General Aspects of

UNIT 1 GENERAL ASPECTS OF Separation Methods

SEPARATION METHODS
Structure
1.1 Introduction
Objectives
1.2 Separation Methods − A Unified Science
1.3 Scope of Separation Methods
1.4 Evolution of Chromatography
1.5 Classification of Separation Methods
1.6 Classification Based on Property Resulting in Separation
Volatility
Solubility
Partition
Ion Exchange
Surface Activity
Molecular Geometry
Electromigration
1.7 Classification Based on Equilibrium and Rate Processes
Classification Based on Equilibrium Processes
Classification Based on Rate Processes
1.8 Criteria for Selection of Separation Methods
Selectivity
Detectability
Reproducibility
Yield, Speed and Convenience
Capability for Hyphenation
Ease in Scaling up and Economics
1.9 Summary
1.10 Terminal Questions
1.11 Answers

1.1 INTRODUCTION
The world around us consists of an innumerable complex materials- organic,
inorganic and those containing both types. In order to know the impact of their
existence on our life and fruitfully recover useful materials from various natural
resources, we have to know their composition and develop chemistry for their
recovery. We may like to look at another scenario where the human population of
today has become very much demanding in terms of purity of materials, better
products and security, particularly in terms of health. Simultaneously, science has
tremendously grown in its dimensions and the need for ultra pure materials is fast
increasing. You will, thus, realize that the entire scenario requires developments in the
methods of analysis including separations. It is pertinent to point out here that
separations are not only important for analysis but assume great significance in the
synthesis and recovery of pure materials. Separations touch every branch of science
and technology and have developed into a well established branch known as
separation science. If you just look at the developments, say in biological sciences
such as biochemistry, biotechnology, clinical pharmacology, therapeutics and
toxicology, the progress has taken place prominently because of the advancements in
the separation methods.

After going through the preceding text, you would realize that separation methods
form an important component of chemistry and particularly analytical chemistry. This
course on ‘Separation Methods’ is designed to include theoretical aspects,

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Classical Methods instrumentation, applications, advantages and limitations of some of the important
methods of separations.

Before you study the individual separation methods, it may be necessary to get an
overview of the separation science. This particular unit deals with the concept of
separations as a unified science, scope of separations highlighting their utility,
classification of separation methods and the criteria for the selection of separation
methods.

Objectives
After studying this Unit, you should be able to
• appreciate the separation methods as a unified science,
• describe the scope and utility of separation methods,
• discuss the evolution of chromatography
• explain the classification of separation methods, and
• list the criteria for the selection of separation methods.

1.2 SEPARATION METHODS − A UNIFIED SCIENCE

The separations play a key role in the various branches of science and technology but
they themselves form a unified branch of science. The subject of separation science
essentially deals with the physical and chemical phenomena involved in achieving the
separations. The outcome of separations is very much dependent upon the
physicochemical principles resulting into separations. It also involves the
development, application and reproducibility of various separation processes. The
separations have assumed such a paramount importance that a common man has
become familiar with the meaning of word separation. However, with its requirement
and usage, the definition of separation has become a little complex. In the simplest
terms, separation is defined as an operation in which a mixture is divided into at least
two components having different compositions. But this particular definition has a
limitation as it does not cover chiral separations in which molecules of same
composition and chemical structure are involved. The molecules differ only in their
stereochemistry. Therefore, a broader definition of separation will be as under:
“Separation is a process by which a mixture is divided in at least two
components with different compositions or two types of molecules with the same
composition but different stereochemistry.”

After having learnt the definition of separation in true chemical sense, you should be
clear about the different objectives for achieving separations:
i) Analysis of different constituents of a mixture.
ii) Procuring pure materials from complex mixtures.
In analysis, referred above in (i), there may be three aspects:
• Removal of interfering constituents before the actual quantitation of one or
more known compounds.
• Isolation of unknown constituents for subsequent characterization.
• Analysis of a complex unknown mixture by subjecting the entire sample to
separation into individual constituents.

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Under “(ii)”, for obtaining the pure materials from complex mixtures, the constituent General Aspects of
with the desired purity may be obtained by applying a single process or using a Separation Methods
number of separation techniques. In some cases, in order to attain the required level of
purity, the separation steps of the same process may have to be repeated.

The mixtures to be separated vary largely in terms of their complexity. They may
contain constituents which differ in their molecular weights, solubility in a solvent,
volatility or other properties. The sizes of species may range from atomic dimensions
through organic molecules and macromolecules to molecular aggregates.

A large number of separation methods are available that utilize selected

characteristics as means of separation. Each of these methods can be further
subdivided into different techniques using unique characteristics. In certain cases, the
properties of the constituents may be so different that very simple techniques of
separation can be applied. A very simple example, in this regard, is the recovery of
common salt from sea water. However, in other cases, the properties of constituents
may be so similar that the separation becomes a tedious job. A very well known
example of a difficult separation is the separation of Zn (IV) and Hf (IV). The other
example in this category is the separation of optical isomers.

Another important parameter which is critical in choosing the separation is the

amount of mixture available. In some cases, the amount may be a few molecules.
However, in industrial processes it may run in tonnes.

SAQ 1
What are the main applications of separations?
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SAQ 2
Define separation in the real chemical sense.
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1.3 SCOPE OF SEPARATION METHODS

We have learnt that the separation science deals with a variety of problems at hand.
Now, it may be necessary to illustrate the utility of separations by citing example from
daily life to various branches of science and technology. The number of even the
important examples is so large that they cannot be recounted here. However, by citing
a few, you will be able to appreciate the significance of separations.

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Classical Methods The art of separations is not new to the present day community of scientists. Even our
ancestors were familiar with the various separation methods and were using them for
their daily needs. A very typical example is the distillation of alcohol for drinking and
other purposes. Isolation of various dyes for coloring purposes from natural materials
is a good testimony of their skill for achieving separations. They were also quite
proficient in isolating metals for their use from ores by applying different separation
procedures. A number of drugs used to be isolated from plants and herbs. The
treatment of waters by solid adsorbents is as old as the civilization. There are records
available that in the time of Aristotle, sand filters were used for the purification of sea
water and impure drinking water. Moses used tree branches to make bitter water
sweet.

Separation processes play a key role in our daily life. We remove undesirable gases
and particles from the air we breathe. The municipal drinking water undergoes several
purification steps. It is well known that the identification and removal of contaminants
from food are largely possible due to separation processes. One of best examples of
use of separations in industry is the availability of a variety of products from crude
petroleum. The nuclear age did really take off due to improvements in the methods of
separation of U238 and U235. The requirement of high purity materials in industry,
particularly for semiconductor, is met due to advancements in separation processes.

It has been possible to understand the different biochemical processes taking place in
our body due to advancements in separation processes. The separation processes have
given a unique gift in the form of artificial kidney. The success in the studies on
human genome and proteomics owes a great deal to advancements in separation
sciences. The synthesis of different medicines is possible due to efficiency of
separation processes. The identification of explosives has been possible due to a key
role of separations.

In a nutshell, there is hardly any walk of life where separations do not play their
dominant role.

It is well known that a large number of separation methods fall under the category of
chromatography and that is why the separation methods have become synonymous
with chromatography. Thus, before proposing a classification of separation methods,
it may be important to give here a brief description of evolution of chromatography.

SAQ 3
Give two examples of separations beneficial for our environment.
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1.4 EVOLUTION OF CHROMATOGRAPHY

There is a large number of separation methods which vary in their utility in a
particular situation. Many of these important methods fall under the category of
chromatography. Therefore, before we discuss classification of separation methods, it
will be appropriate to give an idea of the chromatographic science. In Unit 4 of this
course, a discussion on classification and general principles of chromatography has

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been presented. Following this unit, some of the units discuss important General Aspects of
chromatographic methods in detail. In order to keep the text of this particular unit Separation Methods
properly jointed, a brief idea about the evolution of chromatography is being
presented here.

The subject of chromatography had a very modest beginning. The principles and the
applications were reported in 1906 by a Russian botanist, Mikhail Tswett. He
described the resolution of chlorophylls and other plant pigments in a plant extract. A
petroleum ether solution of chlorophyll was passed through a calcium carbonate
column. By passing the solvent through the column, the pigments were resolved into
various zones. This separation became practical if after the pigment solution, the pure
solvent was allowed to pass through the column. Such a preparation was termed as the
chromatogram and the corresponding method, the chromatographic method. The
term chromatography is derived from the Greek words chroma and graphy meaning
colour writing. The discovery of chromatography was made with the separation of
coloured compounds but its potential for colourless compounds was realized. Tswett Mikhail Tswelt
(1872-1919)
himself anticipated the potential of this technique for a wide variety of compounds.
This technique is now termed as liquid-solid adsorption chromatography.

Following the discovery of original form of chromatography, several new advances

were made in the form of ion exchange chromatography, partition chromatography
and gas chromatography. The logic of naming Tswett method as chromatography
does not hold good today because most of the compounds separated by this technique
are not colored. The name is very well established and is not likely to change. Not
only this, many other techniques leading to the redistribution of components of a
mixture are included under the head chromatography.

The most important advances in chromatography were introduced by James and

Martin. The impact of chromatography has been very great on all the areas of analysis
and on the general progress of science. Recognition of this fact resulted in the award
of Nobel Prize in 1952 to Martin and Synge for their pioneering work in this field.

As has already been mentioned, we see chromatography in its different forms. A

general definition of chromatography covering its various forms is as given under: R. L. M. Synge
(1914-1994)
Chromatography is a method of separation in which the components to be separated
are distributed between two phases, one of these is called the stationary phase and the
other the mobile phase which moves on the stationary phase in a definite direction.
The stationary phase may be a solid or liquid and the moving phase may be liquid, gas
or supercritical fluid. The components of a mixture redistribute themselves between
two phases mainly by the process which may be adsorption, partition, ion exchange
or size exclusion. For the purpose of simplification, in our discussion here, on the
classification of separation methods, we will not include supercritical fluid as one of
the mobile phases. However, this will be taken up later.

SAQ 4
A. J. P. Martin
Define chromatography.
(1910-2002)
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Classical Methods SAQ 5
Cite the main processes which are responsible for separations by chromatography.
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1.5 CLASSIFICATION OF SEPARATION METHODS

The subject of separation science has grown very large in its dimensions. A variety of
methods have come up on the forefront to meet the different needs. A number of well
known techniques have undergone modifications. The growth in the number of
separation methods can be attributed to the following factors:
• Different separation goals,
• Diversity of mixtures to be separated, and
• Utilization of a variety of physicochemical phenomena for separations.
The separation methods are generally named after the forces or phenomena that give
rise to separation. In this respect, we can cite the examples of precipitation,
crystallization, extraction, adsorption and ion exchange. At times, the name is used to
reflect upon a distinct form of operation. Here, you can mention techniques like
filtration, distillation, and chromatography. Chromatography, for example, can
employ any number of forces such as adsorption, partition, ion exchange and size
exclusion.

The above discussion makes it clear that one of the classifications of the separation
methods may be based on the property which results into separations. The other
approach that can be adopted for classification is based on the physicochemical
phenomena responsible for separation. To simplify, we can further divide these
phenomena in two major categories: equilibrium processes and rate processes.

Thus, we can propose two types of classifications for separation methods.

• Based on the property resulting into separation,
• Based on the equilibrium and rate processes.
It may be pertinent to point out that the details of the methods will not be discussed
here because either some of the methods are well known or a few of them are being
discussed in details in other units of this course.

SAQ 6
What are the main reasons for the growth in the number of separation mehods?
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SAQ 7 General Aspects of
Separation Methods
What are the two main criteria employed for classifying the different separation
methods?
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1.6 CLASSIFICATION BASED ON PROPERTY

RESULTING IN SEPARATION
The main properties which result into segregation of components of the mixture are:
• Volatility,
• Solubility,
• Partition,
• Ion exchange,
• Surface activity,
• Molecular geometry, and
• Electromigration.

1.6.1 Volatility
The methods based on volatility mainly include vaporization and distillation in its
different forms. Sublimation is a special case of distillation where a solid is directly
vaporized without passing through a liquid state. Vaporization is simple where solvent
is removed by using heat or air currents such that the material concentrates to a solid.
In separation by distillation, all the components of interest in the mixture are volatile.
Sublimation is an exception to this because of the physical state of the component.
Distillation depends on the distribution of constituents between the liquid mixture and
the vapor in equilibrium with the mixture. The more volatile component is
concentrated in the vapor while the less volatile components remain in the liquid
phase in greater concentration.

There are various forms of distillation such as fractional distillation, flash distillation,
vacuum distillation, steam distillation and azeotropic distillation.

Fractional distillation involves the return of condensate to the distillation unit under
conditions such that this condensate is continuously and counter currently in contact
with the vapors. By this method, you can achieve greater enrichment of vapors of
more volatile component than that obtained by simple distillation.

In flash distillation, there is an instantaneous and continuous vaporization of a

definite component of the mixture such that the total vapor produced is in equilibrium
with the remaining liquid.

Vacuum distillation is actually distillation under reduced pressure. It is used to

separate high boiling mixtures or liquids that decompose below their normal boiling
points. Low pressure reduces the boiling point.

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Classical Methods Steam distillation is employed to separate a component from a nonvolatile impurity.
The boiling temperature of the mixture is reduced by vaporizing it in a stream of
carrier vapour say steam which upon condensation is immiscible with the original
mixture. And thus, a separation can be readily achieved.

Azeotropic distillation is used for separating components of a mixture which boil

very close to each other. The relative volatility of the components of the mixture is
altered by adding another substance. This description will give you an idea about the
different ways the distillation can be carried out for different types of mixtures.

SAQ 8
What type of distillation is used to separate components of a mixture if they
decompose below their normal boiling point?
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1.6.2 Solubility
When we refer solubility as a means of separation it essentially implies precipitating
the constituent of interest from the solution. When the solubility limit of the solute in
the solvent exceeds, the material appears as a precipitate. If this process is carried out
in an appropriately selected solvent and in a controlled manner, it can lead to
crystallization. Precipitation can be brought about in a number of ways out of which
some important ones are discussed below.

Solvent precipitation is achieved by adding another miscible solvent to the solution

such that the solubility of the component of interest is reduced and the material
appears as a precipitate in the mixed solvent. The precipitation brought about by a
chemical reaction is well known. Right from the beginning in a chemistry laboratory,
you have been precipitating different ions by adding appropriate reagents. A typical
example is precipitating Ba2+ by adding SO42-. There are many selective reagents
known which can precipitate one ion in the presence of other ions. A detailed
discussion about this is given in Units 14 and 15 of the Course on ‘Basic Analytical
Chemistry’. However, some organic compounds can be precipitated by suitable
adjustment of pH. It is possible to precipitate weakly basic organic compound from an
aqueous solution by making the solution more basic. Similarly, organic acids can be
precipitated by making the solution more acidic by strong acids.

1.6.3 Partition
The methods based on partition require two phases and there has to be a redistribution
of components between these two phases. Some important types of methods fall under
this category and they are as follows:
• Liquid-liquid extraction
• Liquid-liquid partition chromatography
• Gas-liquid chromatography
Liquid-liquid extraction is popularly known as solvent extraction. When a solute is
brought in contact with two immiscible solvents one of which is invariably water and
the other organic, then it distributes itself in them in a fixed ratio. In certain favorable
conditions, the solute of interest can be more or less completely transferred from one

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phase to another. This purification technique finds applications in separation, General Aspects of
purification and enrichment. This separation method has been discussed in detail in Separation Methods
Units 2 and 3 of this course.

In liquid-liquid partition chromatography, there is a support which holds the

stationary liquid phase and a mobile liquid phase runs over it. Because of the
requirement that the two liquids be immiscible, it follows that they differ markedly in
polarity. Either the more polar or less polar may be immobilized. Most commonly, a
polar solvent is held on the support. If a non polar solvent is held after making the
support hydrophobic, this is called reversed phase chromatography. The
components of the mixture redistribute themselves in the two liquid phases resulting
into separation. It is in some ways similar to liquid-liquid extraction discussed
above. If the support material is packed in a column, the method is known as column
liquid-liquid partition chromatography. The details of this method are discussed in
Unit 5 of this course. A simpler version of this technique is available in the form of
planar or two dimensional chromatography. The support is either a thin layer of inert
material coated over a glass plate or a chromatographic paper. And hence, we have
two types of two dimensional chromatography: thin layer chromatography and paper
chromatography. In these two cases, the mobile phase can be made to move either
from top to bottom or bottom to top and, thus, there are two modes of operations
descending and ascending chromatography. The details of planar chromatography are
discussed in Unit 6 of this course.

An improved version of liquid chromatography is in the form of high performance/

high pressure liquid chromatography (HPLC). It is one of the most widely used
separation techniques. The particle size of the packing material is much smaller and a
high pressure around 6000 psi is applied at the top of the column. A high pressure
version of thin layer (HPTLC) is also available. Unit 8 of this course incorporates the
details of this technique.

In gas-liquid chromatography, the stationary phase is a liquid coated in a column or

on a support packed in the column. The mobile phase is a carrier gas which carries
with it the sample in form of a gas. The sample is volatilized to be carried through.
The partitioning takes place between the carrier gas and the coated liquid. The
different aspects of this separation technique are elaborated in Unit 7.

SAQ 9
Name the two types of liquid-liquid partition chromatography.
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1.6.4 Ion Exchange

In ion exchange, there is an exchange of ions, cations or anions, between an insoluble
solid material and the solution in contact with it. The solid material called 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 charge. 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 and are known as amphoteric

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Classical Methods exchangers. Generally, ion exchange is performed in columns. However, in some
cases, batch operations are carried out. A very special case of ion exchangers is
chelating resins. These resins contain functional groups which are chelating ligands.
They form multiple bonds with complex forming metal ions. These resins have much
higher affinities for transition metal ions than for alkali metal ions.

SAQ 10
Name the type of ion exchanger which shows both cation and anion exchange
properties.
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1.6.5 Surface Activity

In surface activity, it is the property of adsorption which is mainly used for
separation. The methods can be chromatographic and non–chromatographic. The
chromatographic methods are as follows:
• Liquid-solid adsorption chromatography
• Gas-solid adsorption chromatography
In liquid-solid adsorption chromatography, an active adsorbent acts as a stationary
phase and the liquid as a mobile phase. The stationary phase can be in the form of a
column or a thin layer on a glass plate. Paper chromatography cannot be exclusively
classified as liquid-liquid partition chromatography. If the cellulose of the paper is
playing an active role as an adsorbent, it will be justified to put it under the head of
adsorption chromatography. The high pressure/ high performance versions of
adsorption chromatography both on column and thin layer are, in use.

In gas-solid adsorption chromatography, the carrier gas with the volatile

components of the mixture flows over an active adsorbent packed inside the column.
Because of differences in adsorption affinity of the components, the segregation of the
components takes place. As compared to gas-liquid chromatography in which a liquid
is coated over an inert material packed inside the column, here in gas solid
chromatography, an adsorbent is packed.

The details of the two types of adsorption chromatography and the high performance
version of liquid-solid chromatography are discussed in the respective Units 5 and 6
of Block 2 and Units 7 and 8 of Block 3 of this Course.

An ultimate extension of adsorption chromatography is affinity chromatography. It is

relatively a new advancement and is an important tool for biomedical research. The
technique of affinity chromatography exploits the unique biological specificity of in a
ligand-macromolecule interaction. The concept of affinity chromatography is realized
by covalently attaching the ligand to an insoluble support through an spacer arm and
packing the material into a chromatographic bed. If a mixture of several proteins is
passed through the column, only that protein that displays appreciable affinity for the
ligand will be retained or retarded. The others which show no recognition of the
ligand will pass unretarded. The adsorbed protein can be subsequently eluted by
changing the composition of the solvent to permit dissociation from the ligand. The

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potential of this technique for the purification and isolation of biological molecules is General Aspects of
unlimited. Specific adsorbents can be designed for the purification of enzymes, Separation Methods
antibiotics, nucleic acids and proteins.

1.6.6 Molecular Geometry

There are a number of methods based on molecular geometry. They require a
permeable barrier to provide separation. The methods are based on the following:
• Molecular sieves
• Gel filtration
The permeable barrier separation process of practical importance utilizes semi–
permeable membranes as the restrictive surface. The membranes permit the passage of
certain chemical species completely while preventing or strongly retarding the
permeation of others. It may be mentioned here that the transport rate of permeation
has to be high enough to achieve reasonably rapid separation. A good mechanical and
chemical stability of these membranes is important. There are different types of
membranes available which are as follows:
• Microporous membranes,
• Homogenous membranes,
• Charged membranes, and
• Thin membranes.
There are numerous applications of these membranes. Some of these are listed below;
• Ultrafiltration,
• Reverse osmosis,
• Dialysis, and
• Electrodialysis.
Unit 11 of Block 5 of this course is assigned for the detailed discussion on membrane
separations.

Gel filtration has taken the form of a regular chromatography. This is also known as
gel permeation or size exclusion chromatography. The column packing materials are
polymer beads and silica based particles containing a network of uniform pores into
which the solute and solvent molecules can diffuse. In a column operation, the solute
molecules which are small enough to enter the pores of gel, are retarded. While the
molecules large enough not to enter the pores, will spend all their time in the mobile
phase and move rapidly through the column. This is a useful technique for the
separation of high molecular weight natural products from low molecular weight
species and salts. It is also used for the rapid determination of molecular weight. The
separation by gel permeation can be carried out at high pressure with an HPLC
instrument. The details of this branch of chromatography are given in Unit 10.

SAQ 11
What are the main requisites of a semi-permeable membrane to be used for various
applications?
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Classical Methods 1.6.7 Electromigration
The simplest example of separation by migration under electric field is controlled
potential electrodeposition. This method is quite effective for the separation of certain
metal ions in the presence of other metal ions. But in the normal classification of
separation methods, it is not given its due recognition. However, the techniques like
electrophoresis and electrochromatography in which an electric field is utilized to
produce or affect the relative motion of charged species in solution, have gained more
prominence. The two frontline techniques included under this head are
electrophoresis and electrochromatography.

In electrophoresis, only the electric field causes the motion while in

electrochromatography, the movement is caused by the resultant of an electric and a
gravitational (or other non-electrical) forces. Electrophoretic separations are
performed in two different ways. One is called slab electrophoresis and the other
capillary electrophoresis.

In slab electrophoresis, a filter paper, porous glass or a gel cast in the form of a bed
can be used. Samples are introduced as spots or band and a dc potential is applied
across the slab for a fixed period. The separated species are visualized by staining in a
way similar to TLC.

In capillary electrophoresis, a buffer filled capillary tube is used. The tube extends
between two buffer reservoirs that also holds the platinum electrodes. The sample is
introduced at one end and a dc potential is applied. The separated analytes are
observed by a detector at the other end.

The simplest form of electrochromatography is by fusion of electrophoresis and

paper chromatography. The sheet of paper is usually suspended vertically with the
solvent (buffer) descending from the top. The electric field is applied horizontally
along the sides of paper. The capillary electrochromatography is a more sophisticated
version of the paper electrochromatography. It is a hybrid of capillary electrophoresis
and HPLC and offers some of the advantages of the two techniques. The different
aspects of separation by electromigration are discussed in Unit 12.

1.7 CLASSIFICATION BASED ON EQUILIBRIUM AND

RATE PROCESSES
Now we have seen that the different types of separation methods have been classified
under various categories based on property resulting into separation. Practically, all
these methods can be divided into various classes using equilibrium and rate
processes as criteria. The equilibrium processes are based on differences in the
properties of individual components. These processes are generally based on phase
equilibria and involve the distribution of substances between two phases. Rate
processes are based on the kinetic properties of the components. It is already clear that
a majority of important separation processes are chromatography based; therefore, it
may be reasonable to introduce a sub-classification of the method listed under this
head as chromatographic and non-chromatographic methods.

1.7.1 Classification Based on Equilibrium Processes

It has been pointed out in the preceding section that in equilibrium processes there are
two competing phases and they could be as follows:
• Gas-liquid,
• Gas-solid,

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• Liquid-liquid, General Aspects of
Separation Methods
• Liquid-solid.
a) Gas-liquid
Some of the important methods in which gas and liquid are the two phases
involved are as follows:
1. Non-chromatographic methods
i) Distillation
ii) Foam fractionation
When we say distillation, it means distillation in all its forms. The well-
known example of foam fractionation is concentration of ores by froth
floatation process.

