representative of this group of materials are zeolites
which include among others, the minerals like analcite Na[SiAlO6]2. H2O, chabazite
(CaNa)[SiAlO6]2.6H2O and naturalite Na2[Si2Al2O10].2H2O. All these minerals have a
relatively open three dimensional framework with channels and interconnecting
cavities in the aluminosilicate lattice. The zeolite lattice consists of SiO4 and AlO4
tetrahedra. These have their oxygen atoms in common. Because aluminium is
trivalent, the lattice carries a negative charge. The charge is balanced by alkali and
alkaline earth cations which do not occupy fixed positions and are free to move in the
lattice framework. These ions behave as counter ions and can exchange with other
counter ions.
There are other aluminosilicates with loose layer structure having cation exchange
properties. These materials carry their counterions in between the layer of the lattice.
The typical mineral of this type is montmorillonite with the approximate composition
Al2[Si4O10(OH)2].nH2O. Such minerals swell in one direction increasing the interlayer
distance.
It may be important to mention here that certain aluminosilicates can also behave as
anion exchangers. In montmorillonite, kaolinite and feldspar of sodalite and camerinite
groups the exchange of OH for Cl, SO 24 and PO 34 has been observed. There are
some problems with the use of zeolites as ion exchangers because of some of their
properties. The zeolites are soft minerals and thus, are not very abrasive resistant.
They have poor mechanical strength. Their frameworks are more rigid hence less
open. They swell very little and the counter ions in their pores do not move very
freely. Above all, they suffer partial decomposition by acids and alkalis.

Another lesser known variety of natural ion exchangers is some types of coals. They
contain carboxylic and possibly other weak acid groups. They, thus, can be used as
cation exchangers. Most of these materials swell excessively and are decomposed by
alkali. They are, therefore, stabilized before use. Soft and hard coals are stabilized by
metal ion solutions. Most lignites and bituminous coals and anthracites can be
converted into strong cation exchangers by sulphonation with fuming strong sulphuric
acid. These coals have very limited applications.

Ion Exchange
Chromatography

9.3.2 Synthetic Ion Exchangers

Virtually the field of ion exchange has been dominated by organic ion exchange
resins. An almost unlimited variety of resins with different compositions and degrees
of cross linking can be prepared. The resins consist of an elastic three-dimensional
network of hydrocarbons which carry fixed ionic groups. The charge of the group is
balanced by mobile counter ions. As a matter of fact, these resins are cross-linked
polyelectrolytes. In a cation exchanger, the matrix carries ionic groups like
SO3, COO, PO33
and in an anion exchanger, it carries groups such as
NH3+, >NH2 , > N+
An ion exchange resin particle is one single macromolecule. The chemical, thermal
and mechanical stability and the ion exchange behaviour of the resin depend chiefly
on the structure and the degree of cross-linking of the matrix and on the nature and the
number of fixed ionic groups. The degree of cross-linking determines the mesh width
of the matrix which in turn affects the swelling of the resin and the mobilities of the
counter ions. This finally affects the rate of ion exchange and other processes and the
electrical conductivity. It should be clear that ion exchange resins do not have
unlimited chemical and thermal stability. The common causes of resin degradation are
chemical and thermal deterioration. A majority of commercial ion exchange resins are
stable in all common solvents except in the presence of strong oxidizing and reducing
agents. They can generally withstand temperatures slightly higher than 100C.
As pointed out earlier that the ion exchange behaviour of the resin is mainly
determined by the fixed ionic groups. The number of groups determines the ion
exchange capacity. The chemical nature of groups to a great extent affects the ion
exchange equilibria. One of the important factors is the acid and base strength of the
group. This can be illustrated by taking a few examples. The groups COO are ionized
only at high pH and at low pH, they combine with H+ forming the undissociated
COOH. Thus, they no longer act as fixed charges. On the other hand, strong acid
groups like SO 3 remain ionized even at low pH. Similarly, weak base group NH3+
lose a proton, forming an uncharged NH2 when pH is high and strong base groups
such as N(CH3)3+ remain ionized even at high pH. Thus, the operative capacity of
weak acid and weak base exchanges is more pH dependent.
In this unit, we will mainly focus on the properties of organic resins and these will be
discussed in more detail in section 9.5. Inspite of the fact that different types of resins
have a variety of applications, there are some pronounced limitations of these types of
exchangers. They are not very stable at high temperatures and cannot withstand high
dose of ionizing radiations and highly oxidizing media. From 1950s onwards, interest
in the management of nuclear waste grew at a very fact pace. This led to resurgence of
interest in inorganic ion exchange and a complete subject of synthetic inorganic
exchangers became prominently important. A variety of amorphous and crystalline
inorganic ion exchangers have been synthesized. The list of these materials is large.
Many of these exchangers show specificity for particular ions and they are used to
separate them. No doubt the area of synthetic inorganic ion exchangers initially
developed for nuclear waste management purposes but with the time, it has attracted

Chromatographic
Methods-III

the interest of different types of research groups. A detailed discussion on synthetic

inorganic ion exchangers will be taken up towards the end of this unit.

9.3.3 Liquid Ion Exchangers

You can recollect that in Unit 2, sub-Sec. 2.3.4, it was pointed out that high molecular
weight amines and quaternary ammonium salts behave as liquid anion exchangers.
They extract the anions and anionic metal complexes. With a similar analogy, some
authors classify alkylphosphoric acids, sulphonic acids and carboxylic acids as liquid
cation exchangers (Unit 3, sub-Sec. 3.2.4). It was also pointed out at the same time
that this analogy should not be extended too far. Besides other complications, the
operation of transfer of solute in solvent extraction and ion exchange chromatography
is different. However, one situation remains to be considered when these extractants
mainly high molecular weight amines are loaded on inert supports and the supports are
used in columns for separations. This is classified under the head of extraction
chromatography. For this, you may refer to Unit 4, sub-Sec. 4.2.3 where a brief
mention has been made about extraction chromatography. A variety of metal ion
separations are achieved using this technique. In this context, there may be some
justification for having liquid ion exchangers as a distinct class of ion exchangers.
However, this unit does not discuss them in detail. An idea about liquid ion
exchangers has already been given in Unit 2 and 3.

SAQ 3
What are the two distinct classes of aluminosilicates based on their structure?
...
...
...
...

SAQ 4
Under what conditions the organic resinous ion exchangers deteriorate fast?
...
...
...
...

SAQ 5
Is there any justification of including liquid ion exchangers as a distinct category of
ion exchangers?
...
...
...

9.4

SYNTHESIS OF ION EXCHANGE RESINS

It has been made clear earlier that we will mainly focus on synthesis and properties of
organic resins. If we take synthesis, there are too many types of resins and different
chemical routes are followed to prepare them. Therefore, it may be difficult to cite

10

here even the few important ones. Hence, to highlight the synthetic chemistry of ion
exchange resins, some discussion will be taken up on general terms and that will be
accompanied by a few examples of synthesis. One point which is very clear about
synthesis of ion exchange resin is that it must yield a three dimensional cross-linked
matrix of hydrocarbon chains carrying fixed ionic groups. This can be achieved in the
following ways:
i)

Monomeric organic electrolytes can be polymerized in such a way that a cross

linked network is formed.

ii)

The matrix can be built from non- ionic monomers and the fixed ionic groups
are then introduced into the completed network.

iii)

The fixed ionic groups are introduced while the polymerization is still in
progress.

Ion Exchange
Chromatography

While synthesizing resinous exchanger, it should be kept in mind that it should be

sufficiently cross-linked to have negligible solubility. The cross linking should be such
that it should be able to swell. Polymers which are too highly cross-linked cannot
swell. The mobility of counter ions in such resins is so low that ion exchange is
difficult to take place. The method of synthesis should be such that the degree of
crosslinking can be controlled. Most of the ion exchange resins are made by either
condensation polymerization or addition polymerization. Now the addition
polymerization processes have more or less replaced the condensation processes.

9.4.1 Cation Exchangers

A broad variety of cation exchangers with fixed ionic groups of different character and
different acid strength are commercially available. The most common of these are
strong-acid resins with ( SO 3 ) and weak acid resins with carboxylic acid groups
(COO). Even if we consider these two types of resins, the resins of various strength
can be made since dissociation constants are affected by the nature and configuration
of the units to which the groups are attached. The arylsulphonic acids are stronger than
alkylsulphonic acids. Many ion exchangers contain two or more different types of
ionic groups and they are known as bifunctional or polyfunctional.

a)

Condensation polymers
The earliest known cation exchange resin was a condensation product of phenol
and formaldehyde. The list became broader and more extensive. Other
monovalent or polyvalent phenols like resorcinol and naphthol instead of phenol
and other aldehydes instead of formaldehyde can be used. Phenolic group can
act as a fixed ionic group but the resins have a very low acid strength. Groups
with higher acid strength can be introduced by various methods. The easiest
course is sulphonation of phenol prior to polymerization.

b)

Addition polymers
The area of synthesis of ion exchange resins is now dominated by addition
copolymers prepared from vinyl monomers. They are more chemically and
thermally stable than the condensation polymers. Moreover, in addition
polymerization, the degree of cross-linking and particle size are easy to control.
A well known cation exchange resin is obtained by the copolymerization of

11

Chromatographic
Methods-III

styrene and a small proportion of divinylbenzene followed by sulphonation by

treatment with concentrated sulphuric acid or chlorosulphonic acid.