2. Chromatographic method
i) Gas-liquid chromatography
b) Gas-solid
When the two phases are gas and solid, a few examples of the methods are as
given below:
1. Non-chromatographic methods
i) Sublimation
ii) Adsorption
2. Chromatographic methods
i) Gas-solid chromatography
ii) Exclusion chromatography
In the case of sublimation, the solid is directly vaporised and the equilibrium
exists between the gas and the solid. Adsorption of gases by solids is a well
known method of separation and this forms the basis of gas-solid
chromatography. Exclusion of molecules based on shape and size of both gas
and liquid can take place.
c) Liquid-liquid
In this case, two immiscible liquids come in contact with each other. Here, the
separation takes place because of favorable partition of one or more components
in one of the phases.
1. Non-chromatographic method
i) Liquid-liquid extraction
2. Chromatographic methods
i) Liquid-liquid column chromatography
ii) Liquid-liquid planar chromatography
iii) High pressure liquid chromatography
d) Liquid-solid
1. Non-chromatographic methods
i) Precipitation

21
Classical Methods ii) Fractional crystallization
2. Chromatographic methods
i) Adsorption chromatography (column and planar)
ii) Ion exchange chromatography
iii) Affinity chromatography
iv) Exclusion (gel permeation) chromatography

1.7.2 Classification Based on Rate Processes

The separations based on rate processes take place due to differences in the kinetic
properties of the components of the mixture. The separations are mainly achieved due
to the following two reasons.
• Different diffusion rates through permeable barriers such as membranes,
• Different migration velocities under various fields like electrical, gravitational
and thermal

a) Different diffusion rate through permeable barriers

The most commonly used permeable barrier is semi = permeable membrane.
The methods based on its use are
i) Ultrafiltration,
ii) Reverse Osmosis,
iii) Dialysis, and
iv) Electrodyalysis.

b) Field separations
Electrical field is commonly used to affect separations and the different
methods which are based on the application of this type of field are
i) Electrodeposition,
ii) Electrophoresis,
iii) Capillary electrophoresis and
iv) Electrochromatography.
The examples for separations resulting due to application of gravitational and thermal
fields are ultracentrifugation and thermal diffusion, respectively.

After going through both types of classification, one can see that most of the known
techniques are included in one or the other category. But it may be mentioned that the
list of separation methods considered for classification is not exhaustive. Some of the
lesser known methods have not been taken into consideration. The other point which
has to be kept in mind is that in some of the methods, particularly chromatographic,
more than one mechanism is operative and the method may be classified under
different categories.

SAQ 12
Give one example each of a non-chromatographic separation process when the
following two phases are in equilibrium.
i) Gas-liquid

22
ii) Liquid-liquid General Aspects of
Separation Methods
iii) Liquid-solid

…………………………………………………………………………………………..
…………………………………………………………………………………………..
…………………………………………………………………………………………..

SAQ 13
Name the separation methods which are performed under the influence of electrical
field.
…………………………………………………………………………………………..
…………………………………………………………………………………………..
…………………………………………………………………………………………..
…………………………………………………………………………………………..

1.8 CRITERIA FOR SELECTION OF SEPARATION

METHODS
Now we have some idea about a majority of separation methods. The advantages,
applications and limitations of some of the important methods will be discussed in the
different units of this course. It may be a little premature to make a comparison of the
methods, particularly, when we do not have sufficient background of the different
separation methods. Moreover, the assessment of utility of a method is really a
situation based problem. To elaborate this point, one can cite that the selection of a
method will be determined by the physical state of mixture, its complexity, amount of
sample available, the speed required and the level of purity desired. Over and above
this, one important point that has to be kept in mind is that whether the method has to
be used for analysis or synthesis/recovery/purification. If a method has to be used on
an industrial scale, some different considerations also get prominence. In a situation
like this, it is a little difficult task to impart special importance to one or the other
criteria. However, having known about the utility of the separation methods, we can
talk about some of the general criteria for the selection of the separation methods.
They are
• Selectivity,
• Detectability,
• Yield, speed and convenience,
• Capability for hyphenation, and
• Ease in scaling up and economics.
We will now briefly explain each one of them.

1.8.1 Selectivity
The foremost and most important is the selectivity. The selectivity relates to the
capability of the technique to separate the desired component effectively from a
complex mixture particularly containing closely similar components. The term
‘effective separation’ is expressed in terms of resolution, separation factor,
decontamination factor and percentage purity. All these terms, in one form or the
other, will appear in different units of this course.

23
Classical Methods 1.8.2 Detectability
The term detectability refers to the minimum amount that can be detected. It is also
termed as sensitivity. In the case of detectors, it can be calculated based on certain
assumptions such as detection at two or three times the noise level observed at the
baseline. Sensitivity can also be determined practically. Sensitivity can be improved
by properly optimizing the separation conditions using the same detector. Sensitivity
assumes paramount importance when the quantity of mixture to be analyzed is very
small or trace impurities for obtaining an ultrapure material are to be assayed.

1.8.3 Reproducibility
The method should be such that it gives reproducible results of separation. It is
usually expressed in terms of standard deviation or coefficient of variation based on
replicate measurements. Now at this point, it may be important to point out that the
separation conditions should not be such that a slight variation in the conditions may
alter the result significantly. A flexibility in the conditions of separation is always
preferred. This is particularly important if the process is to be scaled up on a
commercial scale.

1.8.4 Yield, Speed and Convenience

In all those methods in which a simultaneous quantification of the separated product
is done, a quantitative recovery of the separated product is a must. Naturally, a
method giving a higher yield is preferred. In cases where the yield is not high, the
remaining portion may have to be recycled.

Speed of the separation is another critical parameter. Any technique which is awefully
slow in achieving the separation goes in the background. By properly adjusting the
experimental parameters, it is sometimes possible to improve the speed of the
separation process. Speed, as a criteria, assumes great significance if the constituents
of the mixture degenerate or decay. A typical example is the separation of
radionuclides with very short half-lives. In such a situation, speed becomes more
important than the yield.

Literally, the convenience of a separation method is a very broad term. The method of
separation should be such that there may be little preparative chemistry before
subjecting the sample to separation. The conditions of separation should not be very
stringent to the extent that it may be difficult to keep a control of the conditions. The
product should be obtained in such a form that it can be easily put to use without
much chemistry. Moreover, the method can be an asset if it is easily put on-line
operation or easily automated.

1.8.5 Capability for Hyphenation

In a majority of chromatographic methods, there is a detector which quantifies the
effluent coming out of the column. These detectors are not very sensitive. Also they
have a limited capability of identifying the unknowns. It is known that a mass
spectrometer is a very powerful universal detector. Therefore, it is being interfaced
with some of the chromatographic techniques. A very important example in this
regard is interfacing of a gas chromatograph with a mass spectrometer (GC-MS).

Gas chromatography is an ideal separator, whereas mass spectrometry is excellent for

identification. The aim of an interfacing arrangement is to operate both a gas
chromatograph and a mass spectrometer without affecting the performance of either
instrument. The problem is compatibility. The interface provides the link between the
two instruments. On a similar line, gas chromatography is coupled with infrared

24
spectrometry. The techniques like high performance liquid chromatography and General Aspects of
simple liquid chromatography are coupled with a mass spectrometer. The interfacing Separation Methods
makes the technique as a powerful analytical tool. Thus, in nutshell, a separation
technique is conveniently interfaced with an effective detecting device like mass
spectrometer or spectrophotometer, this can be an additional advantage of the
technique. There have been serious efforts in this direction and even the simple
techniques like thin layer chromatography has been interfaced with a mass
spectrometer.

1.8.6 Ease in Scaling up and Economics

It has been repeatedly pointed out that one of the main roles of the separations in
technology is in the synthesis, recovery and purification of products. Therefore, the
separation methods do not remain necessarily confined to the bench scale. The basic
data has to be used to scale up the process to plant scale. The method should be such
that it can be conveniently scaled up on a commercial scale without much alteration in
basic experimental parameters. Once we talk of the use of the method on a
commercial scale, the economics of the process figures in. Not only the economics,
the environmental considerations assume significant importance. The commercial
method of separation should also be environmental friendly.

SAQ 14
What is the usual way of expressing the reproducibility of a separation method?
…………………………………………………………………………………………..
…………………………………………………………………………………………..

SAQ 15
In what particular type of separations, the speed of the separation becomes very
important?
…………………………………………………………………………………………..
…………………………………………………………………………………………..

SAQ 16
What different parameters gain prominence when a separation method is to be scaled
up for plant production?
…………………………………………………………………………………………..
…………………………………………………………………………………………..
…………………………………………………………………………………………..
…………………………………………………………………………………………..
…………………………………………………………………………………………..

1.9 SUMMARY
The present unit provides an introduction to the course on separation methods. It
highlights the utility of separations in the analysis and recovery of pure products from
complex mixtures. The scope of separations extends from the needs of everyday life
to complex technological processes. There is hardly any branch of science or
technology which has not been a beneficiary of the developments in separation
science.

25
Classical Methods Separations encompass different physicochemical principles and the subject has itself
matured to a unified science. Most of the well known methods of separations fall
under the category of chromatographic methods.

It is a little difficult task to categorize the variety of separation methods available

today. A simpler classification can be made on the basis of property which results into
separation. The other approach that can be adopted for classification is based on the
physicochemical phenomena responsible for separation. In other words, these
phenomena can be divided under two categories, the equilibrium and the rate
processes. In equilibrium processes, there have to be two competing phases. However,
in rate processes, the constituents move differently through a permeable barrier or
show different migration velocities under various fields, mainly electrical.

In both the classifications, it has been possible to classify most of the well known
separation methods in one or the other category. But some of the methods are such
that they can be put in more than one category.

As regards the criteria to be used for the assessment of utility of a separation method,
the whole problem is situation based. This point can be clarified by the fact that the
selection or the utility of a method will be determined by the physical state of the
mixture, its complexity, amount of sample available, the speed required and the level
of purity desired. It has to be kept in mind that whether the method is to be used for
analysis or synthesis/recovery. But this only does not necessarily determine the
importance of the different criteria cited in the text.

1.10 TERMINAL QUESTIONS

1. In what ways the separations help in chemical analysis?

2. Name the properties which are generally used for achieving separations.

3. What are the different types of distillation processes?

4. What are the different ways of affecting separations by precipitation?

5. What is paper electrochromatography?

6. Name the different criteria which are commonly used for the selection of
separation methods.

1.11 ANSWERS

Self Assessment Questions

1. Separations have the following two main types of applications:
i) In the analysis of materials
ii) In the synthesis and recovery of pure materials.

2. Separation is a process by which a mixture is divided in at least two

components with different compositions or two types of molecules with the
same composition but different stereochemistry.

3. The two important examples beneficial for our environment are as follows:
i) Purification of municipal drinking water.

26
 ii) Removal of undesirable gases and particulate matter from the factory General Aspects of
emissions. Separation Methods

4. Chromatography is a method of separation in which the components to be

separated are distributed between two phases, one of these is called the
stationary phase and the other mobile phase which moves on the stationary
phase in a definite direction. The stationary phase can be a solid or liquid and
the moving phase may be a liquid, gas or supercritical fluid.

5. The main processes responsible for separations by chromatography are as

follows:
i) Adsorption
ii) Partition
iii) Ion exchange
iv) Size exclusion.

6. The different reasons for the growth in separation methods are as under.
i) Different separation goals.
ii) Diversity of mixtures to be separated.
iii) Utilization of variety of physicochemical phenomena for
separations.

7. The two main criteria employed for classifying different separation methods are
as given below.
i) One criteria is based on the property which results in separation.
ii) The other criteria is based on the physicochemical phenomena
responsible for separation. These phenomena can be further divided in
two categories, the equilibrium processes and the rate processes.

8. Vacuum distillation or actually distillation under reduced pressure is used to

separate components of a mixture which decompose below their normal boiling
point.

9. The two types of liquid–liquid partition chromatography are as follows:

i) Column chromatography
ii) Planar chromatography

10. The type of ion exchanger which shows both cation and anion exchange
properties is known as amphoteric exchanger.

11. The main requisites of a semi–permeable membrane to be used for separation

are as follows:
i) It has to permit the passage of certain chemical species completely by
restricting or retarding permeation of others,
ii) The transport rate of permeation has to be high enough and
iii) It should have good chemical and mechanical stability.

27
Classical Methods 12. Phases in Equilibrium Examples of non-chromatographic
Separation Process
i) Gas-liquid distillation
ii) Liquid-liquid solvent extraction.
iii) Liquid-solid precipitation

13. The methods are

i) Electrodeposition,
ii) Electrophoresis,
iii) Capillary electrophoresis, and
iv) Electrochromatography.

14. Standard deviation (σ) or coefficient of variation.

15. If the species degenerates or decays fast with time.

16. The different parameters which gain prominence are

i) Convenience in scaling up.
ii) Economics of the process.
iii) Potential for automation.
iv) Environmental friendliness.

1.12 TERMINAL QUESTIONS

1. The different ways in which the separations help in chemical analysis are stated
below:
i) Removal of interfering constituents before the actual analysis of one or
more constituents of the mixture.
ii) Isolation of an unknown constituent for subsequent characterization.
iii) Analysis of complex unknown mixture by subjecting the entire sample to
separation into individual constituents.

2. The properties which are generally used for achieving separations are
i) Volatility,
ii) Solubility,
iii) Partition,
iv) Ion exchange,
v) Surface activity,
vi) Molecular geometry, and
vii) Electromigration.

3. i) Fractional distillation,
ii) Flash distillation,
iii) Vacuum distillation,

28
 iv) Steam distillation, and General Aspects of
Separation Methods
v) Azeotropic distillation.

4. Separation by precipitation can be affected in the following ways:

i) Solvent precipitation is achieved by the addition of another miscible
solvent such that the solubility of the component of interest is reduced
and it appears as a precipitate.
ii) By chemical reaction between a selective precipitating agent which reacts
with the desired constituent to give a precipitate, and
iii) Some weakly basic and acidic compounds are precipitated by altering the
pH of the solution.

5. Paper electrochromatography is a fusion of electrophoresis and paper

chromatography. The sheet of paper is usually suspended vertically and a
solvent (buffer) is made to travel from top to bottom. The electric field is
applied horizontally.

6. The criteria for the selection of separation method(s) are

i) Selectivity,
ii) Detectability,
iii) Reproducibility,
iv) Yield, speed and convenience,
v) Capability for hyphenation and
vi) Ease in scaling up and economics.

Further Reading
1. Chromatography and Separation Science, By Satinder Ahuja, Academic Press.

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

3. Principles of Instrumental Analysis, By D.A. Skoog, F.J. Holler and T.A.

Nieman, Thomson India.

4. Instrumental Methods of Chemical Analysis, By G.W. Ewing, McGraw Book

Company.

5. Basic Concepts of Analytical Chemistry, By S.M. Khopkar, Wiley Eastern

Limited.

6. Analytical Chemistry, By G.D. Christian, John Wiley & Sons.

29
Classical Methods
UNIT 2 SOLVENT EXTRACTION – I
Structure
2.1 Introduction
Objectives
2.2 General Principles and Terminology
Phase Rule Consideration
Distribution Law and its Limitations
Distribution Ration
Percentage Extraction
Separation Factor
Multiple Extractions
Multiple Extractions with Successive Portions
2.3 Classification of Extraction Systems
Distribution of Simple Molecules
Extraction by Compound Formation
Extraction by Solvation
Extraction by Ion Pair Formation
Extraction by Crown Ethers
2.4 Diluents and Modifiers
Diluents
Modifiers
2.5 Summary
2.6 Terminal Questions
2.7 Answers

2.1 INTRODUCTION
In the world of chemicals a substance is rarely found in a pure form. Also whatever
may be the method of preparation, a chemical entity, in the truest sense, is never
obtained free of impurities. With the rapid growth of chemical technology, the
chemists are called upon to devise methods to obtain substances in a pure form. There
is another problem that if we look into the magic box of analytical techniques there is
hardly a technique which is truly specific for the quantification of a constituent. Both
these scenarios necessitate the development of effective methods of separations. The
analytical chemists have never lagged behind in developing new methods of
separations and bring ingenuity in the existing ones.

In Unit 1 of this course, the general criteria for the selection of a separation technique
have been discussed. In a broader sense, the technique to be adopted for affecting the
separations depends upon the nature of the host matrix and the associated impurities.
Needless to say, the amount to be handled is also important. But whatever may be the
situation you always look for a technique which may be convenient, fast and
economical. It should be one, which, if the need be, can be conveniently scaled up
from the bench level to the plant scale. Liquid-liquid extraction, popularly known as
solvent extraction, comes close to satisfying the above criteria. Besides this, it is a
very versatile technique. It is as effective for organic as for inorganic compounds.
Moreover, such a broad spectrum of extraction systems is available that any given set
of impurities can be dealt with. One definite advantage that the extraction methods
offer over the widely used precipitation technique is that much cleaner separation can
be achieved by the former. In the precipitation methods, contamination by
coprecipitation is a big limitation which is minimized with difficulty, whereas analog
of coprecipitation i.e., coextraction (extraction of impurities which should not extract)
is almost unknown in solvent extraction. Moreover, precipitation methods fail at
micro concentrations because there has to be a sufficient amount of the substance to
get precipitated.

30
Solvent extraction is based on the principle that when a solute is brought in contact Solvent Extraction-I
with two immiscible solvents, one of which is invariably water and the other organic,
the solute distributes itself in a fixed ratio in the two solvents. In certain cases, at
some optimum conditions, the solute can be more or less completely transferred from
one phase to another. Thus, the technique finds application in separation, purification
and enrichment. There is another important aspect of solvent extraction in the form of
extractive spectrophotometry. The absorbance of coloured metal complexes,
particularly metal chelates, extracted in the organic phase is measured. In favourable
circumstances, it may be possible to concentrate the metal, separate it from
interferences and develop the absorbing system in a single step. Thus, the extractive
spectrophotometry invariably scores over normal spectrophotometry in terms of
selectivity and sensitivity.

It may be important to point out here that the general principles, terminology, and
methodology used for the separation of inorganic and organics are the same. The
scope of applications of the technique for the two types of materials is by no means
different. But in order to illustrate the principles more vividly and the variety of
situations that are encountered, our focus will be mainly on the extraction of metal
ions. The different aspects of the technique have been dealt with in two units, the
present one and Unit 3.

The next unit on solvent extraction will deal mainly with different types of extraction
equilibria, factors influencing extraction, different approaches for metal ion
separations and the criteria for the choice of organic phase.

Objectives
After studying this unit, you should be able
• explain general principles and terminology used to express partitioning of solute
and efficiency of separations,
• classify extractants used for metal ions, and
• the role of diluents and modifiers in the extraction of metal ions.

2.2 GENERAL PRINCIPLES AND TERMINOLOGY

This particular section focuses on a system where a solute is brought in contact with
two immiscible solvents. What will be the constraints limiting the partition of the
solute in the two phases? How will be the distribution quantified? Can the distribution
pattern of the solute be evolved into a method of separation or purification of the
solute? Some basic relevant terms are being discussed here.

2.2.1 Phase Rule Consideration

Let us consider the situation when a solute is in contact with two immiscible solvents.
If we apply Gibbs Phase Rule to this system,

P+V=C+2

where P is the number of phases, V is the variance or degrees of freedom and C is the
number of components.

Here, we are dealing with two phases, i.e. two immiscible solvents and one solute
distributed between them. Therefore, variance will be unity. This will amount to the
fact that the concentration of the solute in one phase will fix the concentration of the
solute in another phase. There will be a definite relationship between the solute

31
Classical Methods concentration in each of the two solvent phases. This ultimately forms the basis of the
distribution law.

2.2.2 Distribution Law and its Limitations

It is clear from the above discussion that if the system is composed of two immiscible
solvents and one distributing solute, there is one degree of freedom. The ratio of the
concentration of the solute in the two phases is invariant. It is independent of the total
concentration. Based on this, the distribution law was first enunciated in 1872 by
Berthelot and Jungfleish and later elaborated by Nernst in 1891. The law popularly
known a Nernst distribution law puts greater restraints. It can be stated as that a
solute will distribute itself between two immiscible solvents in such a manner that, at
equilibrium, the ratio of concentration of the solute in the two phases at a particular
temperature will be a constant provided the solute has the same molecular weight in
each of the phases.

For a solute S distributing between solvents 1 and 2, we can write

S1 S2

[S ]2
KD =
[ S ]1
where KD is known as the distribution coefficient or the extraction coefficient. It is
independent of the total concentration of the solute and the phase volumes.

Hence, [S]1 and [S]2 denote the concentrations of the solute in phases 1 and 2,
respectively. If you imagine this total concentrations to be increased until one phase is
saturated and reaches the concentration [sS]1, the second phase must simultaneously
become a saturated solution of concentration [sS]2. The distribution ratio, [sS]2 / [sS]1
then becomes the ratio of the solubilities of the solute in the two phases. This
expression holds reasonably well for materials which are extremely sparingly soluble.

The Nernst distribution law is a useful approximation for the distribution of a species
in the two phases. Careful experiments reveal two serious shortcomings. The first
shortcoming is encountered when the distributing species is involved in chemical
reaction such as dissociation or association and is changed in either phase.

A very typical case in this regard is the distribution of benzoic acid between water and
benzene. In the aqueous phase, benzoic acid is partly ionized while in benzene it is
partly dimerized by hydrogen bonding in the carboxylic group. The pertinent
equilibria dealing with this case will be discussed in the next sub-section.

In the extraction of metal ions, the existence of a single species can be properly
accounted for while considering the distribution of the species in the two phases.
They definitely add complexity to the distribution expression but this does not
represent any essential inadequacy of the distribution law itself.

The second shortcoming arises because Nernst law as stated above is not
thermodynamically rigorous. Strictly in the thermodynamic terms, it is the activity
ratio rather than concentration ratio that should be constant. In other words, the
thermodynamically rigorous partition law would be stated as that the activity of a
chemical species in one phase maintains a constant ratio to the activity in the other
phase. This precisely defined ratio is known as thermodynamic partition coefficient or
distribution coefficient (K´).

32
 {S }2 γ 2 [ S ] 2 γ 2 Solvent Extraction-I
K´= = = KD
{S }1 γ 1 [ S ]1 γ 1

γ1
or KD = K'
γ2
where {S} represents the activity of the solute S and γ is its activity coefficient.

The Variation in the distribution coefficient KD can be seen due to variation in the
activity coefficients in each of the phases. So long the solute concentration is very low
and the activity coefficients approach unity, the value of KD is constant. The use of
radiotracers for distribution studies can be very helpful to investigate the range of
concentration in which the activity coefficients approach unity.

By using radiotracers, the concentration can be kept very low and the distribution of
the species in the two phases can be very accurately and conveniently quantified.
Using radiochemical technique, it has been observed that the distribution coefficient
of gallium chloride between ethyl ether and 6 M HCl remains constant (within 5%)
over a concentration range 10 −12 – 2 × 10 −3 M GaCl3. At higher concentration ranges,
constant values of distribution coefficient might be expected over ranges in which the
ratio of the activity coefficients remains constant. Parallel variations in the activity
coefficients over extensive concentration ranges in two solvents are not likely to
occur.

2.2.3 Distribution Ratio

One particular aspect that should be amply clear to you that the distribution of a
species in the two competing phases is not governed by a simple equilibrium. The
situation is complicated by the chemical interactions in the two phases and they can
eventually markedly affect the concentration of the distribution species. In this
context, you have already been told the case of distribution of benzoic acid between
water and benzene.

It is rarely observed that a single species may be present in the two phases. But as an
analytical chemist, for the purposes of separations, you are concerned with the overall
or stoichiometric distribution of the component of interest in the two phases. In
whatever chemical forms the solute remains in the two phases, it is immaterial. Also,
it is easier to determine the overall distribution of the component in the two phases.
Therefore, to describe the extraction there is a more practical quantity known as
“Distribution Ratio” (D).
Total concentration of S in organic phase
D=
Total concentration of S in aqueous phase
In an ideal condition, if there is no interaction in either of the phases, D would be the
same as KD. If all the interactions of the distributing species are known, they can be
evaluated and an expression showing the effect of various parameters on D can be
obtained. In order to illustrate the point, we discuss two equilibria one from organic
and the other from inorganic chemistry.

A. Distribution of Benzoic Acid Between Benzene and Water

In the aqueous phase, benzoic acid is partially ionized
HBz + H2O H3O+ + Bz − … (2.1)
In the benzene phase, partial dimerization of benzoic acid takes place
2 HBz (HBz)2 …. (2.2)

33
Classical Methods The three species, HBz, Bz¯, (HBz)2 will have their own KD values
[HBz]o
K DHBZ = … (2.3)
[HBz]a

[Bz − ]o
KD = … (2.4)
Bz − [Bz − ]a

[(HBz) 2 ] o
K D( HNz ) = … (2.5)
2
[(HBz) 2 ] a
Subscripts “o” and “a” represent the organic and aqueous phases. It is known
that the benzoate ion remains almost completely in the aqueous phase and the
benzoic acid dimer in the organic phase. As a chemist, you will usually be
interested in knowing where is benzoic acid, whether a part of this acid is
ionized or dimerized.
Total benzoic in the aqueous phase
D = … (2.6)
Total benzoic in the aqueous phase

[HBz]o + [(HBz) 2 ]o
D= … (2.7)
[HBz]a + [Bz − ]a
It is evident that D will not remain constant over a range of experimental
conditions. Suppose we increase the pH of the aqueous phase, D will be
lowered. This is because benzoic acid will be converted to benzoate ion which
does not extract in the organic phase.

B. Distribution of Osmium Tetraoxide between Carbon Tetrachloride and

Water
In the aqueous phase, osmium tetraoxide exists as a dibasic acid, H2OsO5,
which partially dissociates as shown below:
OsO4 H2OsO5 ... (2.8)

H2OsO5 H+ +HOsO 5− ... (2.9)

HOsO5− H+ + OsO 52− … (2.10)

In the organic phase, osmium tetraoxide forms a tetramer
4 OsO4 (OsO4)4 … (2.11)

If we analyse the total scenario with regard to the presence of osmium in its
different forms in the two phases, it is not simple. Osmium tetraoxide monomer
will be the only species present in both the phases. H2OsO5 and the charged
species, HOsO5−, OsO52− will remain totally in the aqueous phase while
(OsO4)4, the tetramer, will remain in the organic phase.

Total concentration of osmium in the organic phase

D=
Total concentration of osmium in aqueous phase
… (2.12)
[OsO 4 ] o + 4[(OsO 4 ) 4 ] o
D= … (2.13)
[OsO 4 ] a + [H 2 OsO 5 ] a + [HOsO 5− ] a + [OsO 52− ]a

34
 The value of D or the total osmium concentration in the two phases can be Solvent Extraction-I
calculated if the values of equilibrium constants of the reactions listed above are
known.

In the two equilibria, one of benzoic acid and the other of osmium tetraoxide,
the distribution ratios have been presented in terms of concentration of certain
species. The expressions can be simplified by bringing in certain equilibrium
constants and minimum number of variables. Finally, the effect of variables on
distribution ratio can be experimentally verified. For reference, see answer of
Terminal Question 1.

2.2.4 Percentage Extraction

Distribution ratio (D) is merely a concentration ratio and the extent of extraction will,
therefore, depend upon the volume ratio of organic to water phases. Since we are
mainly interested in the extent of extraction, we go for another practical term which is
known as percent extraction (% E) or E.

Let f be the fraction of the total metal in the organic solvent at equilibrium, then (1-f)
is its fraction in the aqueous phase. Let Vo and Va be the volumes of the organic and
aqueous phases, respectively. Then
Total metal in organic phase
D=
Total metal in aqueous phase

[M] o
= … (2.14)
[M] a

f/Vo fVa fVa

D= = = … (2.15)
1 − f/Va (1 − f)Vo Vo − fVo

DVo – DfVo = fVa ... (2.16)

DVo= DfVo + fVa ... (2.17)

DVo= f(DVo + Va) … (2.18)

DVo
f= … (2.19)
Va + DVo

100 D
Percentage of metal extracted = 100 f = … (2.20)
D + (Va /Vo )
If the volumes of the two phases are equal, then the denominator simplifies to D + 1.
i.e.,
100 D
% E or E = … (2.21)
D +1
The percent extraction is a more useful term for reporting the analytical data. Fig. 2.1
shows the interconversion of D and % E at a unit volume ratio. It can be seen from the
plot that when the extraction efficiency approaches 100%, the distribution ratio
approaches infinity as a limit. For the extractions to be in the range of 99 – 100% the
distribution ratio will vary from 99 to infinity. Such a large difference in the
distribution ratio is 99 and infinity may be misleading when in reality the extraction
would be nearly complete in both the cases.

35
Classical Methods

Fig. 2.1: Relation between distribution ratio and percent extraction

2.2.5 Separation Factor

Solvent extraction is basically a separation technique. The main objective is to
separate the desired constituent from the other substances present in the mixture. In
order to achieve the objective, we look for a solvent extraction system which may
quantitatively extract the required constituent with practically negligible amount of
the impurities present. The other way to solve the problem is to quantitatively extract
all the impurities leaving behind the desired constituent totally in the aqueous phase.
The situation where none of the impurities or all the impurities may quantitatively
transfer from one phase to the other is rarely encountered. We are likely to face
situations where they differ only somewhat in their tendencies to pass from one
solvent to another. In order to achieve a simple separation, it is necessary that the
distribution ratio of the material of interest and the interference be sufficiently
different. The effectiveness of separation is usually expressed by means of separation
factor “ β ” which is related to the individual distribution ratios in the following way:
(C1 )o / (C 2 )o
β= … (2.22)
(C1 )a / (C 2 )a

(C1 )o / (C1 )a
= … (2.23)
(C 2 )o / (C 2 )a

D1
= … (2.24)
D2
C1 is the concentration of component 1 in the organic and aqueous phases further
labeled by subscripts o and a, respectively and C2 is the concentration of component 2
in the two phases. D1 and D2 are the distribution ratios of components 1 and 2,
respectively. For a good separation, β should deviate from unity as largely as
possible. The ingenuity and knowledge of a separation chemist is tested to find
conditions where β should deviate from unity. With the available data and
knowledge of chemistry, in most of the cases, it is not a problem. An elaboration of
this will be taken up later in Unit 3, Sec. 3.4 where a detailed discussion on the
different approaches adopted for metal ion separation are included. Although most of
the separations involving solvent extraction are based on favourable separation

36
factors, it is occasionally necessary to resort to separations where the distribution Solvent Extraction-I
ratios of the components of the mixture may not be much different. In such situations,
it is necessary to employ fractionation methods in which distribution, transfer and
recombination of different fraction is advised to be performed a number of times to
achieve a certain level of separation.

2.2.6 Multiple Extractions

It should be clear in mind that one transfer does not necessarily lead to a clean
separation. Under these situations, it is better to combine a number of successive
partial separations until the desired level of purity is achieved. While considering how
two phases may be brought together repetitively, the following four types of situations
may be visualized.
i) It is simple where one shot contact between the two phases is made. The two
phases are shaken until an equilibrium is attained.
ii) In this, one phase could be brought repeatedly in contact with fresh portions of
a second phase. This situation would be applicable where one substance
remained quantitatively in one phase while the other one was distributed in the
two phases. This would be like the repeated extraction of an aqueous solution
with successive portions of an organic solvent. The example of Soxhlet
extractor will fall in this category. Another analogy may be provided by
reprecipitation in gravimetric analysis.
iii) In this case, one phase moves while in contact with the second phase which
remains stationary. Like the various chromatographic techniques the mobile
phase moves. This is sometimes designated as countercurrent. But in the real
sense, it is not countercurrent as only one phase moves. Therefore, it is actually
known as discontinuous countercurrent or pseudo countercurrent.
iv) This case is really countercurrent in which both phases move continuously in
contact with each other in opposite directions. A true example of countercurrent
is fractional distillation.

2.2.7 Multiple Extractions with Successive Portions

We have seen the importance of batch extraction because it is most widely used for
analytical separations. In this procedure, a given volume of solution is brought in
contact with a solvent until equilibrium is attained. Even if we suppose that none of
the interfering substances is extracted, the completeness of the extraction is a very
important factor. It has already been pointed out that the distribution ratio is a
concentration ratio and, therefore, the actual fraction of the solute extracted will
depend upon the ratio of volumes of the two solvents competing for the solute.

Let v1 mL of solution (phase 1) containing w g of solute is contacted to equilibrium

with v2 mL of another solvent (phase 2) immiscible with the first. Let w1 is weight of
the solute remaining in the phase 1 after equilibrium is attained.

Now concentration in phase 1 (C1) = w1/v1 g mL−1

And concentration in phase 2 (C2) = w−w1/v2 g mL−1
w − w1 /v 2
Therefore, D = … (2.25)
w1 /v1

 v1 
And, w1= w   … (2.26)
 Dv 2 + v1 

37
Classical Methods If we again extract phase 1 with another portion v2 mL of solvent, w2 g will be the
weight of the solute remaining in the phase 1. After this extraction,

 v1 
w2 = w1 
 Dv + v 
… (2.27)
 2 1 

2
 v1 
Therefore, w2 = w   … (2.28)
 Dv2 + v1 
If the same volume of the extracting solvent is used for each successive extraction and
wn g is the weight of the solute remaining in phase 1, after n extractions wn will be
given by the expression
n
 v1 
wn = w   … (2.29)
 Dv2 + v1 
n
wn  v1 
The fraction remaining in phase 1after n extractions = f1 = =  ....(2.30)
w  Dv2 + v1 
And, the fraction transferred to phase 2 = f2 =1 – f1

If phase 1 is aqueous and phase 2 is organic, then

% Extracted = 10 0 f2

For the most effective extraction, v2 should be taken as small as possible and n as
great as possible for the given amount of a solvent. This amounts to the fact that the
best results are obtained by a relatively large number of extractions with small
amounts of solvent. The fact is illustrated in the answer to Terminal Question 2.

SAQ 1
What will be the conditions when distribution coefficient, thermodynamic distribution
coefficient and distribution ratio are the same?
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................

SAQ 2
The partition coefficient of iodine between chloroform and water is 132. What
percentage of iodine dissolved in 100 mL of water will remain in the aqueous phase if
it is contacted to equilibrium with 50 mL of CHCl3?
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................

38
SAQ 3 Solvent Extraction-I

Two metals A and B form chelates with dithizone and extracted with chloroform.
What should be the ratio of their distribution ratios so that 99% of B remains in the
aqueous phase and 99% of A goes to the organic? Assume equal volumes of organic
and aqueous phases.
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................

2.3 CLASSIFICATION OF EXTRACTION SYSTEMS

It should be now clear to you that the extraction basically takes place in the following
three steps:
i) Formation of an uncharged complex or extractable species.
ii) Distribution of the extractable complex or the species.
iii) Interaction of the complex or the species with the organic phase.
These three aspects are shared by almost all extractions and serve as a basis of a
useful organisational pattern.

In order to discuss in a systematic manner the various extraction systems used for the
extraction of different metal ions, we will have to classify them into certain groups
based on different approaches. Several classification schemes based on different
approaches have been proposed. Such schemes are generally based on the type of
extractants or the chemical reactions involved in the extraction process.

It may be important to point out here that the list of metal ion extractants is very large.
They range from simple to complex molecules and single compound to mixtures. One
or the other aspect of these extractants is more or less thoroughly investigated. From
time to time, various types of extractants with variegated modes of extractions have
been synthesized and investigated. Some of them have desirable attributes and are
able to permeate in the market for commercial applications. It is a known fact that the
use of a majority of extractants is confined up to the bench level and cannot be
extended to plant scale. Our discussion in this section will cover the gamut of metal
ion extractant but the focus will be on the commercial products.

With this background, a logical consequence seems to be that whatever may be the
criteria for classification it may not yield a universal system. However, a simpler
classification incorporating the mechanism of extraction and the extractant used into
different types, is given as under
1. Distribution of simple molecules.
2. Extraction by compound formation.

3. Extraction by salvation.
4. Extraction by ion pair formation.
A special mention is being made of crown ethers as extractants.

39
Classical Methods 2.3.1 Distribution of Simple Molecules
This involves the distribution of simple covalent molecules like GeCl4, HgBr2 and
AsBr3 between aqueous phase and inert organic solvent.

2.3.2 Extraction by Compound Formation

The reagents which fall under this category are called liquid cation exchangers. These
extractants operate, at least, formally by the exchange of the H+ ions of the acidic
organic compound with the cation present in the aqueous phase
M (na+) + n HA(o) MAn(o) + n H (na+)

The process is similar to solid-liquid ion exchange in which HA is equivalent to an

ion exchange resin. Although there is some similarity between the reagents of this
class and solid ion exchangers, very important differences exist as regards their
interaction with the metal ions. These cation exchange extraction systems can be
broadly classified under the following three categories.
i) Extraction by chelating agents.
ii) Extraction by acidic organophosphorus esters.
iii) Extraction by carboxylic and sulphonic acids.
There are some important differences between extraction processes involving chelates
on one side and phosphorus and carboxylic acids on the other. The acids forming
chelates are usually weak and more soluble in organic than in inorganic solvents. The
composition of the chelates is usually unaffected by the nature of the diluents. The
extraction mechanism in these cases is well described by simple equation of Law of
Mass Action. In several classification systems, the chelates forming system, forms a
separate class by itself.

If we look at the extraction equilibria involving carboxylic and phosphorus acids, they
are not easily described by the distribution law equations. The acids are stronger than
those forming chelates. Weak complexes are formed and a high ligand to metal ratio
is required for their formation. They are more water soluble. Extraction of metals by
organophosphorus, carboxylic and sulphonic acids is affected more by solvent phase
properties than it is for chelating agents. Both organophosphorus and carboxylic acids
often form dimers or polymers in the organic phase.

After having discussed the salient differences in the extractants within this category, it
is essential to look into the characteristic features of their interaction and the
important ones available for metal ion extraction.

i) Chelating Agents
The chelating agent acts as a weak acid and contains a donor group so as to
form a bidentate chelate with the metal. The reagent invariably neutralizes the
charge on the metal ion and satisfies the coordination number requirement. If
the coordination sites remain vacant, they may be occupied by the solvating
molecules which sometimes may be ligand itself. Hydrated metal chelates are
poorly extractable in non polar solvents which do not have the tendency to
replace the water of hydration.

The above discussion amounts to the fact that the chelating agents which form
uncharged metal complexes with the metal ion have at least two functional
groups. One of these is either OH or SH not necessarily attached to the carbon
atom. The other is a basic functional group capable of coordination by its donor
properties. The stable ring formed is usually five or six membered. The stability
of the chelate will depend on a number of factors namely basic nature of the

40
 coordinating site, the acidity of the OH/ SH group, coordination number and Solvent Extraction-I
coordination ability of the metal. Both the acidity of the OH/ SH group and the
basic strength of the donor atom is affected by the structural factors. Also, the
relative position of the active sites in the molecule will affect the extractive
effectiveness of the molecule by determining the size of the ring.

The reagents included under this category are weak or very weak acids,
therefore the formation of extractable complexes will much depend upon the pH
of the aqueous phase. Adjustment of pH of the aqueous is a useful way for the
extractive separation of metal ions if the equilibrium constants of the metal ions
in question are sufficiently different. It is possible to achieve selectivity by
factors other than pH control. One of the most popular approaches is by use of
masking agents which form water soluble complexes of higher stability than
those formed by the chelating agents.

The extractability of the metal chelate is affected by its solubility characteristics

in organic solvents. If a methyl group on the molecule of a chelating agents is
substituted by a benzene ring, an increased solubility of metal chelate in non-
polar solvents is observed. Generally, introduction of a hydrophobic group in
the chelating molecule favours the transfer of its metal chelate in the organic
phase. If the coordination number requirements of the metal in the metal chelate
are satisfied by the water molecules, the chelate is poorly extracted in non-polar
solvents. An increased extraction of these chelates is observed by oxygen
containing diluents, polar in nature such as ketones, esters and alcohols. This
increased extraction of metal chelates is attributed to their ability to replace
water molecule in the metal chelate. Such a cooperative effect of a chelating
agent and a solvent with solvating properties to enhance the extraction of metal
will be dealt under the head of “synergistic extraction”. The well-known
reagents under the head of chelating agents are β -diketones, dithizone, 8-
hydroxyquinoline, monoximes, dioximes, nitrosophenols,
nitrosoarylhydroxylamines, hydroxamic acids and dithiocarbamates. Some of
the acidic chelating agents commercially available in the market for the
hydrometlurgical operations are LlX63, LlX64N, LlX65N, LlX70, SME–529,
P–5000 series (hydroxyoximes); Kelex 100 (oxine derivative) and Hostarex
DK16, LlX 54, X 151 ( β -diketones).

ii) Acidic Organophosphorus Compounds

Alkylphosphoric, phosphonic and phosphinic acids fall under this category.
They also extract the metals by a cation exchange reaction. As mentioned
earlier, the experimental data of these extractions do not necessarily fit into the
mass equation of exchange equilibrium. The organophosphorus acids have
pronounced tendency of association into dimers and larger aggregates. The
other problem arises due to solvation of the metal extractant complex by one
more extractant. The extraction of metal by dimers of the extractant can be
represented as
M (ma)+ + m(HX)2(o) M(HX)m(o) + mH (+a )

This will mean that the extraction is proportional to the m-th power of dimer
concentration and inversely proportional to the m-th power of the proton
concentration, where m is the charge on the metal ion.

The type of alkyl or aryl group of the organophosphates will influence the
acidic nature of the reagent. Increase in the chain length or branching of the
substituent will decrease the acid strength. Although the main mode of action of
these extractants is that of cation or hydrogen exchange, there are numerous

41
Classical Methods cases where the coordination of the phosphoryl oxygen occurs. This results in
the formation of chelation products mainly polymers. Under these
circumstances, the substituents on the phosphorus atom play an important part
which frequently, is contrary to their role in hydrogen exchange mechanism.

It is possible to make certain generalizations regarding the extraction of metals

as a function of the properties of the metal ion. As the charge on the metal ion
increases, then so does its extractability. For metals having the same charge,
extraction varies inversely as the ionic radius. This means small ions extract
better than large ions having the same charge. Thus, in general, at a fixed pH,
the monovalent alkali metal exhibits the lowest extractability and ions like Ce4+
and Th4+ exhibit much higher extractability. This is the reason that sodium or
ammonium salt of DEHPA (di-2-ethylhexyl phosphoric acid) can be used for
the extraction of metal ions having charges greater than +1. The type of anionic
species present in the aqueous phase also affect the extraction.

The nature of organic diluent vis-a-vis the polarity and dielectric constant, is
reported to the affect the extraction. The effect is certainly complex, depending
to an unknown extent, on the dielectric constant, dipole moment and
polarizability of the diluent and the complex and the hydrogen bond donor and
acceptor abilities. It has been shown that the extent of polymerization of the
extractants is related to its interaction with the diluent. And, this in turn affects
the extraction of the metallic species. The effect of the diluent may be drastic
enough to affect the composition of the organic phase complex. In diluents
where the extractant is predominantly monomeric, the composition of the
complex is invariably MXm rather than M(X HX)m.

The development of this class of extractants, at the initial stage, was closely
associated with the objective of finding organic phosphorus compounds for
practical solvent extraction applications in the field of processing of nuclear
fuel. At an early stage of the use of tributyl phosphate (TBP) for nuclear fuel
processing, it was recognized that the acid hydrolysis products of this reagent−
the mono and dibutyl phosphoric acids, were themselves very effective
extractants. This observation prompted a systematic survey of alkyl phosphorus
compounds for metal extraction chemistry. The list of this class of extractants is
very big and it may not be possible to mention all of them. Of all the mono
esters, mono-2-ethylhexyl phosphoric acid is the most commonly used
extractant and among the dialkylphosphates, di-2-ethylhexyl phosphoric acid
(DEHPA) has by far received the maximum attention. Besides these two, a
number of them like octylphenyl phosphoric acid (OPPA), diisodecyl
phosphoric acid (DP-1OR), 2-ethylhexyl phosphonic acid (PC-88A), 2-
ethylbenzyl phosphonic acid, dibutyl buylphosphonate (PC-44) and bis (2,4,4-
trimethylpentyl) phosphinic acid (Cyanex 272) are well known. In the nineteen
eighties, American Cynamid, marketed the mono and disulphur analogues of
Cyanex 272, i.e., bis (2,4,4-trimethylpentyl) monothiophosphinic acid (Cyanex
302) and bis (2,4,4-trimethylpentyl) dithiophosphonic acid (Cyanex 301). The
introduction of sulphur in these acids lowers the pKa of the acids and it may be
possible to work with them and extract at a lower pH.

iii) Carboxylic and Sulphonic Acids

The solutions of carboxylic and sulphonic acids, in non-polar organic solvents,
are similar to cross linked resinous cation exchangers. They frequently offer
some advantages and often only require a pH adjustment of the aqueous phase
for achieving the separation of elements similar in properties. Different
carboxylic, alkyl or aryl-alkyl sulphonic and sulphuric acids form salts with a
number of metal ions including alkali and alkaline earths. These salts are

42
 frequently less soluble in aqueous solutions but more in some organic solvents. Solvent Extraction-I
The extractability of these acids generally parallels their basicity.

The metal extraction by these extractants is complicated by their state of

aggregation in solution. The polymerization of these acids, although, does not
go beyond dimers but the extensive aggregation of their salts plays a significant
role in their extraction. The bulk of available data on the extraction by
carboxylic acids is on normal or branched chain mono carboxylic acids with
seven or more carbon atoms in the chain. Under certain specified conditions, the
aliphatic and aromatic hydroxyl carboxylic and dicarboxylic acids can also
extract certain metal ions. Various benzoic acid derivatives, dinitrobenzoic,
cinnamic and phenylacetic acids and amino and perfluoro derivatives of
n-carboxylic acids have also been used as extractants. Out of commercial
extractants of this class, Versatic and Naphthenic acids obtained from the
distillation of crude petroleum are important.

CH3 CH3 CH3

H2
H3C C H3C C COOH
CH3

CH3 H
CH
COOH
H3C

H3C CH3

(56%) (27%)
Versatic 9
Versatic 9

R2

R1 COOH

CH3
(R1,R2, = C4 - C5)

Versatic 9-11
Other Versatic acids having a similar structure are Versatic 10, 13 and SRS-100.

Naphthenic acid is the name given to a group of cyclic aliphatic monocarboxylic acids
having the following general structure:

(CH2)n (COOH)
R

Naphthenic acids
This fraction of crude petroleum has a molecular weight in the range of about
170 – 330.

43
Classical Methods Aliphatic and aromatic sulphonic acids are represented by the formula RSO2OH (R =
straight/ branched chain or aromatic saturated radical). A variety of these extractants
are available and more useful of these reagents are dodecylbenzene and
dinonylnaphthelene sulphonic acids. Aliphatic sulphuric acids with the general
formula ROSO3H (R= alkyl chain usually at least 15 carbon atoms), have been shown
to be potentially useful extractants.

Carboxylic, naphthenic and sulphonic acids are associated in organic solvents. This is
based on considerations of medium effect on the extent and strength of inter
molecular hydrogen bonding in such compounds. The effects of aqueous phase
parameters on the extraction of metals are similar in all the different type of acids.
The major difference between the sulphonic (and sulphuric) and carboxylic acid
extractants is the capacity of the former to extract cations from solutions below pH 1.
As a rule, the distribution ratio decreases with increasing acidity.

Dimerization of carboxylic acids in non-polar solvents is well established. The

extracted species are invariably solvated by one or more extracted molecules.
Carboxylic acids also have a tendency to higher polymerization with increase in
concentration of extracted metal. In the extraction of Ni(II), Co(II) and Cu(II) by
naphthenic acid, the extracted species have been reported as Ni2. A4. 4HA, Co2A4·
4HA, Cu2A4·4HA, respectively.

The composition of the aqueous phase to a considerable extent affects the extraction
of metal by carboxylic and sulphonic acids. As far as pH is concerned, there is no
qualitative difference. Metals are preferentially extracted from aqueous solutions
containing alkali. Sometimes, there is no extraction in its absence. An alternative way
to increase the distribution is to use sodium salt of fatty acid instead of free acids.

Carboxylic acids react with a number of metal ions and the extraction can be made
selective by adjusting the pH. Moreover, in the metal carboxylate extraction, the
effect of electronegativity is so prominent that a cation exchange takes place.
M1Xm(o) + M 2m(+a ) M2Xm(o) + M 1m( a+)

The less electronegative element sodium is quantitatively exchanged in the organic

phase by any more electronegative element say cobalt. Cobalt can be exchanged by
Cu and Cu for Fe. Naphthenic acid extracts metal with increasing pH in the order
Fe3+ < Cu2+ < In2+ < Co2+ < Fe2+ < Mn2+ over pH 1-10. Thus, a metal in the extraction
series can be displaced from the organic phase by a metal to its left in that series.
2Fe 3( a+) + 3CuA2(o) 2FeA3(o) + 3Cu (2a+)

The use of carboxylic acid as metal extractants for commercial purposes is limited
because of extractants loss, emulsion formation tendency and slow kinetics of the
extraction.