The role of divinylbenzene is as a crosslinking agent. Pure divinylbenzene is not

easily available. The commercial product consists of different divinylbenzene
isomers (around 50%) and ethylenestyrene (around 50%). Therefore,
ethylenestyrene is also introduced in the matrix. The degree of crosslinking can
be adjusted by varying the divinylbenzene content.

9.4.2 Anion Exchangers

The earliest anion exchangers synthesized were with weak base amino groups

Subsequently, resins with strong-base quaternary ammonium groups were prepared

It was followed by synthesis of resins with strong-base quaternary phosphonium
groups and tertiary sulphonium groups.

12

Ion Exchange
Chromatography

Like cation exchangers, the earlier known anion exchangers were condensation
polymers and they are replaced by addition polymers.

a)

Condensation polymers
The earliest known anion exchange resins were prepared from aromatic amines
like m- phenylenediamine by condensation with formaldehyde.

The aldehyde reacts with amino groups. In the process, the secondary and
tertiary amino groups are formed. Thus, the resins are polyfunctional. Aliphatic
polyamines which are not as weakly basic can also be condensed with
aldehydes.

b)

Addition polymers
Like cation exchangers, a commonly used anion exchange resin is prepared by
copolymerization of styrene and divinylbenzene followed by chloromethylation
(introduction CH2Cl grouping) say, in the para position and interaction with a
base such as trimethylamine. The polymers containing quaternary ammonium
groups are strong bases and those with amino or substituted amino groups show
weakly basic properties.

9.4.3 Amphoteric Exchangers

The ion exchangers which contain both acidic and basic groups are known as
amphoteric exchangers. A number of exchangers of this type has been synthesized
but only a few have found application.
A well known resin containing both strong base and acid groups is prepared by
copolymerization of styrene, vinylchloride and a cross-linking agent followed by
quaternization and sulphonation of the product.

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Chromatographic
Methods-III

Among the amphoteric resins, the most important are the ones known as snake- cage
polyelectrolytes. They are conventional cation or anion exchangers within which
polycation or polyanions, respectively have been formed by polymerization. A typical
example is that a snake- cage polyelectrolyte can be prepared by converting a strong
base anion exchanger to acrylate form and then acrylate anion is polymerized in the
resin. The linear chains of the poly-counter ions are so intricately interwined with the
crosslinked matrix that they cannot be displaced by other counter ions. The situation is
something like a snake trapped in a cage. One significant difference these snake cage
polyelectrolytes show from other amphoteric exchangers is that the poly-counter ions
are not attached to the matrix. Therefore, the charges of poly-counter ions of the
matrix have more freedom to move. As a result, it is not necessary for the resin to have
mobile counter ions (counter ions to the poly-counter ions) to remain electrically
neutral provided the charges of fixed ionic groups and poly-counter ions are balanced.
These exchangers are excellent reversible sorbents for electrolytes. This will be
discussed later when the applications of ion exchangers are being cited.
At the end of this section on the synthesis of ion exchange resins, it may be important
to point out that the chemical structures of the polymers shown are hypothetical. It is
difficult to establish the resin structure exactly. Furthermore, the structures of the
polymers do not represent repeating identical units since the sequence of the
monomeric component is essentially random.

SAQ 6
What are the advantages of addition polymeric resins over their condensation
counterparts?
...
...

SAQ 7
What is the role of divinylbenzene in the synthesis of styrene-divinylbenzene
polymeric resin?
...
...

9.5

TRADE NAMES AND NOMENCLATURE

A number of manufacturers of ion exchange resins sell their products with different
trade names. Some of these are given in Table 9.1.

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Table 9.1: Some Commercially Available Ion Exchange Resins

Manufacturer

Trade name

Dow Chemical Co., USA

Dowex

Rohm & Hass Co., USA

Amberlite

Permutit Co., UK

Zeo- Karb/ De Acidite

Chemical Process Co., USA

Duolite

Bayer-Farben, Germany

Lewalit

Wolfen-Farben, Germany

Wolfatit

Sicso, India

Seralite

Ion Exchange
Chromatography

Nomenclature
The trade names of resins are generally so named that the basic structure is readily
apparent. Taking the example of Dowex resin, it will include
i)

Type i.e. Dowex 50, 50 W( cation exchangers); Dowex 1, 2, 4, 21K (anion

exchangers)

ii)

X- Number or percent divinylbenzene like X8

iii)

Mesh size i.e. 20- 50 ( based on US Standard screen)

iv)

Ionic form i.e. Na

The label will carry something like

9.6

Type

% DVB

Mesh size

Ionic form

50

X8

20- 50

Na

RESIN PROPERTIES

As a matter of fact, the resin is a very complex material and there are several
properties which are to be known and clearly understood before putting it to any
particular application. Some of the important properties are
i)

Moisture content

ii)

Particle size

iii)

Crosslinkage

iv)

Capacity

v)

Distribution coefficient

vi)

Equivalency of exchange

vii)

Resin selectivity

Let us now study them in detail.

9.6.1 Moisture Content

The moisture content of the resins is determined in the usual manner by heating it at
110 115C overnight to constant weight. However, several precautionary steps are
necessary in this exercise. For example, some resins are thermally unstable in the
hydrogen and hydroxyl form and therefore, these should be converted to a stable form
before oven drying. Samples which decompose at these temperatures are occasionally
dried at room temperature over P2O5 for longer periods of time.
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9.6.2 Particle Size

The importance of particle size for proper column performance in an ion exchange
unit is quite obvious. Rate of exchange, pressure drop and back wash expansions are
all dependent on particle size. The resin beads or particles may be formed with
diameters ranging from 1mm to less than 0.04 mm. For most of the ion exchange
operations, an effective size of 0.4 0.6 mm diameter is preferred. This corresponds to
particle size distribution falling between the 20- and 50-mesh screens. The ion
exchange reactions are mostly conducted in the aqueous media in which the particles
have fully hydrated diameter. This is the value that is to be taken into consideration.
The size of the water swollen resin will depend on the type of functional group and the
amount of cross linking of the polymer.
The size of the particle is one of the parameters affecting the rate of ion exchange
reaction. Besides this, the other parameters affecting rate are size and charge of the ion
involved, degree of cross linking and the temperature. As a matter of fact, decreasing
the size of the particle materially decreases the time required for the equilibrium to be
attained with the contacting solution. Since the time required to achieve the
equilibration is decreased the efficiency of a given volume of resin increases. In other
words, the volume of the resin required to perform a specific operation decreases.
The physical aspects of operation are also considerably altered by the change in the
particle size. With the decreasing particle size, the friction loss or pressure drop of a
liquid flowing through the column increases. This means that for a given flow rate,
with decreasing particle size, the pressure drop in a column increases.
An ion exchange column is usually backwashed at the end of an operating cycle to
remove the foreign material and reclassify the particles. The back washing step expand
the bed to different extents depending upon the specific gravity of the resin. The finer
the mesh size and the lower the density, the greater will be the bed expansion.
Generally, the smaller resin particles (~ 50 mesh) are physically more stable. This is
important when the resin is mechanically moved or it goes through large volume
changes.

9.6.3 Cross Linkages

The second variation which can be introduced into the copolymer bead is that of cross
linkage. As mentioned earlier, the cross linkage in a styrene- divinylbenzene polymer
refers to the fraction of divinylbenzene content. Thus, a resin of 8% crosslinkage is
made with beads containing 8% divinylbenzene and 2% styrene and other monovinyl
monomers.
The cross linkage affects the resin in two ways. As the amount of cross linkage
increases, the dry weight capacity decreases. This decreased capacity results from the
greater difficulty of substituting active groups on the copolymers probably due to
steric factors. However, as compared to this, the change in water content is more
pronounced. Thus, as the cross linkage increases, the resin has a swollen volume for
essentially the same number of sites and the wet volume capacity increases.
There are other properties which are affected by the degree of cross linkage. With the
decrease in the cross linkage, the resin swells more and thus, the diffusion of ions
within the resin becomes faster. This, in turn, gives faster equilibrium rate particularly,
for large ions. On the other hand, if the cross linkage is increased, the diffusion paths
may become small enough for the entrance of large ions. This offers a possibility of
separation of ions based on ionic sizes. A typical example is the separation of sulphate
from high molecular weight sulphonic acid by using highly cross linked anion

16

exchange resin. In the same light, we can say that if the cross linking is decreased, the
permeable selectivity difference is also decreased.

Ion Exchange
Chromatography

Cross linkage affects the physical properties also. Highly crosslinked resin is brittle.
On the other hand, low cross linked resins are highly swollen; therefore, soft and
easily deformed.

9.6.4 Capacity
If we consider an ion exchanger, it can be taken as a reservoir of exchangeable ions. In
the ion exchange operation, it is the counter ions which are put to use. The counter
ions content of a given amount of material is equal to the fixed charges which must be
balanced by the counter ions and thus, is essentially constant. This amounts to the fact
that it is independent of particle size and shape and of the nature of counter ions.
Ion exchangers are characterized in a quantitative manner by their capacity. In the
common usage, it is defined as the number of ion equivalents in a specified amount of
the material. But this simple definition is not sufficient and will have to be qualified.
The definition becomes acceptable when the conditions are given. Capacity and
related data are primarily used for two purposes, for characterizing ion exchange
materials and for use in numerical calculations of ion exchange operations. In the
second case, it is more practical to use other definitions or quantitatives which reflect
the effect of operating conditions. The different types of capacity are given as under.
The total capacity of an ion exchange resin is the number of ionic (or potentially
ionic) sites per unit weight or volume of resin. The dry weight total capacity is usually
expressed in milliequivalents per gram of anhydrous resin. Scientifically, it is usually
expressed as meq/ g dry H+ or Cl form. The wet volume capacity is the number of
sites per unit volume of the water swollen resin. The performance of an ion exchange
resin is generally based on volume and the wet volume total capacity is the theoretical
or maximum capacity which the resin can show in any aqueous ion exchange
application. It may be expressed in milliequivalents per milliliter.
The net number of sites which are utilized in a given volume of resin in a given cycle
in known as the operating capacity of the resin in that particular cycle. It may be
expressed in the same terms as total capacity or as a percent of total capacity.
There is another term which is known as useful capacity which is the capacity when
equilibrium is not attained. It depends on experimental conditions viz. ion exchange
rates etc. There is another capacity which is known as breakthrough (dynamic)
capacity which is utilized in column operation. It depends on operating conditions.
There is also a capacity known as sorption capacity which is the amount of solute
taken up by sorption rather than ion exchange per specified amount of the exchanger.

9.6.5 Distribution Ratio

It should be remembered that we should not speak of a resin to pick up a certain ion
without noting that there is another ion in the resin phase. It is actually the tendency of
an ion exchanger to pick up A+ at the expense of B+. This tendency of the exchanger to
take up A+ will be different if the resin contains other ions C+ instead of B+. Thus, we
can prepare a resin containing a certain counter ion and then compare a series of other
ions containing this counter ion as a reference. For the ions in this series, we may
simply mention distribution ratios. Distribution ratio simply expresses the partitioning
of ion between the solution and the resin phases.
D=

Conc. of an ion in the re sin

Conc. of the same ion in the solution

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Chromatographic
Methods-III

The conventional units are

D=

Amount / kg of dry re sin

Amount / Litre of solution

The amount term, in milligram, moles or whatever may be is proper since the units
cancel in calculating the D ratio.
The D values are generally determined by batch method. A known amount of resin is
brought in contact with a known amount of metal ion in solution until equilibrium is
attained. Because isotherms are non-linear, the D values are taken to be limiting slopes
at very low values (Fig. 9.1). The best solution for this is to determine D values at low
concentrations by taking labeled solutions using radioisotopes. The D value is
determined by simply counting the solution before and after equilibrium with the
resin.

Fig. 9.1: A typical curve of loading of an ion exchanger

Sometimes, the distribution ratio is expressed with different values, say

D =

Amount / L of wet volume

Amount / L of solution

The conversion factor of D to Dv is the bed density, , where is in kg of dry resin per
L of resin bed.
For any ion exchange, the importance is its use for the separation that means
selectivity. For selectivity, the Dvalues should be different for the ions to be separated. It
should be kept in mind that the Dvalues is conditional. It depends upon the nature of
resin and the composition of the solution in contact with it. Composition will include
pH, ionic strength, type and molarity of acid and the presence of water miscible
organic solvents and other ions.

18

Distribution Coefficient
There is a term synonymous to distribution ratio which is known as distribution
coefficient (Kd). This is also used to express the distribution of the ion between the
solution and the ion exchange resin. It is more or less the same as distribution ratio.
This weight distribution coefficient of ion is given by
Kd =

Ion Exchange
Chromatography

Conc. in 1 g of the re sin

Conc. in 1 mL of the solution

It is only the difference in terminology and it is determined in the same manner as

distribution ratio. It is expressed as per gram of the dry resin. It is conditional and
dependent on the nature of resin and the conditions prevailing in the solution.

9.6.6 Equivalency of Exchange

It is well known that in the process, an equivalency of ion exchange is established. It
amounts to the fact that as many ion equivalents of one charge must enter the resin
phase as leave it during a reaction process. But there are a number of things which
occur in an ion exchange to make it appear otherwise. The simplest case is that of an
acid or base neutralization in which the effluent contains only water. There is another
example where precipitates may form and be filtered out on the resin. Then too, many
substances are physically adsorbed or occluded in the resin at least temporarily; e.g.
organic acids and amines. Even so, material balances on an equivalent basis are
usually fairly easy to obtain for an ion exchange processes.

9.6.7 Resin Selectivity

The strong cation exchanger like Dowex 50 is comparable in acid strength with
hydrochloric acid and will form stable salt like bonds with any cation. Similarly, a
strong anion exchanger like Dowex 1 is comparable to sodium hydroxide and will
form stable bonds with any anions. The only ions which cannot be held strongly by
one or the other of these resins are complex ions or organic ions which due to their
size or configuration are hindered from entering the interior of resin particle.
The above statement does not mean that all bonds between the strong resin and the
different ions are of equal strength. The ion exchange resins will have preference for
the particular types of ions they will like to hold if given the choice. It is this
preference which is defined as the selectivity of the resin. In the resin systems, the
typical physical chemistry equilibrium constant is not strictly applicable. It is
substituted by a selectivity coefficient. For a resin containing B ion placed in a solution
of ion A and allowed to come to equilibrium, the selectivity coefficient (K) BA for
monovalent exchange is given as follows.
( K ) BA =

(Conc. of A in the resin ) (Conc. of B in solution )

(Conc. of B in the resin ) ( Conc. of A in solution)

It can also be written as

A + Br

( K ) BA

Ar + B

(9.1)

[ A] r [B]
[A][B] r

(9.2)

Here, r in the subscript represents the resin phase. This definition ignores the activity
coefficient of the ions in the two phases. There is no fully satisfactory method for
determining the activity coefficient of ions in the resin phase and are thus omitted. The
activity coefficient of ions in solutions can be obtained from the literature and can be
applied in the above expressions for accurate results when working with other than

19

Chromatographic
Methods-III

dilute solutions. In the case of concentrated solutions when the activity coefficient is
significantly altered, the selectivity coefficients values should be applied with caution.
It should be kept in mind that selectivity is dependent upon many factors. It varies
with temperature and pressure. The effect of pressure has not been investigated due to
the nature of the ion exchange technique. However, there are several factors which are
of more concern and these are discussed below:

i)

Type of functional group

Beyond the primary question of whether the resin is a cation or anion exchanger,
the effect of functional groups upon the selectivity of the resin is largely a
matter of acid and base strength. The difference between the weak and strong
exchange resin is rather sharp. But there are shades of strength in both the
categories. These differences are largely reflected in the position of hydrogen or
hydroxyl ion occupies in the series. To elaborate this point, a typical example
can be cited. In Dowex-1 (a strong anion exchanger) all the three groups are
methyl groups.

Dowex-2 differs only in that one of the methyl groups is replaced by an ethanol
group. This substitution of methyl group changes the selectivity to give a resin
which can be converted to the free base form much more efficiently.

ii)

Valence and nature of exchanging ions

a)

At low aqueous( less than 0.1 N) concentrations and ordinary

temperatures the extent of exchange increases with the increasing valency
of the exchanging ion, i.e.,
Na+ < Ca2+< Al3+< Th4+
This means that divalent ions are more tightly held by the resin than
monovalent ions and trivalent ions more tightly than divalent ions.

b)

Under similar conditions and constant valence, for univalent ions the
extent of exchange decreases with the size of hydrated cation. Thus,
Li+< H+ < Na+ <NH +4 < K+ <Rb+ <Cs+ < Tl+ < Ag+

c)

In the case of divalent ions, the ionic size is an important factor but the
incomplete dissociation of salts plays an important part.
Cd2+ < Be2+ < Mn2+ < Mg2+ Zn2+ < Cu2+ Ni2+ < Ca2+ < Sr2+ < Pb2+ <
Ba2+

d)

With strongly basic anion exchange resins ( Dowex 1 and 21 K), univalent
anions appear to behave similarly to univalent cations.
F < OH< CH3COO< HCO 3 < Cl< HSO 3 HSO 4 < CN< Br< NO 3 <
I
For Dowex-2, OH falls between HCO 3 and Cl.

iii)

Nature of non-exchanging ions

After getting an idea about exchanging ions, let us now consider the nature of
non- exchanging ions also. The nature of non-exchanging or co-ions has little
effect on selectivity unless they tend to form complexes or slightly ionized
molecules with the exchanging ion. An important example in this respect is that