2.3.3 Extraction by Solvation

An important group of solvent extraction systems is based on the solvation of neutral
inorganic molecules or complexes by electron donor containing extractants. Solvation
increases the solubility of inorganic species in the organic phase. The oxygenated
solvents like ethers, esters, alcohols and ketones and organophosphorus esters solvate
the proton and neutral inorganic species making the extraction of the acids and salts
feasible. The simple examples are Ce(NO3)4. (ether)2, HNO3. TBP, VO2(NO3). (TBP)2
and H+ (TBP)4. ReO −4 where TBP is tri-n-butyl phosphate.

The large variety of solvating molecules can be grouped into two distinct categories as
follows:

44
i) Reagents containing oxygen bonded to carbon such as ethers, esters, alcohols Solvent Extraction-I
and ketones.
ii) Reagents containing oxygen or sulphur bonded to phosphorus e.g.
alkylphosphates or alkylthiophosphates.
Despite the similarity between the two categories, several features emphasize the
differences. It is the strong polar character of compounds of category (ii) which is
responsible for the differences.

A major difference between these extractants types is the role of water. Strongly
polar organophosphorus compounds compete favourably with water and can replace
water molecules in the inner coordination sphere of the metal ion. With ethers and
ketones, water is a necessary part of the complex. Take the example of extraction of
uranyl nitrate, it is transferred to dibutyl carbitol with four molecules of water while it
goes all alone in TBP. Moreover, when phosphorus compounds are used as
extractants, it is easier to evaluate the degree of solvation while in the case of class (i)
extractants, it is difficult. In the latter case really, a number of mixed hydrates –
solvates coexist in equilibrium. In this regard a typical case, worth mentioning is the
variation in the water molecules in the extracted species when iron (iii) chloride is
extracted in ether.

With the above background, we should now look into important specific
characteristics of the two categories of solvating extractant.

1. Extractants Containing Carbon-Oxygen Bonds

As mentioned earlier, the extractants of this class are essentially ethers, ketones
and alcohols. They are electron donating reagents but alcohol being amphoteric,
exhibits both donor and acceptor properties. These extractants did receive
attention during the earlier part of development of metal extraction chemistry.
Diethyl ether and diisopropyl ether were at one time very favoured extractants
for metal halides and halometallic complexes. They were also used as
extractants for metal nitrates resulting into the development of separation
technology for nuclear fuel reprocessing. Metal sulphates and percholates are
generally nonextractable into these solvents. Only one ketone, methyl isobutyl
ketone (MIBK) has been used commercially for the extraction of metals.

It has been shown that inorganic salts, soluble in water immiscible oxygen
bearing organic solvents, are usually weak electrolytes or they involve a
complex ion. The main characteristic of extraction from aqueous halide
solutions by oxygen containing solvents is the extraction of protonated metal
complex anions, preferentially singly charged ones, (H+.FeCl4−). An equally
important feature of the system is the high extractability of essentially covalent
metal halides. The striking difference between the two is that the halo
complexes are extractable into oxygenated solvents only while the halides can
be transferred into nonpolar hydrocarbons also. With some restrictions due to
aqueous complex chemistry of metals in halide solutions, higher extractions are
observed for monovalent complex anions of bivalent and trivalent transition
metals. Inspite of pronounced complexing tendencies of bivalent metals, the
high charge on the complex MX 24− prevents their extraction into relatively high
dielectric constant solvents such as butanol and octanol.

As regards the extraction of metal nitrates, a particular aspect has received

special attention i.e., the role of salting out agents. It has been observed that the
addition of nitrate salts to the aqueous phase greatly enhances the extraction.
The extraction of uranyl and thorium nitrate in ether is greatly enhanced by the
addition of ammonium nitrate. It was found that other metal nitrates could be
45
Classical Methods used for the purpose but the multivalent nitrates with pronounced hydration
tendencies proved to be the most effective. The function of the salting out
agents is considered to be three-fold as is given below:
i) Providing a higher concentration of complexing anion which by the Law
of Mass Action, would increase the concentration of the complex and
thus, improve the extraction.

ii) Water will bind to the ions of salting out agent and thus, become
unavailable as free solvent to compete with the organic phase for
partitioning.

iii) The addition of salt will lower the dielectric constant of the aqueous
phase which will favour the formation of ion association complex. It is
the neutral ion association complex which is getting extracted.

If one looks at the organic phase characteristics, it has been observed that the
extraction power changes with the class and solvent molecule. In other words,
the solvent efficiency remains a specific characteristic of any particular system.
For example, generally ethers are better extractants than ketones for hexavalent
actinide nitrates while trend is opposite for tetravalent metal halides from
aqueous solutions. Within a homologous series, there is a lowering of metal
extraction on increasing the hydrocarbon character of the organic solvent. This
means that the lengthening of alkyl chain in alcohols, ketones and ethers by
introducing methylene group, will cause a decrease in the extractive power. The
dipole moments of ethers and ketones are affected by the symmetry of the
molecules. As a rule, asymmetric ethers and ketones have a greater efficiency
than the symmetric ones. The greater dipole of asymmetric extractants leads to
an increased electron density at the donor oxygen and thus, increased tendency
to coordinate. The distribution ratio of metal decreases with increasing
branching of the alkyl group, the effect is particularly marked when the
branching is near the active oxygen.

As of today, the phosphorus bonded oxygen donor extractants have completely

phased out the ethers and ketones from technological applications.

2. Extractants Containing Phosphorus-Oxygen Bonds

Extractants of this group could be considered as derivatives of phosphoric acid.
The general structures of the esters of organophosphorus acids are given in
Table 2.1.

Table 2.1: General Structure and Examples of Esters of Organophosphorus

Acids
Structure Ester Example

(RO)3P=O trialkyl phosphate tri-n-butyl phosphate (TBP)

R(RO)2P=O dialkyl alkylphosphonate dibutyl butylphosphonate

(TBBP)
R2(RO)P=O alkyl dialkphosphinate butyl dibutylphosphinate

R3P=O trialkylphine oxide tri-n-octylphosphine oxide

46
 (TOPO) Solvent Extraction-I

The first three members of this group are esters of phosphoric, phosphonic and
phosphinic acids and the last member is a derivative of phosphine. The extraction
mechanism for all of them is mainly the same. It is the oxygen of the phosphoryl
group which is responsible for the coordination bond formed with the metal. In the
case of esters, there is a possibility of formation of more than one coordination bond
through other oxygen atoms. The inter or intramolecular bifunctional complex, thus,
formed exhibits different extraction and stripping rates. The solubility of these
extractants in water is very much in the predictable order: phosphates < phosphonates
< posphinates < phosphine oxide. This sequence is in line with the increasing polarity
of the phosphoryl group in the molecule. The solubility decreases with the increasing
chain length.

The high extraction power of neutral organophosphorus esters has been demonstrated
for a large number of metal salts. The nitrates and chlorides have received the most
attention. The extraction from sulphates and phosphate solution is generally poor. The
extraction of metals from halide solutions other than chlorides follows closely that of
the latter. The extraction by these reagents involves the solvation of the electrically
neutral metal salts formed by their depressed ionization in the aqueous solution. The
reagent functions satisfactorily in the presence of high concentration of salting out
electrolytes in the aqueous phase. Thus, the extent of extraction will depend on the
degree of formation of the extractable species and the solvation number of the metal.
There is a strong competition between the extractants molecules and water to occupy
the coordination sites of the metal ion. This will depend upon the type and the
structure of the neutral organophosphorus extractants. Nearly all metal extractions are
increased as the number of direct C − P linkages in the series increase, i.e., in
phosphate < phosphonate < phosphinate < phosphine oxide. The salting out effect
observed in the case of these extractants is more or less on similar lines as with
solvating molecule with carbon oxygen bond. A number of salting out agents have
been investigated for their capacity to draw the metal to the organic phase. The
extraction increases as the radius of the cation of the salting out agent decreases in the
alkali and alkaline earth series. The extraction increases with the increasing charge on
the cation. The effect of the diluent on the variation of the distribution ratio of the
metal ion can be summarized as under:
i) At low metal loadings, the distribution ratio is generally higher in aromatic and
aliphatic hydrocarbons than in ethers and ketones.
ii) Especially low values are obtained in polar alcohols and chloroform.
iii) It still depends frequently on the aqueous phase conditions whether the
unsubstituted aromatic or aliphatic hydrocarbons will show higher distribution
ratio.
The most extensively used reagents of this class are tributyl phosphate,
tributylphophine oxide, trioctyl phosphine oxide (TOPO). In the Nineteen eighties,
the American Cynamid introduced a new extractant Cyanex 923 in the market. It is a
mixture of four trialkylphosphine oxides and has shown a great potential for metal ion
separations.

At this concluding stages of the discussion on the extraction by solvating molecules, it

may be important to make a brief comment on some other extractants with phosphorus
− sulphur bond. This group contains sulphur analogues of the previous group e.g.
alkylthiophosphoric, alkylthiophosphonic and alkylthiophosphinic esters as well as
phosphine sulphides like the Cyanamid reagent, trisobutylphosphine sulphide
(TIBPS), Cyanex 471 X. The importance of having analogues of oxyphosphorus
reagents with sulphur, is of course, the difference between the oxygen and sulphur
affinities for metals. The extractants with oxygen donor are classified as hard bases

47
Classical Methods
The discovery of HMWA as
extractants dates back to
1948 when Smith and Page
observed that their solution
in organic solvents can
extract acids from the
aqueous phase.
Subsequently, the great
potential of these reagents
for the extraction of anions
and anionic metal complex
was realized.
48
while with sulphur donor are soft bases. It is, therefore, expected that hard bases will
associate with hard acids and soft bases with soft acids. For metal ions like Fe3+, La3+,
Th4+ etc. (hard acids), extractants with oxygen donors are a better choice than a
nitrogen or sulphur donor. Metals such as Cu2+, Ag+, Cd2+, Pd2+, etc. are soft acids,
hence, prefer sulphur donor extractants. Cyanex 471 X has been successfully
developed as an extractant for Ag+, Pd2+ and Hg2+.
Another class of extractants which could be of considerable interest is the amide type
extractant (A 101). It is a weakly basic extractant with carbonyl being the functional
group. The reagent has been used for the separation of Nb and Ta and Mo and Re.
Subsequent to development of A 101 in China another reagent N 503, which is
N, N – dimethylheptyl acetamide has been used for the separation of Nb and Ta.
2.3.4 Extraction by Ion Pair Formation
This primarily involves the extraction of a species formed due to an interaction
between an anionic metal species in the aqueous phase and the cation furnished by an
organic base. The strongly basic high molecular weight amines (HMWA) are able to
extract the metals by forming the ion pairs with anionic metal complexes. The other
extractable pairs formed by quaternary phosphonium, arsonium, phenylonium bases
are also included under this category. Some of the examples of different types
2−
areR3NH+FeCl −4 , (R4N+)2.ZnCl 24− .(R3NH+)2. (Cd(C2O4)2) and (C6H5)4As+.MnO −4 .
Under this class of extractants, high molecular weight amines have received
maximum attention.
R3N(o) + H+(a) + A (−a ) ↔ R3NH+A−(o) (salt formation)
R3NH+A (−o ) + B −
↔ R3NH+B (−o ) + A (−a ) (anion exchange).
( a )
The amine salt can undergo anion exchange with anion (B−) in the aqueous phase, B-
can be simple or complex anion like Cl−, CrO 24− or an anionic metal complex like
FeCl −4 , HgCl 24− and ZnCl 24− . The order of preference in the organic amine solution
is similar to that anion-exchange resins, Cl− > NO 3− > HSO −4 >F−.
The amine salt on treatment with sodium or ammonium hydroxide can be reverted to
amine. The popularity of these extractants probably stems from the fact that the
extraction is mainly through ion exchange and thus, they combine some of the
advantages of both solvent extraction and ion exchange. They are popularly known as
liquid anion exchangers.
Generally speaking, liquid ion exchange involves the selective transfer of a solute, an
anion or anionic metal complex, from aqueous to organic phase reversibly. The extent
of extraction of the metal directly depends on the ease of formation of anionic metal
complexes in the aqueous phase. That is to say, aqueous phase parameters like
concentration of ligand, hydrogen and metal ion, charge on the complex metal ion
involved, the presence of other complexing or competing ion and temperature will not
only affect the formation of the extractable species but also, in turn, have a significant
effect on the extent of extraction. Furthermore, such ion association systems are also
sensitive to organic phase parameters like the nature, structure and chain length of the
amine, its concentration and the type of the organic solvent used as diluent. Each of
these factors can change the course of the overall extraction process of a metallic
species unpredictably. It is apparently a general phenomenon that the extraction
power of alkylamines increases from primary to secondary to tertiary to quaternary
amines. An exception to this rule is the extraction by bulky amines where steric
factors generally affect the basicity of amines, which in turn affects the stability and
polarity of their salts. Due to steric factors, change in the sequence of extractability of Solvent Extraction-I
amine salts is also observed in the case of anionic carboxylato complexes.

Several efforts have been made to correlate the nature of diluent with extraction
power of an amine. As a matter of fact, the lack of correlation between the
distribution ratio of a metal and physical characteristics of a solvent such as dipole
moment and dielectric constant have led to the conclusion that the amine-diluent
combination rather than amine alone should be considered as the effective extractant.
There are some limitations in using these reagents as extractants. The most usually
encountered is the formation of emulsion. This problem can be effectively tackled by
choosing a low surface active extractant and a proper diluent. Control of conditions
like temperature, pretreating acid, amount of free acid in aqueous phase and the
volume of the two competing phases help to minimize this problem. In some cases,
spectacular reduction in emulsion formation has been observed by the addition of
2-3 % higher alcohols.

The existing literature on the extraction behavior of high molecular weight amines
reveals that mostly the extraction of metals from mineral acids such as hydrochloric,
nitric and sulphuric acid has been investigated. In particular, the extraction of anionic
chloro complexes has received maximum attention. Some interest has also been
generated in extending the use of HMWA for the extraction of various metal ions
from aqueous carboxylic acids. Some work has been reported on the malonate,
tartrate, citrate and oxalate complexes.

High molecular weight amines are basically aliphatic primary, secondary, tertiary
amines and quaternary ammonium salts with molecular weight in the range 250 to
600. Many of the extractants of this category which are commercially available, are
primary amines – Primene JMT, Primene JMT, Primene 81R; secondary amines
Amberlite LA- 1, Amberlite LA- 2, Adogen- 283; tertiary amines – Alamine 336,
Adogen 364, Adogen 382, and quaternary amines – Aliquat 336, Adogen 464.

Some quaternary phosphonium and arsonium compounds have found extensive use in
the extraction of simple acid radicals, oxyanions of metals, anionic inorganic
coordination complexes involving organic ligands. These extractants behave as strong
electrolytes and are usually water soluble. The metal complexes with a well-known
stoichiometry are formed when reagent is added to a neutral or weakly acidic solution
and they are transformed into a slightly polar organic solvent such as chloroform or
methyl isobutyl ketone. Apart from the effect of anion on the extractability of the ion
pair, the size of the organic cation bears markedly on the extractive property. Another
property which prominently affects the extraction is the nature of the diluent. A very
typical example is the extraction of MnO −4 or ReO −4 in chloroform formed by
tetraphenylarsonium chloride. The extracting Mn(VII) species is proposed to be
(C6H5)4As+.MnO −4 . Some dimerization of the monomer in the organic phase also
takes place.

2.3.5 Extraction by Crown Ethers

A new class of reagents, namely the crown compounds, are fast emerging as potential
extractants. Initially, the importance of these compounds was highlighted because of
the fact that they are good extractants for alkaline and alkali earth metals and thus, the
separation of these metals by solvent extraction became possible. These are
multidentate macrocyclic ligands with O, N or S as donor atoms. The binding of the
metal is determined by the compatability of the cavity size of the crown compound
and the radius of the metal ion.

The first few compounds of this series were crown ethers which consist of cyclic

49
Classical Methods (-CH2-O-CH2-) groups to form a cyclic compound having 12-24 ring oxygen atoms.
Following the synthesis of crown ethers, several new compounds have been prepared
and investigated. These compounds differ in properties owing to the differences in
ring atoms and the number of donor atoms. The variation in the ring size leads to the
changes in the size and hence, the size of the ion which can be accommodated. By
introduction of the linking group, the donor strength of the oxygen can be changed.
Also, by introducing S or N atoms instead of oxygen, crown compound of different
specificity are synthesized. The introduction of oligoether chains in the classical
crown ethers leads to the formation of a new bicyclic type of ligands. These ligands
are known as cryptands and find considerable application in analytical chemistry. It
may be worth mentioning that the discovery of macrocyclic polyether was a chance
but the synthesis of macrobicyclic polyethers is carried out in a planned way.

The crown ethers contain a central varying size hydrophilic cavity which is ringed
with electronegative binding polyether oxygen atoms. These oxygen items are
surrounded by a collar of –CH2 groups imparting it a hydrophobicity. They complex
with the cation converting it into a lipophilic species which extracts in the organic
solvent. The complexes are composed of two ionic species held together by
electrostatic attraction.

The selectivity in extraction is generally explained by the compatibility between

cation and hole or cavity size of the crown ether. But the ion-in-the hole model has
certain limitations. As the number of ring atoms increases the macrocyclic flexibility
increases and it may be difficult to define the cavity diameter. The attachment of
certain groups affects the donor strength of the oxygen atoms. Also, the nature of the
donor atom plays an important role on selectivity. The extent of extraction is affected
by the nature and concentration of the crown ether and the counter ion. The nature of
the diluent also affects the extractant. Generally, it is preferred to use the solvents of
high dielectric constants. Moreover, the solvent should have high solubility for the
crown ethers. The complexation with ethers transforms a relatively small alkaline
earth metal ions into a voluminious organic cation which is more soluble in organic
media. As a consequence of this, solubilization of inorganic salt of low polarity
results. With anions of highly localized negative charge, the solubilization may be
difficult. Therefore, the salts containing hard anions like fluoride or hydroxide can be
solubilized with difficulty in solvents like benzene. But soft anions like picrate, iodide
or tetraphenyl borate are very suitable. The extraction of metals by crown ethers in the
presence of picrates or dye stuffs has the added advantage of employing it as a
colorometric method. However, the cost of crown ethers has been a deterrent for their
application as extractants on a large scale.

SAQ 4
A certain metal complex, MXn.2H2O, formed with the chelating agent HX is poorly
extracted in a nonpolar solvent but its extraction is favoured in a polar solvent.
Explain why?
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................

SAQ 5
What are the two basic approaches adopted to achieve selectivity in the metal ion
extraction by chelating agents?
..........................................................................................................................................
..........................................................................................................................................

50
SAQ 6 Solvent Extraction-I

Why do we generally prefer an alkylphosphorus acid for the extraction of a metal ion
over a carboxylic acid?
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................

SAQ 7
The extraction of uranyl nitrate in a solvating extractant is enhanced by the addition
of equal amounts of LiNO3, NaNO3 and CsNO3 to the aqueous phase. Arrange these
alkali metal nitrates in their capability to enhance the extraction. Give reasons also.
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................

SAQ 8
Generally, what is the order of extraction power of high molecular weight amines?
Give a possible reason if a deviation in the sequence is observed.
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................

SAQ 9
What is the common reason for the selectivity in the extraction by crown ethers?
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................

2.4 DILUENTS AND MODIFIERS

In the previous section, we have seen that different categories of extractants are
available and the range is very broad. The different extractants have their own
advantages and limitations. One particular point which should be kept in mind is that
the majority of extractants are either solids or their viscosities are too much high for
their direct use in the solvent extraction. It is, therefore, a common practice to
dissolve them in a suitable solvent which is known as diluent. Thus, the diluent refers
to the organic liquid in which the extractant is dissolved to form the solvent. In
majority of cases, the diluent comprises the major portion of the solvent. During the
solvent extraction, sometimes the formation of a third phase takes place and to avoid
this, a modifier may have to be added to the solvent system. In view of the importance
of diluents and modifiers to make an extractant system workable, it may be essential
to discuss their characteristics. Proper selection of diluent and modifier can be as
important as selecting the extractant because of their physical and chemical effects on
the process. Also, they may influence the economics of the process to a great extent.

2.4.1 Diluents
The reasons for using a diluent are new clear to you and they can be enumerated as
under:

51
Classical Methods i) They are mainly used to decrease the viscosity of the extractant. Generally, the
extractants used for commercial solvent extraction processes are viscous liquids
and they cannot be used as such.
ii) Depending upon the metal to be loaded, an appropriate concentration of the
extractant is to be used. Thus, the diluent provides the solvent for preparing the
solution of the extractant of the desired concentration.
iii) Another role of the diluent is to decrease the emulsion formation tendencies. A
number of extractants are surface active agents and at high concentration, tend
to emulsify specially at high agitations.
iv) The diluent improves the dispersion and coalescene properties of the solvent.
These are two very important aspects of a solvent extraction process.
After having seen the various roles of diluents, it may be easy to define their essential
characteristics which are listed below:
i) It should be mutually soluble with an extractant or modifier.
ii) It should have high solvency for the extracted metal species; thus, providing a
high metal loading capacity to the solvent and minimizing the problem of third
phase formation.
iii) It should have low volatility and a high flash point. This minimizes the losses
due to volatility and fire hazards.
iv) It should be in its own right insoluble in the aqueous phase.
v) It should have low surface tension.
vi) It should be cheap and readily available in large quantities.
The choice of diluents ranges from simple molecules to complex mixtures.
They are both aliphatic and aromatic. The simple molecules that are routinely used at
the laboratory scale are n-hexane, cyclohexane, benzene, toluene, xylene, chloroform,
carbon tetrachloride and chlorobenzene. The use of some of these is restricted due to
environmental or toxicological considerations. The cost can also be a deterrent.

One of the important cheap diluents for industrial use is kerosene particularly its
1600- 2000 C fraction. For commercial applications, particularly in hydrometallurgy, a
range of diluents has been developed by major oil companies. In general, these
diluents contain a mixture of paraffinic, aromatic and naphthenic hydrocarbons. The
Excaid range from Exxon (Escaid 100, Escaid 110, Escaid 350), MSB 210, Shell 140,
Shell R from Shell and Chevron Ion Exchange solvents speak of the variety of
commercial diluents available.

In the earlier section, we have noticed that the diluents affect the extractability of an
extractant to a great extent. It has become apparent that diluents are not as inert, as
they might appear to be. Various workers have tried to correlate different properties of
the diluents with the extraction efficiency of a system. The mechanism of the role of
the diluent seems to be complex. One property of the diluent which has received
special attention is its polar nature. In the extraction of rare earth nitrates with Aliquat
336, a decrease in the extraction of the metals with the polar nature of the diluent was
observed. Similar effect was noticed on the extraction of anionic chloro species in
tertiary amines. From different observations, one may conclude that the diluent affects
the solvation of the extractant and hence, its extractive properties. Interaction between
the diluent and the extractant lowers the free concentration. The effect of dielectric
constant of the diluent in some other systems was observed and no straight correlation
could be observed. It is difficult to ascribe the change in extraction solely to the
dielectric constant. Other effects such as impurities, degree of aromacity, solubility of
diluent in water, etc. may also be involved.

52
One thing clearly emerges out of the above discussion that the choice of a diluent for Solvent Extraction-I
a particular process cannot be predicted, a priori. A diluent is usually picked up on the
basis of the experimental data. Diluents are usually produced on industrial scale
resulting in some variations in their composition. These variations and the presence of
impurities may alter the behaviour of diluents.

2.4.2 Modifiers
One of the very serious problems in solvent extraction is the formation of a third
phase i.e., two organic phases. Most of the available evidence on third phase
formation suggests that it is essentially a solubility problem. Invariably, it is the
organic phase that splits into two phases to yield a metal complex-rich phase at the
aqueous interface and a diluent rich phase above. In most of the cases, the problem is
overcome by the addition of a third component known as a modifier. This helps to
restore the organic phases to one. Such modifiers are invariably solvating agents like
isodecanol, 2– ethylhexanol, p-nonyl phenol and TBP.

The third phases are of a density intermediate between that of the solvent phase and
the aqueous phase and result from the effects of the diluent on the heterogenous
equilibrium associated with the system. Based on several observations, some
conclusion can be drawn on the third phase formation.
i) The formation of third phase is temperature dependent. Usually increase in
temperature will result in the disappearance of third phase.
ii) The appearance of the third phase is more common with aliphatic diluents.
iii) In the case of high molecular weight amine extractants, the tendency for third
phase formation with different anions follows the order NO 3− < Cl − < SO 24− . A
similar sequence is observed with DEHPA.
Addition of a modifier helps to overcome third phase and emulsion formation
tendencies in a solvent system. As is with diluents and extractants, the modifier
should be very soluble in the organic phase, insoluble in the aqueous phase, be readily
available and cheap. Usually, the amount of a modifier used is 2-5 volume percent. In
some cases, where the extractant concentration is high, the requirement may be as
high as 20% or more.

Experimental evidences suggest that a modifier like a diluent cannot be selected

arbitrarily. The selection for a particular system is to be made on the basis of
experimental data. The amount of a modifier required is also to be determined
experimentally. One point which should be borne in mind is that the effect of a
modifier and a diluent in the extraction stage differs greatly from their effects in
scrubbing and stripping stages, both on mass transfer and kinetics, and also on phase
disengagement and solvent entertainment.

SAQ 10
What are the common requirements for both the diluent and the modifier?
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................

2.5 SUMMARY
Solvent extraction is a popular separation technique because of its convenience, speed
and a favourable economics. This versatile technique can be safely extended from

53
Classical Methods micro levels to macro concentrations. Some of the important theoretical and practical
aspects of the technique have been presented in Units 2 and 3. In Unit 2, the law
governing the partitioning of chemical species, its limitations and the different terms
used to explain distribution have been discussed. The focus of discussion was on the
extraction of metal ions. A classification of different types of extractants used for
metal ions has also been described. The characteristics, advantages and the problems
faced in the use of different categories of extractants have been highlighted.

The role of diluents and modifiers in solvent extraction system mainly depends upon
the composition of the aqueous and organic phases. Finally, the characteristics of
diluents and modifiers have been explained.

2.6 TERMINAL QUESTIONS

1. Derive an expression for the distribution of acetic acid between water and
benzene in terms of its dissociation and polymerization constants. Also analyze
the dependence of distribution on different variables.

2. The distribution coefficient of a certain weak acid between benzene and water
is 100. Calculate the distribution ratio for this acid at pH = 7.00 of the aqueous
phase. Ka = 1.00 × 10 −6 for the acid in the aqueous phase and the acid remains
as a monomer in the benzene phase.

3. The distribution ratio for a solute X in water-carbon tetrachloride is 10.

Calculate the percentage of solute extracted from 50 mL of water by 100 mL of
carbon tetrachloride where (a) the total volume of CCl4 is used at one time and
(b) the 100 mL of CCl4 is divided into five 20 mL portions and employed one
after the other.

4. Highlight the differences between chelating agents and acidic

organophosphorus esters, carboxylic acids as metal ion extractants.

5. High molecular weight amines extract the metal ions by a mechanism which is
similar to their uptake by solid anion exchangers. In what respects, extraction in
high molecular weight amines scores over sorption of metal ions by solid anion
exchangers?

6. What are the essential characteristics of a diluent?

2.7 ANSWERS
Self Assessment Questions
1. The distribution coefficient, thermodynamic distribution coefficient and
distribution ratio will be the same when
i) The activity coefficient of the distribution species in the two phases
approaches unity, and

ii)The distribution species does not undergo any interaction, i.e. association
or dissociation in either of the phases
100 D
2. %E=
D + Va / Vo

100 × 132
Percent of Iodine extracted =
132 + 100 / 50

54
 1320.0 Solvent Extraction-I
=
134
= 98.51%
Iodine remaining in the aqueous phase = 1.49%

100 DA
3. 99 =
DA + 1
Distribution ratio of A (DA) = 99
Likewise distribution ratio of (DB) = 0.01

DA
β= = 99/0.01 = 9900 ≈ 104
DB

4. Polar solvent can replace the water molecules in the complex; thus, making the
species more organic phase loving. Non-polar solvent cannot replace the water
molecules.

5. The two approaches generally adopted are

i) by adjusting the pH of the aqueous phase, and

ii) by adding appropriate masking agent in the aqueous phase.

6. The alkylphosphorus acids are preferred over carboxylic acid because of the
following reasons:
i) Carboxylic acids have more aqueous solubility and therefore, suffer from
the drawback of extractant loss,
ii) Carboxylic acids are more surface active and hence, emulsion formation
tendency is more pronounced, and
iii) Generally, the kinetics of extraction is slower in the case of carboxylic
acids than in alkylphosphorus acids.
7. The capability of enhancing the extraction follows the order

LiNO3> NaNO3>CsNO3

Li+ being the smallest has the highest hydration tendency, followed by Na+ and
then Cs+. Because of hydration tendency, the water molecules in the aqueous
phase may not be available to compete; thus, resulting into enhancement in the
extraction in the organic phase.

8. Generally, the order of extraction power of HMWA is primary< secondary <

tertiary < quaternary. The exception is in the case of bulky amines where the
basicity is affected. Steric factor may also cause change in sequence in the case
of carboxylate complexes.

9. The selectivity in extraction by crown ethers is generally achieved by the

compatibility between the cation and the hole or cavity size of crown ether.

10. The common requirements of a diluent and modifier are;

i) They should be mutually soluble and should have good miscibility with
the extractant.

ii) They should have negligible aqueous solubility.

55
Classical Methods iii) They should be cheap and easily available in large quantities.

2.8 TERMINAL QUESTIONS

1. The distribution of acetic acid in water and benzene can be described as under
(CH3COOH)a (CH3COOH)o

[CH 3 COOH] o
KD = o, and a refer to benzene and aqueous phases,
[CH 3 COOH] a
respectively.

However, acetic acid dissociates in the aqueous phase

CH3COOH CH3COO¯ + H+
[CH 3 COO − ] × [H + ]
Ka =
[CH 3 COOH]
and forms a dimer in benzene.

2 CH3COOH (CH3COOH)2

[(CH 3 COOH) 2 ]o
KD =
[CH 3 COOH] a2
The overall distribution of acetic acid, described by Distribution ratio (D), is
given by

Total conc. of acetic acid in its different forms in organic phase

D=
Total conc. of acetic acid in its different forms in aqueous phase
[CH 3 COOH] o + 2[(CH 3 COOH) 2 ] o
=
[CH 3 COOH] a + [CH 3 COO − ]a
Incorporating the equilibrium constants given above
K D[1 + 2 K D (CH 3 COOH)] o
D=
1 + K a[H + ]
This shows that the distribution of acetic acid varies as a function of the pH and
acid concentration in organic phase.

100(1.00 × 10 −7 )
2. D= = 9.09
(1.00 × 10 −7 ) + (1.00 × 10 −6 )

Va
3. a) Fraction remaining in the aqueous phase =
D
V

o + Va
50
=
(100)(10) + 50
= 0.04762
Fraction transferred to the organic phase = 1− 0.04762
= 0.9524
% Extracted = 95.24

56
 5 Solvent Extraction-I
 50 
b) Fraction remaining in the aqueous phase =  
 50 + (10)( 20) 
= 0.00032
Fraction transfer to the organic phase = 1− 0.00032
= 0.9997
% Extracted = 99.97

4. See sub–Sec. 2.3.2 i) – iii)

5. High molecular weight amines score over solid anion exchanger in the
following respects:
i) The extraction process is much faster than the sorption – desorption on
ion exchangers.
ii) HMWA – diluent systems offers a wider choice of amines and diluent
than that is available with solid anion exchanger. Therefore, several of the
separations which are difficult to achieve on solid anion exchangers can
be easily accomplished by extraction in an appropriate high molecular
weight amine-diluent system.

6. See sub–Sec. 2.4.1

2.9 FURTHER READINGS

1. Solvent Extraction in Analytical Chemistry, By G. H. Morrison and H. Freiser,
John Wiley & Sons Inc.
2. Ion Exchange and Solvent Extraction of Metal Complexes, By Y. Marcus and
A. S. Kertes, Wiley – Interscience.

3. Solvent Extraction : Principles and Applications to Process Metallurgy Part I,

By G. M. Ritcey and A. W. Ashbrook, Elsevier Science Publishers B. V.

4. Solvent Extraction of Metals, By A. K. De, R. A. Chalmers, and S. M. Khopkar,

Van Nostrand-Reinhold Publication.

5. Solvent Extraction of Metal Chelates, By J. Stary, Pergamon Press.

57
Classical Methods
UNIT 3 SOLVENT EXTRACTION – II
Structure
3.1 Introduction
Objectives
3.2 Studies on Extraction Equilibria
Extraction of Metal Chelates
Extraction by solvation
Extraction by ion pair formation
Synergism
3.3 Factors Influencing Extraction
pH
Molarity of the Acid
Metal Ion Concentration
Presence of Salting out Agents
Presence of Masking (Sequestering) Agent
Concentration of the Extractant
Nature of Diluents
3.4 Different Approaches for Metal Ion Separation
Stripping
pH of the Aqueous Phase
Acid Molarity of the Aqueous Phase
Presence of Masking Agents in the Aqueous Phase
Selective Stripping from the Organic Phase
3.5 Criteria for the Choice of Organic Phase
3.6 Summary
3.7 Terminal Questions
3.8 Answers

3.1 INTRODUCTION
In the previous unit, you have been introduced to the technique of solvent extraction
and its potential. The partition law and its limitations have been discussed. The
important terms which are used to express the distribution of chemical species have
been explained. It is clear that the distribution of a chemical constituent will depend
upon the composition of aqueous and organic phases. In other words, the extent of
extraction will depend upon the aqueous and organic phase variables. Amongst the
organic phase variables, the most important is the nature and the type of the extractant.
There are numerous extractants and they keep on flooding the market to meet certain
requirements of the separations. A broad classification of different types of extractants
used for metal ions has been discussed in the earlier unit. In order to fruitfully utilize
the aqueous and organic phase parameters for effective metal ion separations, we will
have to look into the various equilibria existing in the two phases and the over all
extraction equilibria.

This particular unit begins with a discussion on the metal ion extraction equilibria of
some of the important extraction systems. The different steps involved give an idea of
various factors which affect the metal ion extraction. Once the parameters influencing
extraction are known, they can be varied to achieve separations with high separation
factors. The practical utility of the background discussed herein will be demonstrated
by citing examples of various metal ion separations achieved by variation of different
parameters. It may be important to point out here that the discussion on equilibria is
confined to some typical examples. All the different types of systems cannot be
covered because of the variability and complexity involved in the extraction systems.
Towards the end, a brief discussion on criteria for the choice of organic phase is
presented. It becomes particularly important because the technique finds extensive
applications for industrial operations.

58
Objectives Solvent Extraction-II

After studying this Unit, you should be able to

• explain the extraction of metal ions with some important class of extractants,
• enumerate different aqueous and organic phase parameters which affect the
extraction of metal ions,
• describe various approaches which are generally adopted for metal ion
separations, and
• decide the criteria for the selection of the organic phase particularly for
commercial applications.

3.2 STUDIES ON EXTRACTION EQUILIBRIA

The extraction equilibria are usually complicated because we have to take into
consideration the equilibria existing in both the phases. It is not only the metal ion
which has to be considered but the status of extractant has also to be considered. The
existence of different species in the two phases and their partitioning need proper
assessment. Generally, the distribution of the metal in the two phases is expressed in
the form of an equation which involves certain constants and a few experimental
variables. The expression is verified by observing the effect of variables on the
distribution of the metal ion. In this context, the usual methodology followed is that of
slope analysis. In the slope analysis, the experimental condition chosen is such that
the different variables are kept constant except for one. The effect of that particular
variable on the distribution of metal is observed and the slope of the plot indicates the
involvement of that particular variable/ chemical entity in the formation of the
extracting species. The spectroscopic methods particularly absorption spectroscopy
(IR, UV, Visible) are also helpful in identifying the presence of the different species.
Here, it may be worthwhile to point out that usually the infrared spectrum of the
organic phase is of little help because of its complexity.

In this section, some typical extraction equilibria are discussed under the following
heads:
i) Extraction of metal chelates
ii) Extraction by solvation
iii) Extraction by ion pair formation
iv) Extraction due to synergism
It may be noted that a particular class of extractants or an extractant may behave in a
dual capacity. It may act as an acid to neutralize the charge on the metal ion and/or it
may solvate the neutral species. It is just possible that the same extracting species may
play the dual role.

3.2.1 Extraction of Metal Chelates

In the classification of extraction systems (Unit 2, Sec.2.3) under extraction by
compound formation, it has been mentioned that the chelating agents form a very
important class of extractants. Metal chelates represent a type of coordination
compounds in which the metal ion combines with a polyfunctional base, capable of
occupying two or more positions of the coordination sphere of the metal ion, to form a
cyclic compound.

A large number of chelating agents are used for metal ion extractions. It may be a big
task even to list a few important ones primarily because of their availability in large

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Classical Methods number and variety. But as an example, we may consider the reagent 8-quinolinol (8-
hydroxyquinoline) which is often referred to by the trivial name “oxine”.

N
OH
Oxine

This organic compound forms neutral species with a number of metal ions which is
insoluble in water but soluble in chloroform or carbon tetrachloride. If oxine is
abbreviated HOx, the equilibria can be written as

Mn+ + n HOx M(Ox)n + n H+

Another well known chelating agent used for solvent extraction is diphenyl
thiocarbazone known by the popular name “dithizone”.

H
N N
S H
C
N N

Dithizone

Dithizone and its complexes with metal ions are insoluble in water but soluble in
chloroform or carbon tetrachloride. The list of metals forming chelates includes Mn,
Fe, Co, Ni, Cu, Zn, Ag, Cd, Sn and Pb.

Let us consider that a metal ion with a charge ‘n’ reacts with an extracting chelating
reagent to form the metal chelate. When the aqueous phase containing the ligand (HR)
is brought in contact with the organic phase, the reagent distributes itself in both the
phases till the equilibrium is attained.
(HR)a (HR)o
... (3.1)
The distribution coefficient of the ligand, KDR, is given by
[HR ]o
KDR = … (3.2)
[HR ]a
Further, the ligand dissociates in the aqueous phase as follows:

HR H+ + R
… (3.3)
The dissociation constant of the ligand, Ka , is expressed as
[ H + ]a [ R − ]a
Ka = … (3.4)
[ HR ]a

The chelating anion, (R—), reacts with metal ion (Mn+) to form the chelate as shown
below:

60
 M n+ + n R MR n Solvent Extraction-II
… (3.5)
The formation constant of the complex Kf is given as follows:
[MR n ]a
Kf = ... (3.6)
[M n + ]a [R − ]an
The metal chelate formed on equilibration with the organic phase distributes itself
between the aqueous and organic phases till an equilibrium is attained.
(MRn)a (MRn)o
... (3.7)
The distribution constant of the complex, KDX, is given by
[ MR n ]o
KDX = ... (3.8)
[MR n ]a
We assume that the metal in the aqueous phase predominantly exists as Mn+ only and
in the organic phase as MRn only. In other words, these assumptions can be elaborated
as under:
i) The metal ion forms no hydrolysis or anionic complexes in appreciable
amounts.
ii) The chelate concentration in the aqueous phase is negligible.
iii) The concentration of the intermediate chelate species is negligible.
If these assumptions are taken as valid, then
[ M ]o [ MR n ] o
D= = … (3.9)
[ M ]a [M n + ] a
By combining the Eqs. 3.1 through Eq.3.8, the final Eq. 3.9 becomes as follows:
[MR n ]o K f K an K DX [ HR ]on
D= = n
. ... (3.10)
[M n + ] a K DR [H + ]an
This equation has been experimentally verified for various metal chelate extraction
systems. From the equation, it is evident that
n
D ∝ Kf, K a , KDX and [HR] on ... (3.11a)

Also, D ∝ K −DRn and [H+] a− n ... (3.11b)

If we interpret these results, the following conclusions can be arrived at.
i) In order to have greater extraction, Kf should be as large as possible. This will
mean that more of anion of the ligand must react with the metal ion to form the
extractable complex MRn.
ii) D is directly proportional to K na i.e., acid dissociation constant of the ligand.
This means that more is the dissociation of the ligand, HR, the more of free R—
will be available for complexation with Mn+ to form MRn.
iii) Since D ∝ KDX, it will mean that the complex should have maximum
concentration in the organic phase. In other words, the complex should
distribute itself such that [MRn]total → [MRn]org.
iv) The next consideration is that D ∝ [HR ] on + . It will amount to the fact that more
concentration of the ligand should be available in the organic phase. For

61
Classical Methods quantitative extraction, large concentration of the ligand is recommended to be
used.
v) According to Eq. 3.11b, D is inversely proportional to KDR and [H+]n. This
means that KDR should be small. In order to have small KDR, [HR]a should be
large. In other words, the ligand should have maximum solubility in the aqueous
phase to have better extraction. Finally, since the extraction is inversely
proportional to hydrogen ion concentration, the extraction is expected to
increase with the increasing pH.
In Eq. 3.10 for the extraction equilibria, the concentration of the metal ion does not
figure. This means that the extraction is independent of the metal ion concentration. In
other words, it implies that whether it is tracer level concentration or macro amounts
extraction would be the same.

At this point, it may be important to consider the role of [H+] or pH and for this, we
again resort to Eq. 3.10.
K f K an K DX [ HR ]on
D= n
... (3.10)
K DR [H + ]an

K f K an K DX
If n
= K* ... (3.12)
K DR

[HR ]on
D = K* ... (3.13)
[H + ]an

Taking log of both sides,

log D = log K* + n log [HR]o –nlog[H+]a ... (3.14a)

log D = log K*+ n log[HR]o + n pH ... (3.14b)

Therefore, it means that plot of log D vs. pH should be a straight line with slope n and
an intercept equal to (log K* + n log [HR]o). Fig. 3.1 shows such a plot. The slope n
gives the number of molecules of the chelating agent involved in neutralizing the
charge on the metal ion. By plotting the data at different pH, the values of both n and
K* can be found out.

Fig. 3.1: A typical plot between pH and log D

62
We know from Eq. 3.13 that Solvent Extraction-II

[HR]on
D = K*
[H + ]an
If the reagent concentration is constant, then
1
D = K* K*´
[ H + ]an
And, assuming Va and Vo to be equal,
100 D
E= (from Eq. 2.21)
D +1
or
E
D=
100 − E
1 E
D = K*´ + n
= ... (3.15)
[ H ] 100 − E
When E = 50
pH1/2 = 1/n log K*´ ... (3.16)
This indicates that pH at E = 50% is constant. The difference in pH1/2 values of two
metal ions in a specific system is a measure of separability of these two metal ions. A
detailed discussion on the effect of pH on extraction and the application of difference
in pH 12 in the metal ion separations will be taken up in sub- Secs. 3.3.1 and 3.4.2,
respectively.

SAQ 1
While proposing the metal chelate extraction equilibria, two simplifications with
regard to the existence of the metal in the aqueous and organic phase were assumed.
What are they?

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

SAQ 2
The values of which constants should be higher for a higher metal chelate extraction?

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

3.2.2 Extraction by Solvation

During the discussion on the different classes of extractants, it has been pointed out
that a large number of solvent extraction systems are based on the solvation of neutral
inorganic molecules or complexes by electron donor containing extractants. The basic

63
Classical Methods role of a solvating molecule is to increase the solubility of the inorganic species in the
organic phase. In other words, the solvating molecule makes the extracting species
more hydrophobic; thus, promoting its transfer to the organic phase. As already

known, there are two well-known distinct categories of solvating extractants.

i) Extractants with oxygen bonded to carbon such as ethers, alcohols and ketones.
ii) Extractants with oxygen or sulphur bonded to phosphorus such as alkyl
phosphates or alkylthiophates.
It may be important to point out here that some of the acidic extractants play a dual
role of neutralizing the charge on the metal ion and simultaneously solvating the
species. This is true with carboxylic acids and acidic organophosphorus compounds.

In the present day extraction chemistry, the extractants like ethers, alcohols and
ketones have been replaced by organophosphorus extractants but the model extraction
equilibria study is generally presented by taking the former class of compounds. The
main reason is that some of these examples give a better insight of the different
equilibria steps which may be possibly involved in the extraction of metal ion by
solvation. A large number of metal ions are extracted in ethers from aqueous mineral
acid media. The well-known example generally cited in this class is the extraction of
Fe(III) in diethyl ether from HCl medium. It is one of the earliest systems known in
solvent extraction chemistry. The extraction of Fe(III) in ethyl ether from strong
hydrochloric acid solution was reported by Rothe way back in 1892. Since then
several efforts have been made to identify the extracting Fe(III) species. Some
spectroscopic studies have also been carried out to identify the extracting species. The
extracting species is postulated as solvated chloroferric acid i.e. HFeCl4.2(C2H5)2O.
However, the situation is not so simple because of the involvement of different types
of equilibria.

The extraction of Fe(III) increases with the increasing HCl concentration, reaches to a
maximum value (∼99%) at 6M HCl and then starts decreasing with the increasing acid
concentration. A decrease in extraction above 6M HCl is attributed to the high
solubility of ethyl ether in concentrated HCl. This decrease is not observed up to a
much higher acid concentration (∼ 8M) in the case of diisopropyl ether which has
lesser solubility in HCl. If β, β ′ – dichlorodiethyl ether is used, no decrease in
extraction is observed even at 12M HCl. There are other issues involved in the organic
phase as regards the existence of ion association complex. At extremely low iron
concentrations, dissociation has been observed. On the hand, at higher iron
concentrations polymerization has been postulated.

The entire system can be considered in the following steps.

1. Formation of FeCl −4 anion in the aqueous phase

K1 2+
Fe(H2O)3+
6
+ Cl Fe(H2O)5Cl + OH2
… (3.17)

2+ K2
+
Fe(H2O)5 Cl + Cl Fe(H2O)4 Cl 2 + H2O

K3
Fe(H2O)4 Cl+2+ Cl Fe(H2O)3 Cl3 + H2O

64
 K4 Solvent Extraction-II
Fe(H2O)3 Cl3 + Cl Fe(H2O)2 Cl4 + H2O
… (3.18)
The different steps may be combined to give the overall reaction
3+ K1K2K3K4
Fe(H2O)6 + 4 Cl Fe(H2O)2 Cl4 + 4 H2O
… (3.19)
The final equilibrium expression will be

[ Fe(H 2O) 2 Cl 4− ][H 2O]4

K ′ = K1K2K3K4 = … (3.20)
[Fe( H 2O)36+ ][Cl − ]4

This amounts to the fact that at high chloride concentrations, the FeCl −4 is the major
species existing in the aqueous phase.

2. Formation of solvate
The next step is the formation of the solvate favouring extraction in the organic phase.
At high acidity, the water activity decreases and the ether activity in the aqueous phase
increases. As a result of this, solvent exchange may occur .
K5
Fe(H2O)2 Cl −4 + 2 R2O Fe(R2O)2Cl −4 + 2H2O ... (3.21)
where R2O represents the ether molecule. A similar exchange will take place in the
hydronium ion.
K6 +
H3O+ + R2O R2 O H + H2O ... (3.22)

3. Formation of extractable complex

Now we have to look as to how a neutral extractable complex is formed. This has to
result as a consequence of formation of an ion association complex.
K7
H3O+ + Fe(H2O)2Cl −4 [(H3O+. Fe (H2O)2 Cl −4 )] ... (3.23)

K8
R2OH+ + Fe (R2O)2 Cl −4 [(R2OH+. Fe (R2O)2Cl −4 )] ... (3.24)
The above two equations can be written in a general form as follows:
K9
HS+ + Fe (S)2Cl −4 [(HS+. Fe(S)2 Cl −4 )] ... (3.25)
where S = H2O/ R2O

4. Distribution of the reagent and complex

After having considered the formation of extractable complex, the next step will
be to look into the distribution of the reagent and complex.

−
KD
(HS+.Cl )a (HS+.Cl−)o ... (3.26)

KD
+
[HS .Fe(S)2Cl −4 ]a [HS+.Fe(S)2Cl −4 ]o ... (3.27)

65
Classical Methods 5. Polymerization of ion pair in the ether phase
It was indicated earlier in the beginning of the discussion on this system that at
higher iron (III) concentration, the extracting ion pair complex undergoes
polymerization in the organic phase.
K10
n[(HS+.Fe(S)2Cl −4 )]o [(HS+.Fe(S)2Cl −4 )n]o ... (3.28)
where n varies from 2- 4.