20

of ferric ion in concentrated solution of chloride ions. In this case, ferric ion has
a tendency to exist as FeCl 4 (a complex ion) which is strongly held by a
quaternary ammonium anion exchange resin. The iron can be removed from the
resin by rinsing with water or dilute acid since the complex breaks down when
chloride ions are not present in high concentration. Such examples are numerous
in the literature and are successfully exploited for various metal ion separations.

iv)

Ion Exchange
Chromatography

Ionic forms of resin

It should be borne in mind that the selectivity of an ion exchange resin changes,
usually decreases, as the resin is converted to that particular ionic form. In most
cases, this effect is slight. The selectivity coefficient holds for one specific
composition of the resin. The ionic form is usually expressed as the mole
fraction of the resin which in the A form at equilibrium and is designated as XA.
In general, the greater is the value of (K) BA , the greater is its change from XA.

v)

Total solution ionic strength

Mono-monovalent exchanges are usually little affected by the change in the total
ionic strength. However, it becomes important if the exchanges are taking place
in different valence say mono-divalent exchange.
Let us first consider mono-monovalent exchange
HCl + RSO3Na

NaCl + RSO3H
+

(K HNa+ ) =

[ Na + ] r [H + ]
[ Na + ][H + ]r

... (9.3)

... (9.4)

By substituting the values as follows,

X rNa + = Equivalent fraction of Na+ in resin = (Na+)r/ C r

(9.5)

X Na + = Equivalent fraction of Na+ in solution = (Na+) / C r

(9.6)

where C r = total capacity or normality of resin (equiv./ L) and

C = total normality of solution.
Eq. 9.4 takes the following form
r
X Na
+
r
1 X Na
+

= K HNa+

X Na +

1 X Na +

( 9.7)

This equation gives the equivalent fraction of Na+ in the resin as a function of
the solution with which the resin is in equilibrium. It may be noticed that the
terms C r and C do not figure in the Eq. 9.7.
Now consider the exchange of monovalent ion with divalent ion.
CaCl2 + 2 RSO3Na
++

K Ca
=
Na +

[Ca + + ]r [ Na + ] 2
[Ca + + ][ Na + ]2r

2 NaCl + (RSO3)2Ca

... (9.8)
(9.9)

When Eq. 9.9 is expressed in terms of the equivalent fraction of Ca++ in the
resin as a function of the solution, it becomes

21

Chromatographic
Methods-III

r
X Ca
++
r
2
(1 X Ca
++ )

++

= K Ca
Na +

X Ca + +
Cr
C (1 X Ca + + )2

(9.10)
++

In Eq. 9.10, the apparent selectivity coefficient is the term K Ca

(
Na +

Cr
).
C

C r is the total capacity of the resin per unit volume and, therefore, is fixed for
particular resin, the selectivity of the divalent ion in this exchange is inversely
related to the total concentration of the solution. It can be concluded that the
more dilute the solution, the more selective the resin becomes for the divalent
ions. The normality of the resin phase (C r) will depend upon the swollen
volume of the resin and thus, is a function of cross linkage. Similarly, the
apparent selectivity coefficient has this same form for exchanges between
divalent and trivalent ions. However, in the case of exchange between
+++

monovalent and trivalent ion, the expression takes the form (K) AB+ (

Cr 2
) .
C

This means that the selectivity of the resin for the trivalent ions is inversely
related to the square of total solution concentration.
It can be concluded that this polyvalent ion effect makes efficient water
softening possible. The divalent cations ( Ca++ and Mg2+) are easily picked up
from hard water ( a very dilute solution) and yet are easily displaced by Na+ ions
of a relatively concentrated (10 15%) salt solution. For the same reason,
rehardening of water i.e., replacement of Ca++ / Mg++ ions by Na+ is difficult by
ion exchange. This polyvalent ion effect holds good for both cation and anion
exchange.

SAQ 8
What are the main factors on which the swelling of the resin bead will depend when
immersed in water?
...

SAQ 9
What is the main advantage if the degree of cross linkage of the resin is decreased?
...

SAQ 10
Name the important variables of the solution on which D/Kd value of an ion for a
particular resin will depend?
...

SAQ 11
State whether the following statements with regard to the extent of exchange are
TRUE/ FALSE.
i)

The extent of exchange for Fe3+ is more than for Ce4+.

ii)

Under similar conditions, the extent of exchange for Na+ is more than for Li+.

iii)

For divalent cations the uptake of ion is only determined by the ionic size of the
cation.

22

9.7

OPERATING METHODS

Ion Exchange
Chromatography

So far you have learnt about different properties of the resins and their effect on the
resin behaviour particularly with regard to their utility for separations. In the context
of utility of resins, a question arises as to how are the resins operated or brought in
contact with the solution. There are two main techniques for this. They are batch and
column methods. The column method may be further sub-divided as to whether the
resin bed is fixed or moving and whether the feed solution and regenerant solution
flow past the resin in the same relative direction or in opposite direction.

9.7.1 Batch Operation

The batch method consists of immersing the resin in the solution in a container and
allowing the equilibrium to be established. The extent of exchange of ion is limited by
the selectivity of the resin under equilibrium conditions. Therefore, unless the
selectivity is quite favourable, only a relatively small part of the total capacity of the
resin can be utilized. It is convenient to use a resin batchwise but it is generally
impractical to regenerate the resin for reuse batch-wise.

9.7.2 Column Operation

Column operation can be visualized as a large number of batch operations in series.
The extent to which the exchange takes place in each one of these small batch
operations is limited by the appropriate selectivity coefficient, the overall effect may
be much more favourable. The successive batch operation in a simulated column may
be considered to plates in a distillation column. In a majority of units, ion exchange
containers are used and they are taken as vertical columns filled with ion exchanger
(Fig. 9.2). The resin is supported on a bed of graded gravel or some other filter base
and the feed and regenerant solution passed through the column (down-flow
operation) or up through the resin (up-flow operation).

Fig. 9.2: Ion exchange column with fraction collector

Generally, fixed bed units are used with down flow operation. It gives a maximum of
resin solution contact and a minimum of mechanical problems. A fixed bed ion
exchange column may be operated with counter-current flows. In such a system, the
feed is put through the column down flow and the regenerant is put through up-flow
and vice-versa. A large number of column arrangements have been designed in which
multiple column are piped together to give semi-continuous operations, maximum
resin utilization, regenerant recovery or some other improvements.

23

Chromatographic
Methods-III

9.7.3 Moving Bed Operation

A somewhat different type of column operation is that encountered in a moving bed or
continuous counter-current system. In such a system, the resin as well as the solution,
is made to flow through the system. A typical unit consists of two stages in which the
resin is contacted counter-currently with the exhausting stream and the regenerant
stream. The chemistry of such an operation is similar to fixed bed operation.
The advantages of moving bed operation are those with continuous operation say a
constant supply of a product of uniform quality and reduced cost of space, capital and
labour. There are some design problems due to the movement of resin. Maintaining a
counter- current flow of resin and solution depends upon the densities of two phases.

9.8

ION EXCHANGE IN MIXED AQUEOUS-ORGANIC

MEDIA

Up to this point, you may be carrying an impression that ion exchange takes only
when the aqueous solution is brought in contact with the solid exchanger. There must
be ions in both the solution and the solid. The ions must be free to move and the
exchange takes place. With water as a solvent and with solids which qualify as an ion
exchangers, these conditions are usually met. Water, because of its high dielectric
constant, is an excellent solvent for most inorganics and quite a number of organic
acids, bases and salts. This is what justifies the choice of water as a phase for ion
exchange. Water, however, is by no means the only solvent which allows ion
exchange to take place. There are other solvents with high dielectric constant ( ) in
which electrolytes can dissolve and dissociate and in which most of the ion exchangers
are stable. These are ethylene glycol ( = 41), methanol ( =32), ethanol ( = 26) and
acetone ( = 27). The last three solvents, in particular, have importance in ion
exchange. They can be used with or without addition of water.
This particular section is devoted to ion exchange in mixed aqueous organic media. It
has been observed that some irregular trends in the distribution of metal ions between
mixed aqueous- organic media and the ion exchanger are exhibited when the
percentage of the organic content is varied. The organic solvents used are water
miscible oxygenated compounds like tetrahydrofuran, methanol, ethanol and acetone.
The behaviour of the metal ions with varying organic content has been usefully
exploited for achieving some difficult separations. Korkisch pioneered this technique
and named it as combined ion exchange solvent extraction and coined the abbreviation
CIESE for it. In order to explain the behaviour, in chromatography using these
solution two processes are operative: ion exchange and liquid-liquid extraction. The
mechanism can be explained on the following lines.