6. Dissociation of the ion pair complex and the reagent in the organic phase
At extremely low Fe(III) concentrations, the dissociation of extractable complex
and the reagent occurs in the ether phase.
K11
[HS+.Fe(S)2Cl −4 ]o (HS+)o+(Fe(S)2Cl −4 )o ... (3.29)

K12
(HS+.Cl−)o (HS+)o+(Cl−)o ... (3.30)
Now considering the overall distribution of iron in its different forms between
the organic and the aqueous phases.

D≡
[Fe]o
[Fe]a
[(HS + .FeCl 4− ]o + [Fe(S) 2 Cl 4− ]o + n[(HS + .Fe(S) 2 Cl 4− ) n ]o
= ... (3.31)
[FeS 2 Cl 4− ]a + [(HS + .Fe(S) 2 Cl 4− )]a
It can be seen that the distribution ratio is a complex function of different
experimental parameters and by substituting the relations form previous
equations, we get
D = K D′ K7[HS+] [1 + K11{KDK7K11[HS+] [Fe] + K12KD[HS+][Cl−}–1/2 +
nK10(KDK7) n −1 [HS+] n −1 [Fe] n −1 ] ... (3.32)
In the above Equation i.e.,Eq.3.32 the two important variables are acidity and
the total iron concentration. From this equation, the following inferences can be
drawn:

i) In relatively high iron concentration where polymerization takes place to a

significant extent and dissociation is relatively unimportant, Eq. 3.32
simplifies as follows:
D ≅ K D′ K7[HS+] {1+nK10 (KD K7)n–1[HS] n −1
[Fe] n −1 } ... (3.33)
This simplification results because of the fact that the extent of
dissociation is negligible and the terms multiplied by K11 and K12 are
unimportant. From Eq. 3.33, we can infer that the extraction increases
with the increasing iron concentration.

ii) In the region of low iron concentration where dissociation of the complex
remains the only significant organic phase reaction, the terms involving
K11 and K12 are important and those multiplied by K10 become
insignificant. Then Eq.3.32 simplifies to the following expression:
−
D ≅ K D′ K7[HS+] [1 + K11{KDK7K11[HS+] [Fe] + K12KD[HS+][Cl ]}o–1/2]]
… (3.34)

66
 This shows that the extraction increases with decreasing iron Solvent Extraction-II
concentration reaching to a value of
D ≅ KD K7 [HS+] {1+K12KD [H+] [Cl−]}–1/2 ... (3.35)
iii) From Eq. 3.35, it is clear that the extraction of Fe(III) is favoured by
increasing acidity. These equations do not reflect anything on the decrease
in the extraction of Fe (III) at very high acidity which is primarily due to
the solubility effect.

SAQ 3
What are the main categories of solvating extractants?

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

SAQ 4
The extraction of Fe (III) in diethyl ether from HCl medium increases with the
increasing molarity of HCl up to 6 M but starts decreasing thereafter. However, in the
case of β, β ′ - dichloroethyl ether, there is a continuous increase in extraction with no
decrease. Explain why?

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

3.2.3 Extraction by Ion Pair Formation

In the preceding section, we have categorized the extraction of Fe(III) under solvate
formation because the replacement of water by ether makes the species to favour the
organic phase. However, the system can be classified under ion pair formation because
the extracting species is being formed due to electrostatic attraction between cation
HS+ and anion Fe(S)2Cl −4 . Here, we will discuss two extraction equilibria which are
exclusively due to ion pair formation.
A) Extraction of permanganate ion by tetraphenylarsonium chloride.

B) Extraction of anionic metal complexes by high molecular weight amines

popularly known as liquid anion exchangers.

We will now discuss these briefly.

A) Extraction of Tetraphenylarsonium Permanganate

Tetraphenylarsonium chloride is a water soluble salt. This forms chloroform
extractable complexes with anions like permanganate, perrhenate and
pertechnate. The quantitative treatment of the extraction equilibrium is similar
to those proposed for metal complexes.
i) Dissociation of the reagent (R4As+.Cl−), R= C6H5

(R4As+. Cl − )a R4As +a + Cl a− ... (3.36)

67
Classical Methods
[ R 4 As + ]a [Cl − ]a
K= … (3.37)
[(R 4 As + Cl − )]a
The dissociation constant K has a high value.
ii) Formation of ion association complex
The tetraphenylarsonium cation combines with the permanganate anion to
form the complex as shown below:
+
R4As a + MnO −4 (R 4 As + . MnO −4 ) a ... (3.38)

[(R 4 As + .MnO −4 )]a

Kf = ... (3.39)
[ R 4 As + ] a [MnO −4 ]a
The value of Kf is small.
iii) Distribution of the reagent and the complex
After we have considered the formation of the complex, the next step will
be its distribution between the aqueous and the organic phases. Once we
are considering the distribution of the complex, we will have to consider
the distribution of the reagent also.
Distribution of the reagent

[(R 4 As + .Cl − )]o

KDR= ... (3.40)
[(R 4 As + .Cl − )]a

Distribution of the complex

[(R 4 As + .MnO −4 )]o

KDX = … (3.41)
[(R 4 As + .MnO −4 )]a

iv) Dimerization of the reagent and the complex in the organic phase
In the organic phase, the reagent and the ion pair can undergo
dimerization and the relevant equilibria are
2 (R4As+.Cl−)o (R4As+. Cl − )2o ... (3.42)

[(R 4 As + .Cl − ) 2 ]o
KP = ... (3.43)
[(R 4 As + .Cl − ) ]o2
And,
2 (R 4 As + .MnO −4 ) (R 4 As + .MnO −4 ) 2 o

[(R 4 As + .MnO −4 ) 2 ] o
K P′ = ... (3.44)
[(R 4 As + .MnO −4 )]o2
From the different equilibria, the distribution ratio of permanganate in the
two phases can be described as under given below:

[MnO -4 ]o −
[(R 4 As + .MnO 4 )]o + [(R 4 As + .MnO 4 ) 2 ] o
D≅ =
[MnO -4 ]a [MnO −4 ]a + [(R 4 As + .MnO 4 − )]
… (3.45)

68
 If the MnO −4 concentration is low, the dimer formation may be neglected. Solvent Extraction-II
Also, the concentration of the ion pair [(R4As+.MnO4−)] in the aqueous is
negligible. With these assumptions, the expression of D simplifies to be
following:
[(R 4 As + .MnO −4 )]o
D= ... (3.46a)
[MnO −4 ]a

= KDX. Kf [R4As+]a ... (3.46b)

i) This means that the distribution ratio of the permanganate complex
is solely a function of the equilibrium concentration of the
tetraphenylarsonium cation. The extraction increases with the
reagent concentration.
ii) We know that the chloride ion concentration tends to reduce the
concentration of tetraphenylarsonium cation; thus, reducing the
extraction of the complex.

K [(R 4 As + .Cl − )]o

[R4As+] = … (3.47)
K DR [Cl − ] a
Substituting the above relation in Eq. 3.46, we get
K DX K f K [(R 4 As + .Cl − )]o
D= . ... (3.48)
K DR [Cl − ] a

B) Extraction of Anionic Metal Complexes by High Molecular Weight Amines

In Sec.2.3, we have discussed that one of the best examples of extraction by ion
pair formation comes from extraction of anionic metal complexes by high
molecular weight amines. It was also pointed out that some phosphonium and
arsonium compounds also find extensive use as extractants of this category. As
an example, we have already discussed the equilibria involved in the extraction
of MnO −4 by (C6H5)4 As+.Cl−. We now discuss the mechanism of extraction by
high molecular weight amines. These include primary, secondary and tertiary
amines as well as quaternary ammonium salt.

When the organic solution of the amine is equilibrated with aqueous solution of
the acid, the amine is converted to its corresponding salt.

R3No + HCla R3NH+Cl − ... (3.49)

When the amine salt is equilibrated with an anion (A − ) , the (Cl − ) will be
exchanged.
R3NH+Cl o− + A a− R3NH+ A o− + Cl a− ... (3.50)

A − can be a simple anion like NO 3− , a complex anion like CrO 24− or an anionic
metal complex such as FeCl −4 , CdCl 24− or ZnCl 24− .

Fe(III), Cd (II) and Zn (II) are known to be extracted by high molecular weight
amines from hydrochloric acid medium. The relevant equilibria steps for
extraction by a tertiary amine or a quarternary ammonium salt are given below:
Fea3+ + 4 Cl a− FeCl −4 ... (3.51)

69
Classical Methods
R3No + HCla R3NH+ Cl o− ... (3.52a)

R3NH+Cl o− + FeCl −4a R3NH+·FeCl −4o +Cl a− … (3.52b)

Likewise, in quaternary ammonium salt, the extraction will follow the step:
R3R´N+Cl o− + FeCl −4 R R´N+. FeCl −4o + Cl a− ... (3.53a)

The extraction equilibria steps for Zn(II) and Cd(II) chlorocomplexes will be as
follows:
Zn a2+ + 4Cl a− ZnCl 42−a … (3.53b)

2 R3NH+Cl o− + ZnCl 42−a ( R3NH+)2. ZnCl 24o− +2 Cl a− ... (3.54)

2 R3R´N+Cl (−o ) + ZnCl 24−a (R3R´N+)2.ZnCl 240− + 2 Cl a− ... (3.55)

Cd a2+ + 4 Cl a− CdCl 24−a … (3.56)

2 R3NH + Cl o− + CdCl 24−a ( R3NH+)2.CdCl 2−

40 + 2 Cl − ... (3.57)

2 R3R´N+Cl (−o ) + CdCl 24−a (RR´N+)2 CdCl 240− + 2 Cl a− … (3.58)

Likewise, the nitrate and sulphate complexes of different metals are extracted from the
corresponding mineral acids. Not only this, the extraction of anionic organic
complexes like oxalate, citrate, malonate takes place by similar mechanism. It is clear
from the above examples that the transfer of an ion pair to the organic phase is by a
mechanism similar to uptake by a solid anion exchanger. This is why the high
molecular weight amines are popularly known as liquid anion exchangers. Generally,
the pattern of the extraction behaviour is similar to the uptake of the metal ion on the
solid anion exchange resin. One feature which is clear from the above equilibria steps
is that the extraction (D) of the metal ion will increase with the increase in amine
concentration. A plot of log D vs log [Amine] should be linear (see Fig.3.2) and the
slope of this straight line will give the number of amine molecules involved in the
formation of the extracting species. This will give the charge on the anionic metal
complex and the extracting species can be postulated.

Fig. 3.2: Dependence of distribution ratio of the metal ion on the amine concentration at
constant aqueous phase conditions.

70
In the case of iron (III) chlorocomplex, the slope will be one and for Zinc (II) and Solvent Extraction-II
Cd(II) chlorocomplexes, it will be two. Ideally, for drawing the plot, it should be the
concentration of the free (unbound) amine. This should be the amine concentration at
equilibrium. Since the amine concentration taken is about 103times more than the
metal ion concentration, the free amine concentration is taken to be the same as the
initial one. In this regard, the use of radiotracers for the determination of D is very
useful because the metal ion concentration required is almost negligible ~ 10 −6 M.
This means that the free amine concentration can be safely taken as the initial one.

There are other methods, including the spectroscopic, which are used for confirming
the postulated extracting species or the proposed extraction equilibrium.

From the above examples of extraction in high molecular weight amines, similar to
anion exchange, some authors draw analogy to classify alkylphosphoric acids,
sulphonic acids and carboxylic acids as liquid cation exchangers. These acids, in the
organic phase, generally exist as dimers. The equilibrium step resulting into the
transfer of the metal ion in the organic phase will be somewhat to a cation exchange.
M an + + n (HX)2o M(HX)n o + n H a+ ... (3.59)
It may be important to point out here that the analogy of high molecular weight amines
and that of the acids to anion and cation exchangers should not be extended too far.
Here, we have taken some simple equilibria. However, the parameters which can
complicate the situation are role of diluent, dimerization of the extractant and the
extractant simultaneously acting as an exchanger and a solvating agent. One needs to
be cautious in this regard.

SAQ 5
In the extraction of Cd(II) from oxalic acid medium in a high molecular weight
quaternary ammonium oxalate the log- log plot of D vs free amine concentration gave
a straight line of slope two. Propose the extraction equilibria.

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

SAQ 6
Generally, the extraction efficiency of the various HMWA follow the sequence
primary < secondary < tertiary < quaternary. In what situations a deviation in the
above sequence is generally observed?

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

71
Classical Methods 3.2.4 Extraction by Synergism
The word synergism literally means working together. It is a matter of fact that the
two extractants work together to increase the extraction by a huge factor. This word in
solvent extraction was introduced by Blake et al in 1958. They observed that when a
dialkylhydrogen phosphate (RO)2PO.OH is used in conjunction with certain
organophosphorus solvating molecule like TBP, the extracting power of the mixture
exceeds the sum of the extracting power of the individual extracting reagents. In
synergism, one of the two extractants is a ligand or an organic acid (HA) which
neutralizes the charge on the metal ion and the other a solvating molecule (S) which
either replaces the water molecule from the coordination sphere or forms an adduct
which is less hydrophilic. One of the most thoroughly investigated synergistic
mixtures of extractants is the theonlytrifluroacetone (HTTA) and tri-n-butylphosphate
(TBP). In its simplest form, the equilibria can be written as
M an + + n HAo MA n o + n H+ ... (3.60)

MA n o + m Bo MA n Bmo ... (3.61)

Here, HA = HTTA, B = TBP

HTTA has been used with different solvating molecules like TBP, TOPO and TPP
(triphenyl phosphate). It was observed that the synergistic effect increases with the
increasing basicity of the ester TOPO > TBP > TPP. The extracting species of some
actinides with the above systems were reported as UO2(TTA)2S, UO2(TTA)2S2,
Th(TTA)4S, Am(TTA)3S2, Cm(TTA)3S2. Based on the above discussion, some
generalization about the formation of a synergist adduct can be drawn.
i) One of the extractants, a ligand or an acid (HA), neutralizes the charge on the
metal ion preferably by forming a chelate. The list of ligands is very large. The
acids can be organophosphorus or carboxylic acids.
ii) The solvating reagent (S) should displace residual coordinated water from the
neutral metal complex rendering it less hydrophilic. The solvent should not be
itself hydrophilic and coordinated less strongly than HX. The commonly used
solvating molecules are organophosphorus compounds and nitrogen containing
bases.
iii) The maximum coordination number of the metal and the geometry of the ligand
should be favourable.
iv) A little more complexity in the formation of a synergistic adduct is being
presented by taking the extraction equilibria of Zn (II) and Cd (II) in the
chloroform solution of propionic, butyric and valeric acid in the presence of
amines. The extraction of both the metal ions independently in carboxylic acid
and amine is very low (~ 10 – 20%). It is observed that the addition of amine to
the solution of the acid enhances the extraction of metal ion to an unpredictable
extent. This may probably be ascribed to the formation of less hydrophilic
species due to the removal of the water molecules from the coordination sphere
of the metal ion. It has been separately established that amines form an integral
part of the extractable species of the metal ion. Because of low dielectric
constant of chloroform it is expected that the bond between the proton and the
acid anion is much stronger in chloroform than in water; consequently, neither
could one rule out the hypothesis of the absence of any reaction between the
acid proton and the amine. By nmr spectroscopy, it has been confirmed that
there is a formation of a salt of the acid with amine. It has also been
experimentally confirmed and known that the acid in the organic phase mostly
exists as a dimer.

72
 The equilibrium between an aqueous metal ion solution and chloroform solution Solvent Extraction-II
of aliphatic monocarboxylic acid and that of amine can be represented as
n− p+x
M an + + p (BHA)o + (H2A2)o (MBpAn.xHA)o + n H a+
2
... (3.62)
n+
where M = metal ion
n = valency of metal ion
p = number of amine molecules coordinated
HA = monomeric acid molecule
B = amine
x = number of acid molecules required for solvation
(H2A2)o = dimeric acid molecules in organic phase

Hence, the equilibrium constant is given by

[M.Bp A n .xHA]o [ H + ]on
K= ... (3.63)
[ M n + ]a [ BHA]op [H 2 A 2 ]on − p + x / 2
Assuming that the metal ion does not form any other complex in the organic phase and
exists only as Mn+ in the aqueous phase
[ M.B p .A n .xHA]o
D= ... (3.64)
[M n + ]a
Substituting the value of D in Eq. 3.63, rearranging it and expressing in the
logarithmic form, we get
n− p+ x
log D = log Kex + n pH + log [H2A2]o + p log[BHA] ...(3.65)
2
Eq. 3.65 on differentiation with respect to pH at constant acid concentration gives
[δ log D]
=n ... (3.66)
[δpH]
Thus, the slope of log D vs. pH at constant acid and amine concentration in the organic
phase will give the number of protons liberated due to consumption of acid molecules
in the complex formation. Similarly, a plot of distribution ratio vs dimeric acid
concentration at constant pH and amine concentration will give the slope equal to
n− p+x
from which the number of acid molecules required for the solvation of
2
extracted species can be calculated. To find out the number of amine molecules
coordinated with the extracted species, log – log plots of distribution ratio vs amine
concentration at constant pH and acid concentration will have to be drawn. The results
of different plots drawn at different conditions gave the following results:
i) the plot of log D vs pH at constant metal ion, acid and amine concentration for
both Zn (II) and Cd (II) gave straight line with slope near two. This suggests
release of two protons by the utilization of two acid molecules per metal atom to
neutralize the charge on the metal ion.
ii) The plot of log D vs log [amine]o at constant metal ion, pH and acid gave
straight lines for both the metal ions with all the three acids. The slopes for
aliphatic and heterocyclic amine were one and two, respectively. This suggests
the incorporation of one molecule of n- butylamine, dibutylamine and
tributylamine and two molecules of β- picoline, pyridine or quinoline when
either of the three acids is used.

73
Classical Methods iii) To calculate the acid molecules required for solvation of the extracted species
the concentration of the acid viz. propionic butyric and valeric at constant metal
ion, pH and amine concentration. It is found that with the increase in the
concentration of the acids, the extraction increases. It is also observed that with
the increase in the number of carbon atoms in the acid, the extraction efficiency
increases and shows the following order:
propionic < butyric < valeric
iv) Log – log plots of distribution ratio vs dimeric acid concentration in the organic
n− p+ x
phase gives straight lines with slope corresponding to . For both the
2
metal ions and with all the three acids, this value comes to around two and one
for aliphatic and heterocyclic amines. By substituting the values of n and p, the
value of x is calculated. It is clear from the result that in the case of both the
metal ions, three molecules of acid are involved while only two acid molecules
solvate the species in the case of heterocyclic amines.

On the basis of above results, the composition of the extracted species with propionic,
butyric and valeric can be represented as follows:

Aliphatic Amine System

Zn (II) – ZnA2. 3HA.B
Cd (II) – CdA2. 3HA.B

Heterocyclic Amine System

Zn (II) – ZnA2. 2HA. 2B
Cd (II) – CdA2. 2HA. 2B

Eq. 3.65 is used for the calculation of extraction constants at different amine and
constant acid concentration. The values of extraction constant reveal that the
heterocyclic amines are better synergists than the aliphatic counterparts because of
higher basicity of the former.

It may be interesting to note that there is also a phenomenon known as antisynergism

which is the reverse of synergism. It was observed in the case of an alkyl phosphoric
acid - phosphorus ester (HX – S) and in the HTTA –TBP (HX – S) system, due to the
addition of excess of S. It appears that in the first case, the addition of excess of
solvating molecule (S) reduces the concentration of free chelating agent by increasing
interaction between HX and S through hydrogen bonding. As a result of this, the
extraction is lowered. In the second example, the decrease in extraction is supposedly
caused due to water content of the organic phase and the destruction of anhydrous
synergistic species M(TTA)xSy.

SAQ 7
In the above given examples of synergism in carboxylic acid – amine systems, arrange
the following three systems in increasing order of extraction:
i) propionic acid – tributyl amine
ii) valeric acid – tributyl amine
iii) valeric acid – pyridine

…………………………………………………………………………………………...
…………………………………………………………………………………………...

74
 Solvent Extraction-II
3.3 FACTORS INFLUENCING EXTRACTION
The discussion of the previous section clearly indicates the fact that the extraction
efficiency of an extractant will depend upon a number of variables. Thus, to explore
and successfully exploit some of these variables for effective metal ion separations, a
clear understanding of the effect of these variables on extraction is necessary.

On a broader basis, these parameters can be grouped under the category of aqueous
and organic phase parameters. Besides these, there can be parameters, say
temperature, which can affect both. Moreover, these variables are being discussed with
an assumption that equilibrium has reached. The present discussion will deliberate on
some of the well known variables with one or two examples in each case to illustrate
the point or general trend. The aqueous phase parameters are being discussed first.

3.3.1 pH
When we say pH of the aqueous phase, it necessarily means the equilibrium pH i.e.,
the pH attained after the two phases have been contacted to equilibrium. This is a
dominant variable where H+ ion is involved in the formation of the extracting species.
This will mean that pH will be of great significance in extraction systems listed in the
classification scheme under “Extraction by compound formation”. The extraction by
chelating agents, carboxylic and sulphonic acids and acidic organophosphorus
compounds are susceptible to pH variation. To illustrate the point, the extraction
behaviour of some metal ions by dithizone, Versatic 9. and DEHPA is shown in Fig.
3.3 (a), (b) and (c), respectively. As expected, the extraction increases with the
increasing pH.

Fig. 3.3 (a): Qualitative extraction curves for metal dithizonates

75
Classical Methods

Fig. 3.3(b): Extraction of Fe, Cu, Zn, Ni and Co with Versatic 9

Fig. 3.3(c): Extraction of some metals by DEHPA from sulphate solution

76
A detailed discussion on the extraction equilibria of this class of extractants is given in Solvent Extraction-II
Sec. 3.2. It has already been mentioned in Sec. 2.3 that out of these reagents, the
extraction by chelating agents may be easier to describe by simple mass equations.
The situation in case of extraction by carboxylic, suphonic and alkylphosphorus acids
is likely to be more complicated due to self association of the acids in the organic
phase or the solvation of the extracting species by the extractant.

The dependence of the distribution ratio of the metal chelate, formed by the metal ion
Mn+ by the chelating agent HR, on pH, is given by the following equation.
[HR ]on
D =K* ... (3.13)
[H + ]an
where K is a constant involving some constants.

n
If [HR ]o remains constant, then

E
D = K´* [H + ]an = , where E is percent extraction ...(3.15)
100 − E
And,
log D = log E – log (100 – E) = log K´* + n pH
The above equation represents a family of symmetrical sigmoid curves with the
position of each along the pH axes depending only upon the value of K´* and the slope
of each depending on n. Fig. 3.3 (a) shows a set of curves qualitatively representing
the extraction of metal dithizonates in carbon tetrachloride. The above relation will not
be strictly applicable where hydrolysis of metal ion occurs or intermediate chelate
formation takes place. The slope of the curve instead of corresponding to n, will be
significantly lower. The pH value at % E = 50 has been designated as pH1/2
1
pH1/2 = – log K ′ * … (3.16)
n
You will see in the next section that the difference in pH1/2 values of the metals in a
specific system is a measure of the separability of the two ions.

3.3.2 Molarity of the Acid

When we say the molarity of an acid, it invariably implies the range of acidity which
is not going to be covered by the pH scale. The study of the effect of molarity of the
acid on extraction is carried out on the extraction of metals by solvation or ion – pair
formation. These investigations are mainly confined to the mineral acids and that too
mostly to HCl and HNO3.

Figs. 3.4 – 3.7, depict the extraction behaviour in the two types of extraction systems.
Fig. 3.4 gives the extraction behaviour of 3d transition metal ions viz. Ti (IV), V (IV),
Cr (III), Fe(III), Mn(II) Co(II), Ni(II), and Cu(II) from HCl solution in a toluene Cyanex 923, a solvating
solution of Cyanex 923. The extraction profile of some commonly associated elements commercial extractant, is
like Ce(IV), Al(III), Ga(III), Mg(II), Cd(II) and Pb(II) commonly encountered in some a mixture of four trialkyl
of the matrices is also given. phosphine oxides viz.
R3P = 0, R2 R ′ P = 0,
The dependence of percent extraction from 1- 10 M HCl is shown. The extraction of R R ′2 P = 0 and R´3P = 0
Zn(II) and Cd (II) is more or less quantitative (>95%) over the entire acidity range. (R is n- octyl and R ′ is
The extraction of Ti (IV), V (IV), Fe (III), Co (II), Ga(III) and Pb (II) increases with n-hexyl chain).
the increasing acidity. The extraction of Cu (II) shows a maxima around 5 M HCl. Mn

77
Classical Methods (II) shows a negligible extraction (< 5%) upto 5 M HCl; thereafter, it increases to a
maximum of 30% at 10 M HCl. The extraction of Mn is not shown in the figure.

The extraction of Ce (IV), Al (III), Cr (III), Mg (II) and Ni (II) is negligible over the
entire acidity range and is not shown in the figure. The extraction observed here is
governed by a complex mechanism promoting the formation of solvated neutral chloro
species. Sometimes, the mutual solubility of the two phases plays a significant role.
The maxima are observed due to competing factors coming into play to determine the
magnitude of extraction.

Fig. 3.4: Extraction behaviour of metal ions from HCl medium.

Conditions: [Metal ion] = 1x10-3M; [Cyanex 923] = 0.5 M
Figs. 3.5, 3.6 and 3.7 exhibit the extraction behaviour of Zn (II), Cd (II) and Hg (II) in
various high molecular weight amines as a function of HCl concentration. In order to
illustrate the trends and project the extraction efficiency of various amines, Primene
JMT, Amberlite LA – 1 and Amberlite LA – 2, Alamine 336 and tribenzylamine and
Aliquat 336 have been included for discussion as representatives of primary,
secondary and tertiary amines and quaternary ammonium salt, respectively. In the case
of Zn (II) and Cd (II), the behaviour in two diluents namely chloroform and benzene
and that of Hg (II) only in chloroform is shown. The curve for tribenzylamine diluted
in benzene in not shown because of formation of a precipitate at all molarities of the
acid. The curve for Zn (II) in Primene JMT is not shown because of less than 1%
extraction over the entire range of acidity.

78
 Solvent Extraction-II

Fig. 3.5: Extraction of Zn(II)from HCl solutions by various 0.1 M amines in chloroform
and benzene. Chloroform solvent: curve 1, Amberlite LA-1: curve 2, Amberlite LA-2;
curve 3, Tribenzylamine ; curve 4, Alamine 336 ; curve 5, Aliquat 336. Benzene
solvent : curve 6, Primene JM-T ; Amberlite LA-2, : curve 7, Amberlite LA-1, : curve 8,
Amberlite LA-2 ; curve 9, Alamine 336 ; curve 10, Aliquat 336

Fig. 3.6: Extraction of Cd(II) from HCl solutions by various 0.1M amines in chloroform
and benzene. Chloroform solvent: curve 1, Primene ; curve 2, Amberlite LA-1 ; curve 3,
Amberlite LA-2 ; curve 4, Tribenzylamine, curve 5, Alamine 336 ; curve 6, Aliquat 336 ;
Benzene solvent : curve 7, Primene JM-T , curve 8, Amberlite LA-1, curve 9, Amberlite
LA-2 ; curve 10, Alamine 336 ; curve 11, Aliquat 336.

79
Classical Methods

Fig. 3.7: Extraction of Hg(II) from HCl solutions by various 0.1M amines in chloroform:
Curve 1 – Primene JM-T; Curve 2- Alanine 336; Curve 3- Amberlite LA-2; Curve 4-
Amberlite LA-1 Curve 5- Tribenzyl amine; Curve 6- Aliquat 336
The trend in the behaviours of Zn (II) and Cd (II) is similar to each other. In both the
cases, there is a broad maxima in extraction around 2 M HCl. This behaviour is quite
analogous to their sorption on solid anion exchangers from HCl medium. The
similarity can be explained on the fact that the extraction in these amines is due to an
anion exchange mechanism. We see more or less similar trend in all the amines diluted
in both the diluents.

For Hg (II), the extraction efficiency increases with decreasing HCl concentration with
a tendency to attain a limiting value around 0.2 M HCl. The only exception to this is
Aliquat 336 in which the extraction is very high and remains almost constant over the
entire range. Of all the liquid anion exchangers discussed here, the behaviour in
Aliquat 336 is the closest to solid anion exchangers.

The extractive power of various amines for all the three metal ions follows the
expected order i.e., primary amine < secondary amine < tertiary amine < quaternary
ammonium salt. Moreover, the extractions of these elements in a particular amine are
in accordance with the stability of their chlorocomplexes in aqueous solution i.e., Zn <
Cd < Hg.

It may be important to point out that if these amines are equilibrated with 1M HCl and
the extraction of the said metal ions is observed as a function of molarity of LiCl, the
trends are similar to those observed with HCl. Slightly higher extractions are observed
with LiCl due to higher hydration tendency of Li+ ions.

3.3.3 Effect of Metal Ion Concentration

It has been emphasized in the beginning that there is no effect of the metal ion
concentration on the distribution ratio of the metal. This will mean that both tracer and
macro amounts of metals may be expected to extracted to the same extent under
similar equilibrium conditions provided the solubility of the extracting species in the
organic phase is not exceeded. The relationship between Maq. and Morg. with the
increasing metal ion concentration is used to find the loading capacity of the
extractant. These plots known as loading curves or extraction isotherms for the
extraction of Ti (IV), V (IV), Fe (III), Cu (II) and Zn (II) in toluene solution of Cyanex
923 are shown in Fig. 3.8.

80
 Solvent Extraction-II

Fig. 3.8: Effect of metal ion concentration on extraction of Ti(IV), V(IV) Fe(III), Cu (II)
and Zn (II). Conditions : [Cynex 923] = 0.2 M; [HCl] = 5M
In all these plots, the linear part of the curve means that the extracting species does not
change with the increasing metal ion concentrations, thereafter, at a certain point, the
loading condition sets in and no further increase in the metal content of the organic
phase is observed. From this, the amount of the metal ion that can be loaded on a
particular amount of the extractant can be calculated and the results expressed in terms
of molar ratio. Sometimes from this, you can infer the stoichiometry of the extracted
species.

3.3.4 Presence of Salting Out Agents

Spectacular results in the enhancement of the extraction by solvating extractant
systems by the addition of metal salts has already been discussed earlier. It was
pointed out that the addition of inorganic salts increases the distribution of metal in
favour of the organic phase. The salting out effect is explained in part by the effect on
the activity of the distributing species and strong ability of these ions to bind water
thereby depleting aqueous phase of the water molecules to compete. The magnitude of
enhancement in extraction by the added salt depends upon the charge and ionic size of
the cation for a given anion.

If you go from this yardstick, polyvalent cations provide a better salting out agents and
for a given charge, the smaller the size, the greater the effect on extraction. Some
anomalies may be observed due to specific interactions. If you look at the efficiency in
enhancing the extraction, aluminium and ferric salts are stronger salting out agents
than ammonium salts but analytically, the latter are more convenient because it is
easier to remove them in the aqueous phase by repeated evaporation with HNO3 and
HCl. Generally, large amounts of these salts are added. One has to make sure that the
added salt does not extract in the organic phase to an appreciable extent. It is obvious
that the presence of large concentrations of the salt in the aqueous phase may present
problems in further processing unless easily removed or destroyed. Another point that
one has to keep in mind is that although the enhancement in the extraction of the metal
of interest occurs, it may also cause an enhancement in the extraction of impurities.
Therefore, it is necessary to choose an agent that produces favourable separation factor
between the element of interest and the impurities.

81
Classical Methods 3.3.5 Presence of Masking (Sequestering ) Agents
Masking agents also known as sequestering agents are themselves complex formers
not necessarily forming chelates. They are mainly used to prevent particular metals
from taking part in their usual reactions and therefore, the interference of the
undesirable elements is removed without the actual separation step.

The masked metal forms a water soluble complex most often negatively charged. In
solvent extraction, the masking agents are used to prevent certain metal ions from
forming extractable complexes and thus, they increase the selectivity. The use of
masking agents like cyanide, tartarate, citrate, fluoride and EDTA is restricted largely
to metal chelate extraction systems. In highly acidic solutions encountered in many
extraction systems, most of the masking agents do not function effectively.

The masking agent forms sufficiently strong complexes with the interfering metals to
prevent their extraction either altogether or at least until the pH is much higher than
the value needed for the quantitative extraction of the metal ion of interest. It should
be known that very often the desired metal of interest also forms a complex with the
masking agent and a much higher pH is needed for its extraction. In some cases, the
rate of formation of chelates has been slowed down by the presence of masking agents
like EDTA; thereby, reducing the rate of extraction. Some of the different examples on
the use of masking agents will be discussed in the next sub-Sec 3.4.4 on different
approaches for metal ion separations.

After having known some of the important variables of the aqueous phase, we now
discuss two important variables of the organic phase.

3.3.6 Concentration of the Extractant

As expected, the extraction increases with the increasing extractant concentration.
Invariably, a straight line is obtained in the plots of log [Extractant] vs log D. The
slope of the straight line corresponds to the number of extractant molecules involved
in the formation of the extracting species.

Ideally, for making these plots, the equilibrium concentration of the extractant in the
organic phase should be used. It is difficult to find out the unbound concentration of
the extractant in the organic phase. Moreover partitioning of the extractant between
the organic and aqueous phase may also take place. This partitioning of the extractant
between the two phases can be evaluated and if the need be, the correction is to be
introduced.

The problem of finding out the unbound extractant in the organic phase is resolved in
an indirect way by the use of radiotracers preferably carrier – free. When we say
radiotracers preferably carrier – free, the metal ion concentration used is several order
of magnitude lower and the extraction of the metal ion does not make a significant
change in the concentration of the extractant. Thus, the equilibrium concentration of
the extractant concentration is taken to be the same as the initial concentration.

Sometimes, these plots are drawn by taking the total concentration of the extractant
without the use of radiotracers. This is based on two assumptions. The first one is that
under the specified conditions, negligible transfer of the extractant from the organic
phase to the aqueous phase takes place. The second is that the extractant concentration
is so high compared to the metal ion concentration that the concentration of the
extractant is taken equivalent to the total concentration. The two types of examples
cited below refer to both type of situations – one using a radiotracer and the other
without it.

82
 Solvent Extraction-II

Fig. 3.9: Variation of the distribution coefficient for Cd tracer in HCl as a function of
Alamine 336 concentration in benzene. Curve 1, 0.25 M HCl; Curve 2, 2.0 M HCl;
Curve 3, 6.0 M HCl
Fig. 3.9 gives the log- log plots of [Alamine – 336] vs distribution ratio of cadmium
from different molarity of hydrochloric acid. The slopes of the straight lines
correspond to 1.82, 1.90 and 1.98 at 0.25, 2.0 and 6.0 M HCl, respectively. This
suggests that at all the three different molarities of the acid, the extracting species is
CdCl 24 − .

Fig. 3.10: Effect of Cyanex 923 concentration on the extraction of Ti (IV), V(IV) Fe(III),
Cu(II), and Zn (II). Conditions: [Metal ion] = 1x 10-3 (M); [HCl] = 5M

83
Classical Methods Fig. 3.10 shows the variation in the partitioning of Ti (IV), V (IV), Fe (III), Cu (II) and
Zn (II) at 5 M HCl using Cyanex 923 solution of varying (0.001 – 0.5 M)
concentration. The extraction increases with the increasing extractant concentration
and the log – log plots give a slope of around 2 for all the metal ions. This means that
two extractant molecules are involved in the formation of the extracting species.

Sometimes, the results of this slope analysis are not very straight forward and
conclusive. These slopes may sometimes suggest the extraction of more than one
species.

3.3.7 The Nature of Diluent

The role of diluent on the extractability of an extractant has been discussed in detail in
the sub-Sec. 2.4.1. It has become quite apparent that the diluents are not as inert as
they might appear to be. The mechanism of their role is quite complex. In some
instances, a decrease in the extraction of metal with the polar nature of the diluent has
been reported. But from the data available in different systems, it is difficult to ascribe
a single property of the diluent to change in its extractability.

SAQ 8
What is the main role of a masking agent in the extraction equilibria of a metal
chelate?

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

3.4 DIFFERENT APPROACHES FOR METAL ION

SEPARATIONS
In the previous section, we have seen the effect of some of the variables on extraction.
It is not practically feasible to use all of them for affecting separations. However, it is
up to you to use some of them intelligently to optimize the conditions for the
separation of a given set of metal ions. The conditions are to be so chosen that the
separation factor is as large as possible. It is possible to separate individual metal ions
from multimetal ion mixtures by involving several steps. In devising the separation
procedures, besides the decontamination factor or purity, emphasis is generally laid on
yield or recovery. Another point that has to be kept in mind is that the recovered metal
ion should be in such a form that it can be processed further easily. At this point, it
becomes important to realize the importance of stripping in liquid- liquid extraction.

3.4.1 Stripping
Stripping is the removal of the extracted solute from the organic phase for further
processing or analysis. It is the reverse of extraction. The usual procedure is to shake
the organic layer with a volume of water alone or water containing an appropriate
concentration of acid, an oxidizing or reducing agent or a masking agent. The metal
ion is then back extracted in the stripping aqueous phase. The conditions employed
depend upon the metal ion and the particular extraction system and are such that they
promote the reversal of extraction. Pure water or water adjusted to an appropriate pH/
molarity of acid are the more popular and convenient stripping agents. Washing the
organic layer with an oxidizing or reducing agent changes the metal ion to be stripped
in an oxidation state in which it is not extracted under the specific conditions.
Similarly, by washing with aqueous solution containing a masking agent like cyanide,

84
tartarate, citrate, EDTA etc. the metal ion may be brought back to the aqueous layer Solvent Extraction-II
because these complexing agents form a stronger complex which is not itself
extractable.
Here, we will discuss only those variables which are commonly used for affecting
metal ion separations. Some of the data cited in Sec. 3.3 will be used to elaborate the
point with only a few typical examples from the literature. The different approaches
being deliberated upon are as follows:
i) pH of the aqueous phases
ii) Acid molarity of the aqueous phase
iii) Presence of masking agents in the aqueous phase
iv) Selective stripping from the organic phase

3.4.2 pH of the Aqueous Phase

If we refer to the Eqs. 3.16 and 3.15 as given below.

pH1/2 = 1/n log K*´

log D = log E – log (100 – E) = n (pH – pH1/2)
The separation factor, β, may be expressed as
log β = log D1 – log D2 = n1 pH1/2 – n 2 pH 1 ... (3.17)
2

If we rake the criteria of a successful single stage separation by pH control, a 99%

extraction of one (D1 = 99) with a maximum of 1% extraction of the other (D2 = 0.01)
gives a minimum value of β is 104 (log β = 4). Using the above equation for bivalent
metals, a difference of two pH units in pH1/2 values would be necessary. For
tetravalent metal ions, the necessary difference is less. Fig. 3.3 depicting the extraction
of dithizonates, shows a pH1/2 difference of at least two units for Hg2, Bi3+ Sn2+ Pb2+
and Cd2+. Thus, it should be possible to employ a systematic separation of these ions
by simply pH adjustment. For a separation of Hg2+ from other four ions, the pH should
be adjusted to 1.0 so that Hg2+ will be quantitatively extracted while the others will
remain in the aqueous phase. If the extraction of Cd2+ is desired, the pH should be just
under 10 at which all the other metal ions will be extracted leaving behind Cd2+ in
solution. If the metal ion of interest is neither the most nor the least extractable of the
mixuture, as is the case of Sn2+, the pH should be adjusted to about 6 which will lead
to the extraction of Hg2+, Bi3+ and Sn2+ leaving Pb2+ and Cd2+ in the solution. The
organic phase is now back extracted with a fresh aqueous phase of pH~ 3 when Sn2+
returns to the aqueous phase leaving behind Hg2+ and Bi3+ in the organic phase.

The pH1/2 values may be altered by the use of masking agents. The pH1/2 values of
Hg2+, Cu2+, Ag+ Zn2+ and Cd2+ are raised to much higher values by the addition of
cyanide. EDTA also moves the pH1/2 values of most of the metals to the right, Ag+
being an exception. Cu2+ is more affected than Hg2+ so that the latter is separated from
the former.

SAQ 9
How can the pH1/2 of extraction of a metal chelate be altered?

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

85
Classical Methods 3.4.3 Acid Molarity of the Aqueous Phase
In order to demonstrate the utility of the variation in extraction with the changing
molarity of the acid for the separation of metal ions, we will use the data of extraction
in Cyanex 923 and HMWA (sub-Sec. 3.3.2).

We will confine the discussion to binary separations. But before proposing conditions
for separations, the stripping agents for back extracting metal ions remaining in the
organic phase of Cyanex 923, may be mentioned. The 0.5 M oxalic acid is able to
recover all the metal ions from the organic phase. However, 0.1 M H2SO4 can also be
used to strip all the metal ions except Ga (III). Washing the organic layer with less
than 0.01 M HCl or H2SO4 can bring about quantitative recovery of Cu (II), Zn (II)
and Cd (II) free from Fe (III). Water is also an effective reagent for the recovery of Cu
(II), Zn (II) and Cd (II). In all the above cases, two volume wash of the stripping agent
is required for the quantitative recovery of the metal ion from the organic phase.

The data on the extraction in Cyanex 923 have been used for a variety of binary
separations involving 3d transition metal ions. These separation along with the
conditions of separation and recovery are listed in Tables 3.1 (a) and (b).

Most of these separations have been achieved by selective extraction of a metal ion at
an appropriate acidity. Ti (IV) / V (IV) was separated from Fe (III) / Ga (III) / Zn (II) /
Cd (II) by selective extraction of the latter from 2 M HCl; however, for the separation
of Ti (IV) / V (IV) from Ai (III) / Mg (II), the former was extracted from 10 M HCl
solution.

For obtaining mutual separation of Ti (IV) and V (IV), both the metal ions were first
extracted from 10 M HCl solution followed by stripping of V (IV) using 10 M H2SO4.

The data on the extraction in Cyanex 923 have been used for a variety of binary
separations involving 3d transition metal ions. These separations along with the
conditions of separation and recovery are listed in Tables 3.1 (a) and (b).

Most of these separations have been achieved by selective extraction of a metal ion at
an appropriate acidity. Ti (IV) / V (IV) was separated from Fe (III) / Ga (III) / Zn (II) /
Cd (II) by selective extraction of the latter from 2 M HCl; however, for the separation
of Ti (IV) / V (IV) from Al (III) / Mg (II), the former was extracted from 10 M HCl
solution. For obtaining mutual separation of Ti (IV) and V (IV), both the metal ions
were first extracted from 10 M HCl solution followed by stripping of V (IV) using 10
M H2SO4 and that of Ti (IV) employing 2 M HCl. In between the washings by the two
stripping agents, the organic layer was washed with water. Cr (III) can be separated
from Fe (III) / Co (II) / Cu (II) / Zn (II) by extracting the latter at an appropriate
molarity of HCl.

The separations of some binary mixtures containing Mn (II) were achieved at an

appropriate molarity of HCl wherein Mn (II) is left in the aqueous phase and the other
metal ion is transferred to the organic phase. The constituents of binary mixtures
containing Fe (III) in combination with Al (III) / Mg (II) / Ni (II) / Cu (II) Zn (II) / Cd
(II) were isolated by selectively extracting Fe (III) at conditions indicated in the table.
Co (II) was separated from Ni (II) by selectively extracting it at 8 M HCl whereas for
its isolation from Cu (II) / Zn (II), it was made to remain in the aqueous phase. The
components of Cu (II)- Zn (II) and Cu (II) -Cd (II) mixtures were separated by
selectively extracting the second one from 2 M HCl. Zn (II) and Cd (II) were isolated
by subjecting their aqueous mixtures to extraction using 0.1 M HCl. At this acid
concentration, Zn (II) gets extracted while Cd (II) remains in the aqueous layer.

86
 Table 3.1 (a): Some important binary separations involving 3d metal ions from Solvent Extraction-II
HCl solutions using Cyanex 92.3 (toluene)
Metal ions Molar HCL Cynex Metal ions Metal ions
Ratio M 923 M remaining* in the re cov ered*
(x 10 −3 ) aqueous phase (%) from the organic
M phase (%) a
Ti (IV)- 1 : 10 10 0.5 98.8 V (IV )a
V(IV) 98.1 V (IV )
10 : 1 b
Ti (IV)- 1:10 10 0.5 97.2 Ce(IV) 96.2 Ti ( IV ) b
Ce(IV) 97.7 Ti ( IV )
10:1 97.1 Ce(IV) b
Ti (IV)- 1:10 10 0.5 98.2 Al(III) 97.4 Ti ( IV ) b
Al(III) 10:1 99.1 Al(III) 98.3 Ti ( IV )
c
Ti (IV)- 1:10 2 0.2 97.0 Ti(IV) 98.1 Fe ( IV ) c
Fe(III) 98.9 Fe( III)
10:1 97.2 Ti(IV) d
Ti (IV)- 1:10 2 0.2 98.3 Ti(IV) 98.8 Ga ( III) d
Ga(III) 98.7 Ga ( III)
10:1 97.6 Ti(IV) b
Ti (IV)- 1:10 10 0.5 99.1 Mg(II) 98.0 Ti ( IV ) b
Mg(II) 98.2 Ti ( IV )
10:1 98.1 Mg(II) e
Ti (IV)- 1:10 1 0.2 97.5 Ti(IV) 96.4 Zn ( II) e
Zn(II) 96.9 Zn ( II)
10:1 98.0 Ti(IV) h
Ti (IV)- 1:10 3 0.2 97.1 Ti(IV) 99.0 Cd ( II) h
Cd(II) 98.5 Cd ( II)
10:1 98.1 Ti(IV) a
V (IV)- 1:10 10 0.5 98.2 Ce(IV) 98.6 V ( IV ) a
Ce(IV) 98.3 V ( IV )
10:1 99.1 Ce(IV) a
V (IV)- 1:10 10 0.5 97.7 Al(III) 97.9 V ( IV ) a
Al(III) 97.0 V ( IV )
10:1 99.0 Al(III) c
V (IV)- 1:10 2 0.2 98.0 V(IV) 98.7 Fe ( III) c
Fe(III) 98.3 Fe( III)
10:1 98.5 V(IV) d
V (IV)- 1:10 2 0.2 98.3 V(IV) 98.7 Ga ( III) d
Ga(III) 98.5 Ga ( III)
10:1 97.2 V(IV) a
V (IV)- 1:10 10 0.5 99.3 Mg(II) 95.3 V ( IV ) a
Mg(II) 95.1 V ( IV )
10:1 99.2 Mg(II) c
Cr(III) – 1:10 2 0.2 99.7 Cr(III) 99.0 Fe ( III) c
Fe(II) 98.2 Fe( III)
10:1 99.2 Cr(III) e
Cr(III) - 1:10 8 0.5 96.4 Cr(III) 95.7 Co ( II) e
Co(II) 97.5 Co( II)
10:1 97.2 Cr(III) f
Cr(III) – 1:10 2 0.2 95.7 Cr(III) 98.0 Cu ( II) f
Cu(II) 98.1 Cu ( II)
10:1 97.3 Cr(III) g
Cr(III) – 1:10 2 0.2 99.7 Cr(III) 99.1 Zn ( II) g
Zn(II) 98.7 Zn ( II)
10:1 98.9 Cr(III)
a b
V (IV) stripped using 3(v) × 10 M H2SO4 Ti(IV) stripped using 3(v) × 2 M HCl
c d
Fe (III) stripped using 3(v) × 0.1 M H2SO4 Ga (III) stripped using 2(v) × 0.5 M H2SO4
e f
Co(II) stripped using 2(v) × 5 M H2SO4 Cu (II) stripped using 2(v) × 2 M H2SO4
g h
Zn(II) stripped using 2(v) × 0.1 M H2SO4 Cd(II) stripped using 3(v) × 0.1 M H2SO4
*
An average of minimum of three determinations

87
Classical Methods Table 3.1 (b): Some important binary separations involving 3d metal ions from
HCl solutions using Cyanex 92.3 (toluene)
Metal ions Molar HCL Cynex Metal ions Metal ions
Ratio M 923 M remaining* in the re cov ered*
(x 10−3 ) aqueous phase (%) from the
M organic phase
(%)
Mn - Fe(III) 1:10 2 0.1 98.1 Mn(II) 98.2 Fe (III)c
10:1 96.5 Mn(II) 97.5 Fe (III)c
Mn - Cu(II) 1:10 5 0.3 98.9 Mn(II) 96.0 Cu (II)f
10:1 98.6 Mn(II) 95.1 Cu (II)f
Mn - Zn(II) 1:10 2 0.2 99.3 Mn(II) 97.0 Zn (II)g
10:1 96.2 Mn(II) 98.2 Zn (II)g
Fe(III) - Al(III) 1:10 2 0.2 99.0 Al(III) 97.5 Fe (III)c
10:1 99.2 Al(III) 97.3 Fe (III)c
Fe(III) - Mg(II) 1:10 2 0.2 99.7 Mg(II) 97.1 Fe (III)c
10:1 98.7 Mg(II) 97.9 Fe (III)c
Fe(III) - Ni(II) 1:10 2 0.2 99.8 Ni(II) 98.1 Fe (III)c
10:1 99.7 Ni(II) 98.1 Fe (III)c
Fe(III) - Cu(II) 1:10 2 0.2 96.8 Cu(II) 96.3 Fe (III)c
10:1 97.4 Cu(II) 98.9 Fe (III)c
Fe(III) - Zn(II) 1:10 2 0.2 96.8 Zn (II)i
97.5 Fe (III)c
10:1 98.8 Zn (II)I
97.7 Fe (III)c
Fe(III) - Cd(II) 1:10 3 0.2 98.9 Cd (II)j
97.4 Fe (III)c
10:1 98.0 Cd (II)j
Co(II) – Ni(II) 1:10 8 0.5 99.8 Ni(II) 94.1 Co (II)e
10:1 99.2 Ni(II) 96.1 Co (II)e
Co(II) – Cu(II) 1:10 3 0.5 96.2 Co(II) 98.5 Cu (II)f
10:1 96.2 Co(II) 95.0 Cu (II)f
Co(II) – Zn(II) 1:10 2 0.1 99.2 Ni(II) 97.2 Zn (II)g
10:1 99.7 Ni(II) 97.4 Zn (II)g
Cu(II) – Zn(II) 1:10 1 0.1 98.0 Cu(II) 98.2 Zn (II)g
10:1 96.1 Cu(II) 97.5 Zn (II)g
Cu(II) – Cd(II) 1:10 1 0.3 95.2 Cu(II) 97.1 Cd (II)h
10:1 96.0 Cu(II) 93.2 Cd (II)h
Zn(II) – Cd(II) 1:10 0.1 0.3 96.3 Cd(II) 93.2 Zn (II)g
10:1 96.7 Cd(II) 92.9 Zn (II)g
c
Fe(III) stripped using 3(v) × 0.1 M H2SO4 e Co(II) stripped using 2(v) × 5 M H2SO4
f
Cu(II) stripped using 2(v) × 2 M H2SO4 g Zn(II) stripped using 2(v) × 0.1 M H2SO4
h
Cd(II) stripped using 3(v) × 0.1 M H2SO4 I Zn(II) stripped using 3(v) × water
j
Cd(II) stripped using 3(v) × water
*
An average of minimum of three determinations

Now we focus our attention to the extraction of Zn (II), Cd (II) and Hg (II) from HCl
solution in different representatives of primary, secondary and tertiary high molecular
weights amines and a quaternary ammonium salt for their separations.