24

i)

The addition of organic content reduces the dielectric constant of the solution
promoting thereby ion pair formation between the ionic species and fixed ions
of the ion exchanger. Consequently, with increasing organic content, the uptake
of ionic species on the ion exchanger may increase.

ii)

Sometimes, the addition of organic content of the aqueous solution causes a

decrease in the distribution coefficient of the ion. This is probably due to the
attachment of the anionic complex to the protonated organic solvent making
thereby the anionic complex less available for the solid anion exchanger. It may
be worthwhile to explain the formation of this ion-pair between the protonated
organic solvent and the anionic metal complex on the lines similar to that
discussed in sub-Sec. 3.2.4 of Unit 3. This mechanism in this case can be
illustrated as follows:

( Protonated organic solvent)

(Organic solvent) + H+
(Protonated organic solvent) + ( Anionic complex of the metal)

Ion Exchange
Chromatography

{(Protonated organic solvent) ( Anionic complex of the metal)}

Ion association complex
It may be important to point out that the force of attraction between the two
ionic components of the ion association complex increases with the increasing
organic content i.e., decreasing dielectric constant.
iii)

In some rare cases, the organic solvent may form complexes with the metal ions
bringing a change in their distribution coefficient values.
The ion exchange and solvent extraction may operate simultaneously in a
particular system and compete with each other resulting in to some irregular
trends. Sometimes, the irregularity of these trends is difficult to explain.
Nevertheless, it does not reduce the potentiality of the technique for separation
purposes. In order to highlight the utility of the technique, the distribution
coefficient of Au (III) and Hg(II) for Amberlite IR 400 (anion exchanger) at
0.6 M HCl with changing percentage of tetrahydrofuran (THF) are given below
in Table 9.2.

Table 9.2: I Values Data

THF
Concentration
Au (III)
Hg (II)

90

20

40

60

80

5232

4308

241

2.6

2.0

0.1

>104

370

368

282

201

200

In Table 9.2, there is a decreasing trend in the distribution coefficients of both

the metal ions with the increasing percentage of THF content. Without any THF
at 0.6 M HCl, both Au(III) and Hg(II) are strongly adsorbed on Amberlite
IR-400 and it is difficult to separate them. The best condition for separation is
achieved at 0.6 M HCl with 90% THF.

SAQ 12
From the data given in Table 9.2, comment on the mechanism operating leading to
decrease in the values of distribution coefficients of the two metal ions.
...
...

9.9

SPECIFIC CATION EXCHANGERS

In the beginning of this Unit, it was mentioned that there have been so much
developments in the field of ion exchange that you can more or less have ion
exchangers tailor made for a specific job. Attempts in this direction led to what are
known as specific cation exchangers. This means these ion exchangers show unusual
selectivity towards a cation or a group of cations. If we look at the common general
purpose cation exchangers,s they prefer certain counter ions. There is some sort of
specificity. But here we mean the ion exchanger to be exclusively specific. The basic
idea to synthesize such resins come from the fact that a reagent which either
precipitates a cation or forms a strong complex may be introduced in the matrix of the

25

Chromatographic
Methods-III

resin. The first attempt in this direction was made by Skogseid who synthesized a resin
containing group with a configuration similar to that of dipicrylamine.

Dipicrylamine
Dipicylamine is a known specific precipitating agent for K+ ions. The resin is
synthesized from polystyrene by nitration, reduction, condensation with picrylchloride
and again nitration.
Many compounds which form chelates with metal ions have been incorporated into
resins while polycondensation with phenols and aldehydes. To cite an example, there
is one with anthranilic acid. It is selective for zinc and other transition metal ions.

Other compounds which have been used are o- aminophenol, anthranilic aciddiacetic acid, m-phenylenediglycine.
There are chelating resins containing groupings similar to those of the more
conventional chelating compounds, e.g., EDTA (ethylenediamine tetracetic acid) but
attached to a cross linked matrix for gross insolubility. These compounds tightly bond
certain metal species which tend to form highly stable structures. Dowex A- 1,
chelating resin, contains iminodiacetate groups attached to a cross linked polystyrene
matrix.

The resin has a very greater affinity for chelate forming di- and trivalent cations than
for cations like Na+ or K+. This resin is particularly useful where one wishes to
overcome the competing effect of high concentration of one or ions. Thus, it will
effectively remove traces of heavy metal ions such as Fe3+, Cu2+ and Zn2+ from
concentrated solutions of alkali and alkaline earth cations can be removed. Metals can
be eluted from the resins with mineral acids. Selectivity among transition metal ions
can be attained by adjustment of pH.
There is one unattractive feature which is common to all specific ion exchangers. As a
matter of fact, the desired selectivity for certain ions is attained by introducing certain

26

groups for which the counter ion has the affinity. As a result of this, the mobility of
counter ions is greatly reduced. Thus, the gain in selectivity is at the cost of rate of ion
exchange. There is another problem which arises due to extreme specificity. It is
difficult to replace the preferred counter ion except when it is replaced by H+ ions.
This will mean that it may be difficult to regenerate the resin. In light of the above,
one should choose a resin keeping in mind a compromise between selectivity, rate of
ion exchange and ease of regeneration.

Ion Exchange
Chromatography

SAQ 13
What are the two main limitations of chelating resins?
...
...

9.10 SYNTHETIC INORGANIC ION EXCHANGERS

In sub-Sec. 9.3.2, it was pointed out that the resinous exchangers cannot withstand
high temperatures and radiation dose. Moreover, they get degenerated in highly
oxidizing media. Towards the end of 1950s, there was a great deal of activity in
nuclear fuel technology, particularly, reprocessing of nuclear fuel and the need of ion
exchangers which can withstand high temperatures and radiation dose was felt. This
revitalized the interest in inorganic ion exchangers and the chemists started
synthesizing inorganic ion exchangers. In a span of about three decades, a huge variety
of inorganic ion exchangers were synthesized and put to use for different separations
and other applications. Most of these materials are amorphous in nature, almost gel
like materials which after drying, are ground to the desired mesh size. Only a few
compounds have been synthesized in a well-defined crystalline structure.
Let us now study about different types and their characteristics.

9.10.1 Different Types and Their Characteristics

The different synthetic inorganic ion exchangers can be broadly classified under the
following categories.
i)

Hydrous oxides of polyvalent metals.

ii)

Insoluble acidic salts of polyvalent metals.

iii)

Salts of heteropolyacids.

iv)

Insoluble ferrocyanides.

v)

Synthetic aluminosilicates.

vi)

Miscellaneous inorganic ion exchangers e.g., synthetic apatites, end sulphides.

i)

Hydrous oxides of polyvalent metals

The hydrous oxides are of particular interest because most of them can function
both as cation and anion exchangers above and below a certain pH value. These
substances are mostly amphoteric in nature and their behaviour mainly depends
upon the basicity of the central atom and the strength of the M O and O H
bonds. The hydrous oxides of tetravalent elements e.g., Zr (IV), Ti (IV),
Mn(IV), Sn(IV) and Ce(IV) are the most studied compounds of this class.
Mixed hydrous oxides of di- and tetravalent metals, tri- and tetra-valent have
also been investigated. The hydrous oxides of quinquevalent and sexivalent
metals generally show cation exchange properties and are stable towards most of

27

Chromatographic
Methods-III

the commonly used reagents. The hydrous oxides are useful for column
operations and can be easily regenerated for use. Apart from enabling routine
separations of various cations and anions, hydrous oxides have been used for the
purification and isolation of transuranium elements from highly radioactive
fission products. Titanium oxides columns have been used for the recovery of
uranium and plutonium from the spent nuclear fuels.

ii)

Insoluble acidic salts of polyvalent metals

The acidic salts of multivalent metals form one of the most extensively studies
class of compounds. A wide range of compounds of this type has been described
as ion exchangers. They include phosphates, arsenates, antimonates, vanadates,
molybdates, tungstates, tellurates etc. mostly of trivalent and tetravalent metals
like Al(III), Cr(III), Fe(III), Ti(IV), Zr(IV), Sn(IV), Ce(IV) and Th(IV). These
salts mostly act as cation exchangers and their exchange properties prominently
arise from the presence of readily exchangeable hydrogen ions associated with
the anionic group. A bewildering array of these acidic salts are known, mostly in
the form of gels. Mixed acidic salts like zirconium arsenophosphate, tin (IV)
arsenophosphate etc. have also been explored as ion exchangers.
Gels of these acidic salts have a potential of use for separation of heavy metal
cations by column chromatography. They have been used for paper
chromatography by impregnating the papers with them. The gels do not have a
definite composition and are not very stable towards the hydrolysis of the acidic
group. Because of uncertainity about the exact composition and structure of
gels, it is very difficult to understand the exact mechanism of ion exchange
reaction. A real breakthrough in these exchangers came when some of them
were prepared in definite crystalline forms. Phosphates and arsenates of Zr(IV),
Ti(IV), Sn(IV), Th(IV) and Ce(IV) have been obtained in crystalline forms. One
of the most studied compounds of this series is zirconium phosphate which has
been obtained with different degree of crystallinity and in different crystalline
forms.

iii)

Salts of heteropoly acids

The parent acids of the compounds are 12-heteropoly acids of the general
formula Hm XY12 O40. nH2O (m = 3, 4, 5) where X may be phosphorus, arsenic,
silicon, germanium and boron and Y different elements such as molybdenum,
tungsten and vanadium. Amongst the exchangers of this category, work has
been mainly reported on 12- molybdophosphates. Ammonium
molybdophosphate and ammonium tungstophosphate are the two widely
investigated compounds for their physicochemical behaviour and practical
applications. Salts of heteropoly acids act mainly as cation exchangers. They
have been mainly used for concentration and purification of Cs137from fission
products. The behaviour of heteropoly acid salts with quaternary organic cations
like pyridinium, picolinium, collidinium has been studied as ion exchangers.

iv)

Insoluble ferrocyanides
The ion exchange properties of a large number of insoluble ferrocyanides of
various metals e.g., Ag(I), Zn(II), Cd(II), Cu(II), Ni(II), Co(II), Pb(II), Mn(II),
Fe(III), Ti(IV), Zr(IV), V(V), Mo(VI), W(VI), U(VI), have been studied. The
ferrocyanides act as cation exchangers with a high affinity for heavy alkali metal
ions, specially for Cs+. The ion exchange mechanism in ferrocyanide is rather
complicated and not yet clear. In order to improve the mechanical properties of
ferrocyanides for use in column operations, the exchanger has been prepared by
precipitation on solid inert supports e.g., bentonite, silica gel, etc., freezing the

28

gel or bonding the precipitate particles to insoluble polymers such as polyvinyl

acetate.

v)

Ion Exchange
Chromatography

Synthetic aluminosilicates
These compounds represent a great family of inorganic ion exchangers and
depending upon their structure they may be divided into the following three
main groups:

Amorphous

Two dimensional layered aluminosilicates, and

Aluminosilicates with rigid three dimensional structures (zeolites)

Among these groups, synthetic zeolites have attracted increasing attention

because of their molecular and ion-sieving properties. They have been
successfully employed in gas adsorption and catalysis.

vi)

Miscellaneous inorganic ion exchangers

Exchangers like apatites and sulphides are included in this class. The anionic
and cationic components of the apatite structure, M10 (XO4)Y, are exchangeable,
where M = Ca, Sr, Ba, Cd and Pb; X= P, As, V, Cr, Mn, Si, Ge and Y= F2, Br2
(OH)2, O and CO 32 . The structure, physicochemical properties, thermal
stability and ion exchange properties of these materials have been reported. The
ion exchange properties of a wide range of sulphides e.g., Ag2S, FeS, CuS, ZnS,
PbS, CdS, NiS, As2S3 and Sb2S3 have been studied. The sulphides are selective
towards cations forming insoluble sulphides. The metal of the sulphide is
displaced by the appropriate ion in solution.

9.10.2 Special Properties and Applications

Here, it may be important to point out that earlier a complete section has been devoted
to the properties of ion exchange resins and the next section will be presenting a
detailed overview of applications of ion exchange resins. In such a situation, this subsection for the properties and applications of synthetic inorganic ion exchanger may at
first sight appear out of place. But in this section, we are going to discuss about some
unusual characteristics of some inorganic ion exchangers and the applications based
upon them. One important point that has to be kept in mind is that it is difficult to
highlight all the unusual features shown by different classes of inorganic exchangers
and the applications based upon them. Therefore, only some important characteristics
and applications are being discussed below.

i)

Radiation and thermal stability

Generally, it is taken as more or less granted that the synthetic inorganic ion
exchangers are more resistant to radiation damage than their organic
counterparts. However, the studies have shown that it is not justified to make a
generalization about them. Each ion exchanger needs to be tested for its
radiation stability. A large number of them have been used for processing fission
products. The ferrocyanides and salts of heteropoly acids are used for the
recovery of Cs137. The radiation stability combined with separation capability
yields a system which is known as isotope generator. A radionuclide
generator is a system/ device which makes the repeated recovery of a shortlived isotope in a pure form from a relatively long- lived parent isotope. A
typical example is a Ba131- Cs131 generator on hydrous zirconium oxide. Short
lived isotopes find use in nuclear medicine for diagnosis and therapy.

29

Chromatographic
Methods-III

By now a fairly good amount of data is available that the thermal stability of
inorganic ion exchangers particularly of those amorphous in nature has been
over emphasized. A number of amorphous materials start losing their ion
exchange capacity on heating. However, some of them are quite resistant to
heat. Hydrous Ta2O5 is quite heat resistant upto 300C and is used for
decontaminating nuclear reactor cooling waters. A promising use of these
exchangers could be in fuel cells at high temperatures or for concentrating the
nuclear waste. Thermally stable ion exchanger in the transition metal forms are
used as high temperature catalysts. Layered zirconium phosphate as such or in
other metal form has been used for catalyzing different organic reactions.

ii)

Unusual selectivity
Many of these inorganic ion exchangers show high selectivity for particular ions
and therefore, the separation of these ions can be more conveniently carried out
than on typical organic resins. Such examples are numerous in literature.
Zirconium antimonate exchanger has been used for the separation of Rb+ and
Cs+. Cerric antimonate is more or less specific for Hg2+ and is used for the
separation of Hg2+ from Cd2+/ Pb2+. Zirconium phosphate like ferrocyanides and
heteropoly acid salts shows unusual selectivity for Cs+ and is used for the
removal of Cs+ from the nuclear reprocessing solution. Because of high capacity
of zirconium phosphate for NH +4 , it is used in artificial kidney machine. The
selectivity features are not only confined to column separations but they have
been extended to paper chromatography in which the papers are impregnated
with the inorganic ion exchangers.
The unusual selectivity and stability of synthetic inorganic ion exchangers make
them suitable for use in ion selective electrodes. They have been investigated for
use as materials for membranes.
Apart from the uses mentioned above, the studies on inorganic ion exchangers
throw light on problems such as sorption of ions by precipitates, electrophoretic
behaviour of suspensions, isotopic exchange in heterogenous systems and many
other areas of solid state chemistry.
Towards the concluding stage of discussion on synthetic ion exchangers, it is
important to point out that very few inorganic exchangers have been used on
commercial scale. The main reason seems to be that among the useful ones, the
majority are based on metals which are costly. The other deterent seems to be
that their regeneration power is not as good as that of their organic counterparts.

SAQ 14
What are the main advantages of majority of inorganic ion exchangers over their
organic counterparts?
...
...

SAQ 15
Which is the most thoroughly studied class of inorganic ion exchangers? Which
particular compound has received the maximum attention?
...
...

30

9.11 APPLICATIONS

Ion Exchange
Chromatography

Ion exchange is one of the very powerful tools for separations. It has a very broad
spectrum of applications and the simple property of exchanging the ions has been very
intelligently exploited for various purposes of separation, enrichment, recovery and
decontamination in various areas of science and technology. In the limited space of
discussion available here, it may not be possible even to simply list the applications
and therefore, it is difficult to accommodate a detailed explanation about them. But for
the purposes of clarity in presentation in a concise form, the entire range of
applications is being subdivided into the following heads:
i)

Separation of metal ions and anions

ii)

Separation of organics

iii)

Separation of ionized from nonionized

iv)

Separation of actinide elements

v)

Miscellaneous applications.

These are briefly presented below:

9.11.1 Separation of Metal Ions and Anions

One of the largest uses of ion exchangers is their capability to separate metal ions. Ion
exchangers show natural selectivity among cations but it can be enhanced by proper
choice of aqueous medium, type of ion exchanger and eluting agent. The literature is
full of examples where separations of topical interest are conveniently achieved.
The choice of different cation exchangers for the separation of different cations looks
logical but it may be important to point out that almost equal number of separation of
metals are achieved on anion exchangers. The metals on anion exchangers are not
separated as cations but as anionic metal complexes. In this context, the best example
is the separation of metals as anionic chlorocomplexes. The ease of formation of these
complexes and their stability determine the selectivity on the anion exchangers. There
is a full periodic table type chart available for the sorption behaviour of different metal
ions on Dowex-1(strong anion exchanger) in the complete range of acidity of
hydrochloric acid. The data given therein have been very useful in designing metal ion
separations. As a typical example Co(II) and Ni(II) are separated from hydrochloric
medium on a strongly basic anion exchanger (Dowex-1). The separation is based upon
the fact that Co(II) but not Ni(II) forms an anionic chlorocomplex (probably CoCl 3 )
in 9M HCl presumably because of instability of the chlorocomplex. The retained
Co(II) is washed from the column by water because the complex is decomposed and
cobalt is recovered as cobaltous chloride.
There are numerous example like this. The extremely high selectivity of the
quaternary ammonium type anion exchange resins for the metallic anionic complexes
is one of the most amazing examples of ion exchange chromatography. The industrial
application of cation exchangers for water softening is well-known where mainly the
Ca2+, Mg2+ and other heavy metal ions are removed by the sodium form of the
exchanger. For complete deionization of water, it is passed through a cation exchanger
and then an anion exchanger or a mixed bed of both types of ion exchangers.
The best illustration of potential of ion exchange to separate closely similar metal ions
is the separation of rare earths. A cation exchange resin alone can provide separation
since the affinities of the lanthanide ions for the resin vary inversely with their
hydrated radii and these, in turn, vary inversely with the crystallographic radii. Thus,
the order of elution is LuLa. The similarity of various rare earths necessitates the use
of complexing agents to increase the separation factor. The use of carboxylic acids
31

Chromatographic
Methods-III

such as citric, glycolic and tartartic, adjusted to appropriate pH, as eluting agents
markedly enhances the separation. Among the other useful ligands employed as
eluting agents are -hydroxyisobutyric acid, EDTA, and 2-hydroxy-EDTA.
The rich deposits of the metals are exhausting and the metallurgists have to depend
upon low grade reserves and other leaner sources like the metal wastes. For the
recovery of metal from low grade ores or the metal wastes, the matrices are first
leached with various reagents. The resulting leach liquors besides the metal of interest
contain several ionic impurities. The ion exchange technique has proved to be very
useful in increasing the metal values of the leached liquors. Besides this, the resins are
used to recover metal values in the tailings of other hydrometallurgical operations. Ion
exchange resins have also been employed for the upgrading of impure concentrates. In
the metallurgy of uranium, it is quantitatively recovered from the leach liquor by
means of anion exchange. Ion exchange has been used for the recovery of gold.
Another example of the successful use of ion exchange is in the recovery of chromium
from electroplating waste.
The separations like molybdenum from rhenium, zirconium from hafnium and
niobium from tantalum have been achieved using ion exchange chromatography and
the conditions developed are used in metallurgical operations.Several anions interfere
in the estimation of various cations and vice-versa. In such situations, ion exchange
chromatography is confined to inorganics.

9.11.2 Separation of Organics

Ion exchange is equally effective for the separation of organic molecules like amino
acids, sugars, nucleic acid and peptides. The purification of several important organic
molecules have been achieved by ion exchange chromatography. The use of
carboxylic acid cation exchange resin for recovering and purifying the antibiotic,
streptomycin, is one of the classic examples of industrial use of ion exchange
chromatography. It should be kept in mind that streptomycin is a cation.

9.11.3 Separation of Ionized from Nonionized

The separation of ionized materials from nonionized or slightly ionized materials
when both are present in water is accomplished by a process known as ion exclusion.
The process utilizes conventional ion exchange resins. If we look at a column of ion
exchange resin, it contains three phases; the solid network of resin beads, the liquid
inside the beads (resin liquid) and the liquid surrounding the beads (interstitial liquid).
Most low molecular weight solutes diffuse freely in and out the resin liquid phase.
However, the organic non-ionic solutes tend to exist at the same concentration in both
the resin liquid and the interstitial liquid phases.
The ionic materials, because of Donnan membrane effect, exist at a considerably lower
concentration in the resin liquid than in the interstitial phase. Thus, if a solution
containing ionic and nonionic substances are fed to the column and the column is
rinsed with water, the ionic solution will reach the bottom first because it has to
essentially displace the interstitial liquid. The non-ionic solution must displace the
interstitial liquid and the liquid inside the beads. Thus, the nonionic material will
emerge out of the column after the ionic solute has passed out of the column.
Hence, ion exclusion offers a method of deionizing or removing majority of ionic
constituents from organic products without the use of heat, electricity and chemical
regenerants. Typical examples of applications of ion exclusion are separation of acids
and salts from glycerine, alcohol and amino acids, the separation of strongly ionized
and weakly ionized materials such as acetic and mineral acids, mono-, di- and
triethanolamine and mono-, di- and trichloroacetic acid.

32

9.11.4 Separation of Actinide Elements

Similar to the separation of lanthanides ion exchange chromatography has played a
major role in the separation of actinides, especially trans plutonium elements.
Glen T. Seaborg used ion exchange equipment to identify each element of the 5f series
beyond any doubt by the sequence of their appearance analogues to the sequence of
the corresponding 4f elements. The primary valency of all the actinides is +3 similar
to the lanthanides which also exhibit decreasing ionic radii (cf lanthanide contraction).
In practice, solution containing all the actinides is sorbed on the top layer of a column
containing acidic cation exchanger. Individual actinides are eluted from the resin bed
by passage of an eluent solution through the column of resin as shown in Fig. 9.3.

Ion Exchange
Chromatography

Fig. 9.3: Elution of tripositive actinide and lanthanide ions

The elution is accomplished by the use of another metal ion (i.e. M3+) which shifts the
equilibrium of the exchange reaction through competition with M+ for position in the
resin. Alternatively, it is also achieved by adding a complexing anion to the solution
which, by reducing the concentration of free metal ions, also shifts the equilibrium to
the left. In Fig. 9.2 is shown the elution sequence for the separation of the lanthanide
and actinide cations from a column of cation exchange resin using a complexing agent.
It was considered as the big triumph for ion exchange chromatography for the
separation of various actinides which was otherwise considered as impossible.

9.11.5 Miscellaneous Applications

The mosaic of applications of ion exchange will be incomplete if we do not mention
the applications from other areas of science. Here too, it is difficult to enumerate even
some of them because they are too many to list. Thus, only a few of them are being

33

Chromatographic
Methods-III

mentioned here. Ion exchange resins are polymeric materials that may be considered
insoluble acids and bases. They can be used to promote reactions which can be
catalysed by conventional acids and bases. Some advantages of solid substantially
insoluble ion exchange catalysts are as follows:
i)

ease of separation by filtration or decantation,

ii)

reduction of cost because the catalyst can be used repeatedly usually without
regeneration,

iii)

increased product yield and efficiency, and

iv)

elimination of corrosion problem.

The major disadvantage of using ion exchange resins as catalyst appear to be thermal
and chemical stability limitations. In some cases, this particular problem is resolved by
use of inorganic ion exchangers. Some of the examples of ion exchange catalyzed
reactions are acetal formation, alcohol dehydration, aldol condensation, esterification
and ester hydrolysis.
The utilization of ion exchange in food processing has been quite successful in both
beverage and canning industries. In the bottling of carbonated beverages, the presence
of carbonate and bicarbonate in water supplies has to be removed. They neutralize the
citric and phosphoric acids added to carbonated beverages. The treatment of raw wines
and whiskeys with ion exchange resins is of considerable interest. The anion exchange
resins remove aldehyde and catalyze several esterification reactions thereby improving
the taste and bouquet of the product.
Ion exchange resins have been scanned as therapeutic agent or additives in host of
medical disorders or ailments. A purified highly subdivided weak base anion
exchanger has been quite successfully used as antacid in peptic ulcer therapy and other
gastrointestinal disorders. The use of cation exchangers as means of removing sodium
from the body in the treatment of edemas and hypertension has been very encouraging.
Ion exchange finds a very useful application in agricultural science in the form of
formulations for plant nutrients. Ion exchange formulations containing nitrogen,
phosphorus and potassium in addition to the minor nutrients that may be deficient
have been found useful in fortifying a wide variety of potting soils. Such a fortified
soil may retain a large supply of nutrient without injury to plant. The need for frequent
fertilization is eliminated, nutrition is continuous and self-regulatory.
Before we conclude this section, it may be mentioned that preceding text simply acts
as pointer to the great scope of ion exchangers in different areas of science and
technology.

SAQ 16
Give two important examples of use of ion exchange from organic chemical
technology.
...
...

SAQ 17
How does ion exchange help in improving the quality of alcoholic drinks?
...
...

34

9.12 SUMMARY

Ion Exchange
Chromatography

The unit begins with a historical background of the process of ion exchange and
focuses on the point that the most important breakthrough in the field was the
discovery of ion exchange resins. The cation, anion and amphoteric exchangers are
known. The basic features of ion exchange mechanism are discussed. There are
organic and inorganic ion exchangers but the former dominate the field. Some
important features of synthesis of ion exchange resins are discussed.
There are two main routes of synthesis-condensation polymerization, and addition
polymerization. Because of certain advantages, the addition polymerization has taken
an edge over the condensation polymerization route. An idea is given about the trade
names of different types of ion exchangers assigned by the manufacturers and the
information generally provided on the labels.
The ion exchange polymers are very complex materials and some of their
characteristics have to be properly understood before they are put to use. The different
properties discussed in detail are moisture content, particle size, cross-linkage,
capacity, distribution ratio, equivalency of exchange and resin selectivity.
The different methods used for operating ion exchangers are elaborated. The
mechanism operating during the uptake of cations in mixed aqueous organic media is
explained. This is followed by discussion on chelating resin and synthetic inorganic
ion exchangers. The important features, classes, advantages and drawbacks of these
types of exchangers are discussed.
The unit concludes with a discussion on applications. There are too many applications.
But for the purposes of clarity of presentation, only a few representative ones are cited
and they are discussed under different groups.

9.13 TERMINAL QUESTIONS

1.

What are the important characteristics of a useful ion exchanger?

2.

What are the broad parameters on which the chemical, thermal, and mechanical
stability and ion exchange behaviour of the resins depend?

3.

What are the advantages if the particle size of the ion exchange resin bead is
decreased? Is there any serious drawback in decreasing the particle size?

4.

Name the factors on which the selectivity of an ion exchanger for an ion
depends.

5.

What are the apparent selectivity coefficients for a mono-divalent and monotrivalent exchange? What are the implications of the term?

6.

Suggest the best possible ion- exchange based method for the following:
i)

Separation of K+ from Na+

ii)

Separation of Co2+ from Mg2+

iii)

Recovery of Cs137 from highly radioactive fission product waste.

iv)

Separation of HCl from CH3COOH.

State only the broad outlines.

35

Chromatographic
Methods-III

7.

What are the broad categories of synthetic inorganic ion exchangers? Which one
of these shows anion exchange properties?

8.

What particular property is responsible for the separation of lanthanides by ion

exchange chromatography? How is the separation potential of this technique
enhanced?

9.

What is the principle involved in ion-exclusion method?

10.

What are the advantages of using ion-exchange resins as catalysts?

9.14 ANSWERS
Self Assessment Questions
1.

The characteristic difference between adsorption and ion exchange is that the
later is a stoichiometric process. Every ion removed from the solution is
replaced by an equivalent amount of another ionic species of same sign.
However, in adsorption solute may be taken up without any species being
replaced.

2.

3 XCl + Na3PO4(aq)

X3PO4 + 3 NaCl(aq)

Here, X represents the structural unit of the ion exchanger and PO 34 is present in
the solution.

36

3.

The two distinct classes of aluminosilicates are one with three-dimensional

network and the other with loose layered structure.

4.

The organic resinous exchangers deteriorate fast at high temperature, under high
dose of ionizing radiations and in highly oxidizing media.

5.

Yes, there is some justification because of the following two reasons:

i)

The mechanism of transfer in both cases is ion exchange

ii)

The column loaded with liquid ion exchanger ( extraction

chromatography) behaves more or less in a way similar to that shown by a
column packed with solid ion exchanger.

6.

The addition polymeric resins are chemically and thermally more stable than the
condensation polymers. Moreover, in addition polymerization, the degree of
cross linking and particle size is easy to control.

7.

The role of divinylbenzene in the synthesis of styrene-divinylbenzene polymeric

resin is as a cross-linking agent. The degree of cross-linking can be adjusted by
varying the amount of divinylbenzene content.

8.

The size of the swollen bead will depend on the type of functional group and the
degree of cross linking of the polymer.

9.

If the degree of cross-linking is decreased, the resin swells more and thus, the
diffusion of ions within the resin becomes faster. This, in turn, gives faster
equilibrium rate particularly for large ions.

10.

The D/Kd value depends on the composition of the solution. This includes pH,
ionic strength, type and molarity acid and presence of water miscible organic
solvents and other ions.

11.

12.

i)

FALSE

ii)

TRUE

iii)

FALSE

Ion Exchange
Chromatography

From the decreasing trend in the Kd value data with increasing THF content, it
can be proposed that the anionic chlorocomplexes of both the metal ions are not
being available to the solid anion exchanger. They are being held as ion
association complex by the protonated organic solvent. The prominent
mechanism is
(Organic solvent) + H+
( Protonated organic solvent)
(Protonated organic solvent) + ( Anionic complex of the metal)

(Protonated organic solvent) ( Anionic metal complex )

Ion association complex
The force of attraction between the two is increasing with increasing organic
solvent, i.e. lowering of dielectric constant of the medium.
13.

14.

The two main limitations of chelating resins are as given below:

i)

By introduction of certain groups, the mobility of counter ions is reduced;

hence, the kinetics of exchange is slowed down.

ii)

It is difficult to regenerate the resin.

The main advantages of synthetic inorganic ion exchanger over their organic
counterparts are
i)

higher thermal and radiation stability

ii)

higher chemical stability in highly oxidizing media, and

iii)

unusual selectivity for particular ions.

15.

The most studied class of inorganic ion exchanger is acidic salts of polyvalent
metal ions and zirconium phosphate has received maximum attention.

16.

The two examples are as follows:

17.

i)

separation of amino acids, and

ii)

recovery and purification of streptomycin.

The quality of alcoholic drinks is improved by anion exchange treatment

because it removes the aldehydes and catalyzes several esterification reactions.

Terminal Questions
1.

A useful ion exchanger must have the following requisites:

i)

It should have negligible solubility in the medium to be used.

ii)

It must contain sufficient number of accessible ion exchanger groups and

it must be chemically stable.

iii)

It must be sufficiently hydrophilic to permit diffusion of ions through the

structure at a finite and usuable rate.

iv)

The swollen exchanger must be denser than water.

37

Chromatographic
Methods-III

2.

The different types of stability and the exchange behaviour of the resin depend
chiefly on structure and the degree of cross-linking of the matrix and on the
nature and number of fixed ionic groups.

3.

By decreasing the size of the bead, the time required for the equilibrium to be
attained with the contacting solution materially decreases. Since the time
required for the equilibrium is decreased, the efficiency of a given volume of
resin increases. In other words, the volume of resin required to perform a
specific operation decreases. It may be pointed out that by decreasing the
particle size, the pressure drop in a column increases.

4.

The factors on which the selectivity of an ion exchanger for an ion depends are
as follows:

5.

i)

Type of functional group of the resin.

ii)

Valence and nature of exchanging ion

iii)

Nature of non-exchanging ion.

iv)

Ionic forms of the resin.

v)

Total solution ionic strength.

The apparent selectivity coefficient for the exchange of a divalent ion with a

Cr
) and for the exchange of a trivalent ion with a
C
3+
Cr 2
monovalent ion it is K AB+ (
) . This means the concentration term of the
C
2+

monovalent ion is K AB+ (

exchanging ion figures. In the first case, it is inversely related to the

concentration in solution and in the second case, it is inversely related to the
square of the total concentration. This implies that for such types of exchange to
take place, the solutions of the exchanging ions should be very dilute.
6.

The best possible ion exchange based methods are

i)

For the separation of K+ ion from Na+ ion is the use of dipicrylamine
based specific cation exchanger. It is highly selective for K+ ion.

ii)

The best alternative for the separation of Co2+ from Mg2+ is the use of a
strong anion exchanger with HCl as the medium. From conc. HCl (more
than 6M) Co2+ will be retained as anionic metal complex on the resin
column and Mg2+ will pass as it does not form anionic metal
chlorocomplex. Co2+ can be eluted by use of water.

iii)

Since the solution is highly radioactive, the use of inorganic ion exchanger
will be recommended. The ferrocyanide exchangers and zirconium
phosphate are selective for Cs+ ion and therefore, either of them can be
used for its recovery from fission products waste.

iv)

7.

38

Since HCl and CH3COOH differ sufficiently in their degree of

dissociation, the best alternative will be the use of ion exclusion
technique. HCl will elute first followed by the elution of CH3COOH.

The broad categories of synthetic inorganic ion exchangers are

i)

Hydrous oxides of polyvalent metals.

ii)

Insoluble acidic salts of polyvalent metals.

iii)

Salts of heteropoly acids.

8.

iv)

Insoluble ferrocyanides.

v)

Synthetic aluminosilicates.

vi)

Miscellaneous like synthetic apatites and sulphides.

Ion Exchange
Chromatography

The hydrous oxides of polyvalent metals prominent show anion exchange

properties below a certain pH. They are basically amphoteric exchangers.
The separation of lanthanides is based on lanthanide contraction. This means
that the crystallography radii decreases from La to Lu but the hydrated radii
increases in the same order. Thus, the order of elution from a cation exchanger
follow the order Lu to La. This trend is enhanced by the use of complexing
agent at an appropriate pH. The complexing agents prefer the bare ions and thus,
enhance the tendency of the ions to elute in the order Lu-La. Among the useful
ligands are citrate, -hydroxybutyric acid and EDTA.

9.

For understanding the principle of ion exclusion, we will have to visualize that a
column of ion exchange contains three phases; the solid network of resin beads,
the liquid inside the bead ( resin liquid) and the liquid surrounding the bead
(interstitial liquid). Most low molecular weight solutes diffuse in and out of the
liquid phase inside the bead (resin liquid). However, the organic nonionic
solutes tend to exist at the same concentration in both the resin liquid and
interstitial liquid phases. The ionic materials, because of Donnan membrane
effect, exist at a considerably lower concentration in the resin liquid than in the
interstitial liquid phase. Therefore a solution containing an ionic and nonionic
component is placed on the top of column and washed with water the ionic
material will reach the bottom first followed by elution of nonionic component.

10.

The advantages of using ion exchangers as catalysts are given under:

i)

Ease of separation of catalyst

ii)

Reduction of cost because the catalyst can be used repeatedly usually

without regeneration

iii)

Increased product yield and efficiency

iv)

Elimination of corrosion problem.

Further Reading
1.

Ion Exchange, By F. Helfferich, Mc Graw Hill Book Company.

2.

Ion Exchange Resins, By R. Kunin, John Wiley and Sons.

3.

Ion Exchangers in Analytical Chemistry, By O. Samuelson, John Wiley and

Sons.

4.

Inorganic Ion Exchangers, By C.B. Amphlett, Elsevier Publishing Company.

5.

Inorganic Ion- Exchange Materials, By A. Clearfield, CRC. Press.

6.

Quantitative Analysis, By R. A Day, Jr. and A. L. Underwood, Prentice-Hall of

India, Private Limited.

39