From the extraction curves, it is apparent that mercury (II) can be separated
quantitatively from Zn (II) and Cd (II) only at a very low concentration of
hydrochloric acid (≤ 0.25 M). These separations can be carried out either in
chloroform or benzene solutions of Prime JM – T, Amberlite LA – 1 and Amberlite
LA – 2 or chloroform solutions of tribenzylamine and Alamine 336. The best

88
conditions for the separation of Hg (II) from Zn (II) and Cd (II) in these systems are Solvent Extraction-II
given in Table 3.2 (a) and (b). The efficiency of separations, for comparison, is
indicated by the separation factors given therein.

In all the above mentioned systems, Hg (II) is quantitatively extracted in the organic
phase leaving behind zinc and cadmium in the aqueous solution. The Hg (II) of the
organic phase can be stripped using 4 M or higher concentration of nitric acid.

The separations are not possible in Aliquat 336 because Zn (II) and Cd (II) also show
higher extractions in this amine even at lower acid concentrations. Chloroform, in
general, is a better diluent than benzene for the above mentioned separations.

Table 3.2 (a): Separation of Hg (II) from Zn (II) at 0.1 M HCl by various amines
(0.1M) in chloroform and benzene

Amine Diluent Separation factor

(0.1 M) (β)

Primene JM – T Chloroform ~ 104

Benzene > 104

Amberlite LA – 1 Chloroform >105

Benzene ~ 105

Amberlite LA – 2 Chloroform >105

Benzene ~ 105

Tribenzylamine Chloroform ~ 104

Chloroform >106

Alamine 336 Benzene 2 × 103

Table 3.2 (b): Separation of Hg (II) from Cd (II) from HCl solutions by various
amines (0.1 M) in chloroform and benzene
Amine Diluent Molarity of HCl Separation
(0.1 M) factor
(β)
Prime JM – T Chloroform 0.1 > 104

Benzene 0.1 ~ 104

Amberlite LA – 1 Chloroform 0.1 >105

Benzene 0.05 5 × 103

Amberlite LA – 2 Chloroform 0.1 ~105

Benzene 0.05 ~ 104

Tribenzylamine Chloroform 0.1 >104

Alamine 336 Chloroform 0.1 ~ 105

The separation of Zn (II) from Cd (II) poses problem because of similar trends in their
behaviour in most of the HMWA extraction systems discussed here. However,

89
Classical Methods detailed information available in different amines makes it possible to offer conditions
for their separation. Zn (II) can be separated from Cd (II) by employing 0.1 M
Amberlite LA – 1 / Amberlite LA- 2 solution in benzene. Cd (II) is extracted in the
organic phase at 0.25 M HCl leaving behind Zn (II) in the aqueous phase. The
separation factors in Amberlite LA – 1 and Amberlite LA – 2 are 2.3 × 102 and 3.8 ×
102, respectively. Cd (II) can be stripped from the organic layer by washing it with 4
M HNO3.

3.4.4 Presence of Masking Agents in the Aqueous Phase

The role of masking agents in solvent extraction has been discussed in sub-Sec. 3.3.5.
Their presence can be made use in carrying out separations which are otherwise
difficult to achieve. This amounts to the fact that the presence of the masking agent
can improve upon the separation factor. It has been mentioned earlier that the masking
agent forms sufficiently strong complexes with the interfering metals to prevent their
reaction with the extractant either altogether or raise the pH of extraction to a value
below which the metal of interest can be extracted quantitatively without interference.
The presence of masking agent is known to slow down the rate of extraction due to
slower kinetics of formation of the complex. The applicability of a particular masking
agent to an extraction system of interest can be gauged by considering the complex
forming constants of both the masking agent and the extracting agent. Masking agents
have been used successfully mostly in chelating extraction systems. There are
numerous examples and only a few are cited here.

An example of usefulness of masking agent is provided by the extraction of

aluminium in the presence of iron with 8 - quinolinol, in chloroform. Iron interference
is avoided by the addition of an alkali cyanide prior to extraction to form very stable
ferrocyanide ion. Nickel may be extracted with dimethylglyoxine in the presence of
cobalt if CN − is added to mask cobalt. Ni(CN) 24 − is destroyed by hydrogen peroxide
or formaldehyde but Co(CN) 24 − is very stable. The CNS − and S 2 O 32− have been used
to increase the selectivity in dithizonate extractions. EDTA is one of the most useful
masking agents. It forms anionic metal complexes with quite a few metal ions and has
been applied with success to extractions by dithizone, 8 - quinolinol, carboxylic acids,
acetylacetone and many more. The possibility that a longer equilibrium time may be
required in the presence of masking agent can be explored for separations. EDTA
forms chelates whose rates of dissociation are low. This has been observed in the
extraction of iron and copper 8 - quinolinates and copper thiocarbamate where the
presence of EDTA made necessary either longer extraction time or higher pH for
complete extraction. There are examples where interfering anions may be masked by
using masking cations. Thus, the interference of F − in UO22+ extraction may be
masked by adding an excess of Al3+ or B3+.

3.4.5 Selective Stripping from the Organic Phase

This approach has been partly explained in the sub-Sec. 3.4.1. The major difference is
that out of the different metal ions extracted in the organic phase, the stripping agent
selectively strips the metal ion of interest there. The desired metal ion can be stripped
in a subsequent step. The stripping agents are the same as already cited in the
sub-Sec. 3.35. Again, the examples are too many and only a few can be cited here.

Fe (III) and Ga (III) are extracted in diisopropyl ether from 6 M HCl. Iron can be
selectively stripped from the organic layer by washing it with hydroxylamine
hydrochloride dissolved in 6 M HCl. This is because Fe (II) formed shows negligible
extraction in ether from HCl medium. Ga (III) remaining in the organic layer is back
washed by using < 1 M HCl.

90
Ce (IV) an Th (IV) are extracted in TBP from nitrate medium. Ce (IV) can be back Solvent Extraction-II
extracted from the organic phase by washing it with a reducing agent like
hydroxylamine because Ce (III) is not extracted under those conditions.
If we refer to the three examples of separations, viz. Ti (IV) – V (IV), Fe (III) – Zn (II)
and Fe (III) – Cd (II) given in Tables 3.1 (a) and (b), these separations are based on
selective stripping. In each case, both the metal ions are extracted by Cyanex 923 and
this is followed by selective stripping. Before deciding upon the reagents for selective
stripping, a complete information on the extraction behaviour of the metal ions under
consideration from different aqueous media is required. In the Ti(IV) – V (IV) case,
the latter is selectively back extracted by 10 M H2SO4. In the other two cases, Zn (II)
or Cd (II) are selectively back extracted with water followed by stripping of Fe (III) by
0.1 M H2SO4.

3.5 CRITERIA FOR THE CHOICE OF ORGANIC PHASE

We are now at the concluding stages of this unit and have learnt that a variety of
extractants are available for the extraction / separation of metal ions. There are various
aqueous and organic parameters which affect the extraction. An intelligent utilization
of the variation in some of the parameters can result into separation of metals with
high separation factors. This makes the technique to be very useful for various
industrial operations and it finds applications in hydrometallurgy, nuclear fuel
reprocessing and environmental engineering (decontamination of metal loaded waste).
Because of the industrial utility of solvent extraction, we have to define the parameters
of the system in such a way that the process has industrial viability. The success of a
solvent extraction system depends upon the composition of both the contacting phases
i.e., aqueous and organic. The organic phase contains the extractant alone or the
extractant dissolved in a suitable diluent. In this context, it may be important to spell
out the criteria for the choice of organic phase. Some of these criteria may look
innocuous or insignificant when the technique is being applied for simple analytical
separations at bench level but they may have great importance in plant operations of
industrial applications. These criteria are listed below and are not necessarily in the
order of their importance.
i) The components of the organic phase should be immiscible with the aqueous
phase.
ii) It should have good stability. This will amount to the fact that the organic phase
should be capable of withstanding many recycling operations in a solvent
extraction circuit without degeneration.
iii) A difference in densities of the contacting phases is essential and should be as
great as possible.
iv) Low power requirement for pumping and agitating, rapid extraction and settling
of dispersion and high heat and mass transfer rates are corollaries of low
viscosity of the organic phase. Hence, low viscosity is a desirable property.
Dissolution of the extractants in low viscosity diluents modifies this property to
a favourable degree.
v) The interfacial tension should be high for rapid coalescence.
vi) The solvent should cause no corrosion difficulties with common materials of
construction to reduce the cost of equipment.
vii) The solvent should have low toxicity, high boiling and flash points. These
mainly avoid environmental pollution and fire hazards.
viii) It should have high metal loading capacity.
ix) It should be easily stripped of the loaded metal.

91
Classical Methods x) The extractant should have high extraction and regeneration power.
xi) The extractant should be selective to extract one component of a solution in
preference to the others.
xii) It should have good kinetics of extractions.
xiii) It should be relatively inexpensive. Low cost and ready availability in adequate
quantities parallel each other and are of course essential solvent attributes.
xiv) The extractant should be highly soluble in aliphatic and aromatic hydrocarbons.

Of all the desirable properties described selectivity, recoverability, interfacial tension

and density are essential for the process even to be envisaged for detailed
investigation.

SAQ 10
What will be the problem with the extraction system if the density difference of the
contacting phases is low and the interfacial tension of the organic phase is also low?

…………………………………………………………………………………………...
…………………………………………………………………………………………...

SAQ 11
What will it result to if the extractant has poor metal loading capacity and regeneration
power?

…………………………………………………………………………………………...
…………………………………………………………………………………………...

3.6 SUMMARY
This unit begins with a discussion on as to how the extraction of a metal ion in the
organic phase is possible. In this context, the extraction equilibria of some typical
extraction systems are discussed. These systems include extraction of metal
complexes, extraction by solvation, extraction by ion pair formation and extraction by
synergism. The role of different aqueous and organic phase parameters has been
explained. Taking a clue from the discussion, one gets into a position as to be able to
identify the factors influencing extraction. The role of the different parameters has
been elaborated by taking some appropriate examples. Once these factors are
identified, it becomes possible to usefully employ them for separations. A section is
devoted to illustrate some of the approaches which are generally adopted to achieve
separations of metal ions. The discussion is supported by citing examples from
extraction systems which have been exemplified earlier in this unit. It has been
pointed out that solvent extraction has a wide variety of utility for industrial
applications. Particularly, in this context, the choice of organic phase becomes very
critical. The unit concludes with general criteria for the choice of the organic phase.

3.7 TERMINAL QUESTIONS

1. In the extraction of MnO −4 by tetraphenylarsonium chloride, cite the final
equilibria steps which show the increase or decrease in extraction by change in
the experimental variables.

2. What should be the general criteria for the selection of a suitable salting out
agent?

92
3. Give suitable explanation for the following: Solvent Extraction-II
i) Al (NO3)3 is a better salting out agent than NH4NO3 as for the
enhancement in extraction is concerned but the latter is generally
preferred over the former in different extraction systems.
ii) In making log- log plots of [Extractant] vs distribution ratio, the use of
metal ion solutions of a carrier free radioisotope is generally
recommended.
iii) In the extraction of chloro complexes of Zn (II), Cd (II) and Hg (II) by
high molecular weight amines, in most of the cases, the extent of
extraction follows the order Zn < Cd < Hg.

4. Explain synergism and the role of the two types of extractants used to observe
the phenomena.

5. What is the loading capacity of an extractant? How is it determined?

6. What are the different types of stripping solutions?

7. In what different ways a masking agent can help in achieving selectivity in

metal ion separations?

8. Using the extraction data in toluene solution of Cyanex 923, suggest schemes
for the separation of individual metal ions from the following ternary mixtures:
i) Ti (IV) – Al (III) – Fe (III)
ii) Ti (IV) – Al (III) – Ga (III)
iii) Cr (III) – Fe (III) – Zn (II)

3.8 ANSWERS
Self Assessment Questions
1. The two simplifications assumed are
i) In the aqueous phase, the metal exists as Mn+ only. No hydroxyl or anionic
complexes are formed.
ii) In the organic phase, the metal exists as a single complex MRn only.

2. The values of the following constants should be higher for a higher metal
extraction.
i) (Ka) dissociation constant of the ligand.
ii) (Kf) formation constant of the complex.
iii) (KDX) distribution constant of the metal chelate.

3. The two main categories of the solvating extractants are

i) Extractants with oxygen bonded to carbon such as ethers, esters, alcohols
and ketones.
ii) Extractants with oxygen or sulphur bonded to phosphorus such as
alkylphosphates or alkylthiophosphates.

4. A decrease in the extraction of Fe (III) from HCl medium in diethyl ether beyond
6 M HCl is observed due to the high solubility of diethyl ether in concentrated
HCl. No decrease in the extraction of Fe (III) in β, β ′ - dichloroethyl ether is

93
Classical Methods observed because β, β ′ - dichloroethyl ether has low solubility even in
concentrated HCl.

5. The slope of log – log plot of D vs free amine concentration being 2 suggests
that two molecules of the quaternary ammonium salt are involved in the
formation of the extracting species. The equilibria are thus as follows:
Cd (2a+) + 2 H2C2O4 (a) Cd(C2O4)2 (2a−) + 4 H (+a )

(R3R´N+)2. C2O 24−o + Cd (C2O4)2 (2a−) (RR´N+)2. Cd (C2O4) 22o− + C2O4 (2a−)

6. A deviation in the extraction efficiency of HMWA is generally observed due to

steric problem caused due to branching in the amine or the large size of the
anionic complex being extracted.

7. The extraction efficiency of the three carboxylic acid – amine synergistic

systems follows the order:
Propionic acid – tributylamine < valeric acid – tributyl amine < valeric acid –
pyridine.

8. If the masking agent forms a stronger complex with the metal ion than that
formed by the extractant the extraction of the metal may be checked.

9. The pH1/2 for the extraction of a metal chelated can be raised by the addition of a
masking agent.

10. It will lead to an emulsion formation.

11. Poor loading and recycling capacity will need more of the extractant thereby
increasing the cost of the process.

3.9 TERMINAL QUESTIONS

1. The equations which express the dependence of extraction of MnO −4 by
(C6H5)4 As+. Cl− on experimental parameter are

[(R 4 As + .MnO 4− )]o

i) D=
[MnO −4 ]a

= KDX Kf. [R4 As+]a

The extraction will increase with the increase in the extractant, R4As+
concentration

K DX K f K [(R 4 As + .Cl − )]o

ii) D= .
K DR [Cl − ]a

The extraction will decrease with the increase in chloride ion

concentration.

2. The general criteria for the selection of a suitable salting out agent are
i) It should increase the activity of the distributing species.
ii) It should have strong ability to bind to water molecules thereby depleting
the aqueous phase of the water molecules to complete.

94
 iii) It should not itself extract in the organic phase to an appreciable extent. Solvent Extraction-II

iv) It should preferably increase the extraction of the metal of interest not the
impurities.
v) It should be easy to remove or destroy the reagent from the aqueous phase
for further processing.
3. i) NH4NO3 is preferred over Al (NO3)3 because it is easier to destroy
NH4NO3 for subsequent processing of the aqueous phase.
ii) In the log – log plots, it should be the equilibrium concentration of the
extractant in the organic phase. It is difficult to find the unbound
concentration of the extractant. The problem is partly resolved if
extremely low concentration of the metal ion is used. Thus, the
equilibrium concentration of the extractant can be taken the same as its
initial concentration. In the labeled metal ion solution with no additional
carrier, the concentration is very low and there is no difficulty in the
quantification of the distribution of the metal in the two phases.
iii) The observed order in extraction follows the sequence of the formation
constants of chloro complexes in the aqueous phase. It is the anionic
chloro complexes which are getting extracted in the solution of high
molecular weight amines.

4. In synergism, there are two extractants which work together to increase the
extraction by a huge factor. The extracting power of the mixture exceeds the sum
of the extracting power of the individual extractants. In synergism, one of the
two extractants is a ligand or an organic acid (HA) which neutralizes the charge
on the metal ion and the other, a solvating molecule (S) which either replaces the
water molecule from the coordination sphere or forms an adduct which is less
hydrophilic.

5. Loading capacity of an extractant is the maximum amount of the metal ion that
can be extracted by the extractant. It is usually expressed in terms of metal
extractant mole ratio. For the determination of loading capacity, please refer to
sub-Sec. 3.3.3 on “Effect of Metal Ion Concentration.”

The loading capacity is determined at specific aqueous and organic phase

conditions. In the organic phase, the extractant concentration is kept constant. In
the aqueous phase, the molarity of the acid/ pH is kept constant and the
concentration of the metal ion is varied. With the increase in the metal ion
concentration, there is an increase in concentration of the metal ion in the
organic phase.

There is a linear relationship between [M]aqueous and [M]organic up to a point. But

when the organic phase gets saturated, there is no further increase in the
concentration of the metal ion in the organic phase. These curves (Fig. 3.8) are
known as extraction isotherms.

The molar ratio of metal to extractant at the loading conditions can be

computed. From this data, the loading capacity of the extractant is found out.

6. The different types of stripping agent solutions are:

i) Pure water or water adjusted to an appropriate pH or molarity of acid.
ii) Water containing an oxidizing or reducing agent.

95
Classical Methods iii) Water containing an appropriate masking agent.

7. The masking agent may help in achieving the selectivity by

i) Suppressing the extraction of the interfering cations altogether.

ii) By raising the pH 12 of the extraction of the interfering cations such that
the metal of interest is quantitatively extracted before this pH.
iii) By slowing down the kinetics of extraction of the interfering cations.

8. i) Separation of Ti(iv) – Fe (III)

Solution Ti(iv) + AI(III) + Fe(III)

i) Acidity 1 M HCl
ii) Extract by 0.5 M Cyanex 923 (toluene)

Organic Phase
Aqueous Phase Ti(IV), Fe(III)
AI(III) Strip by 2 M HCl

Organic Phase
Fe(III)
Aqueous Phase
Ti (IV) Strip by 2 M H2SO4

Aqueous Phase Organic Phase

Fe (III)

iii) Separation of Cr(III) – Fe (III) – Zn (III)

Solution Ti(IV) + AI(III) + Ga (III)

i) Acidity 10 M HCl
ii) Extract by 0.5 M Cyanex 923 (toluene)

Organic Phase
Ti (IV) , Ga (III)
Aqueous Phase
Strip by 2 M HCL
AI (III)

Organic Phase
Ga (III)
Aqueous Phase Strip by 2 M H2SO4
Ti (IV)

Aqueous Phase Organic Phase

Ga (III)

96
 iii) Separation of Cr (III) – Fe (III) – Zn (III) Solvent Extraction-II

Solution Cr (III) + Fe (III) + Zn (II)

i) Acidity 2 M HCl
ii) Extract by 0.5 M Cyanex 923 (toluene)

Aqueous Phase Organic Phase

Cr (III) Fe (III) , Zn (II)
Strip by water

Aqueous Phase Organic Phase

Zn (II) Fe (III)
Strip by 0.5 M H2SO4

Aqueous Phase Organic Phase

Fe (III)

Further Readings
1. Solvent Extraction in Analytical Chemistry, By G. H. Morrison and H. Freiser,
John Wiley & Sons Inc.

2. Ion Exchange and Solvent Extraction of Metal Complexes, By Y. Marcus and

A. S. Kertes, Wiley – Interscience.

3. Solvent Extraction: Principles and Applications to Process Metallurgy Part I, By

G. M. Ritcey and A. W. Ashbrook, Elsevier Science Publishers B. V.

4. Solvent Extraction of Metals, By A. K. De, R. A. Chalmers, and S. M. Khopkar,

Van Nostrand-Reinhold Publication.

5. Solvent Extraction of Metal Chelates, By J. Stary, Pergamon Press.

Acknowledgements
i) The data on the extraction of Zn (II), Cd (II) and Hg (II) in high molecular
weight amines in part has been quoted from
Om Vir Singh and S. N. Tandon, J. Inorganic Nuclear Chemistry 36, 2083
(1974); 37, 609 (1975); 36, 439 (1974).

ii) The data on the extraction of metal ions in Cyanex 923 in portions has been
cited from B. Gupta, A. Deep, P. Malik and S. N. Tandon, Solvent Extraction
and Ion Exchange 20, 81 (2002).

97
Classical Methods
INDEX
β, β′ – dichlorodiethyl ether 64
Acid Molarity 85
Aqueous Phase 85
Cyanex 92.3 83, 84, 85, 86, 87
HMWA 85
Alamine – 336 83
Aliquat 336 80
Antisynergism 74
Ascending chromatography 17
Capability for Hyphenation 24
Carboxylic and Sulphonic Acids 42
Chelating Agents 40
Choice of organic phase
Criteria for 91
Chromatography 12
Chromatogram 13
Chromatographic method 13
Evolution 13
Gas Chromatography 13
Ion exchange chromatography 13
Liquid-solid adsorption chromatography 13
Mobile phase 13
Partition Chromatography 13
Stationary phase 13
Classification Based on Property Resulting in Separation 15
Cyanex 272 42
Cyanex 301 42
Electromigration 15
Ion exchange 15
Molecular geometry 15
Partition 15
Solubility 15
Surface activity 15
Volatility 15
Classification of separation methods 14
Classification 14
Equilibrium processes 14
Physicochemical phenomena 14
Property 14
Volatility
Solubility
Partition
Ion exchange
Surface activity
Molecular geometry
Electromigration
Rate processes 14
Column liquid-liquid partition chromatography 17
Concentration of the Extractant 82
Alamine – 336 83
Cyanex 923 83, 84
Radiotracers 82
Criteria for Selection of Separation Methods 23
Capability for hyphenation 23
Detectability 23
economics 23
scaling up 23
Selectivity 23
Yield, speed and convenience 23

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Cryptands 50 Solvent Extraction-II
Cyanex 923 47
Cyanamid reagent 47
Descending chromatography 17
DEHPA 42, 53
Detectability 24
Dialysis 19,22
Diluent 84
Diluents and Modifiers 51
Diluent 51
Distribution of Simple Molecules 40
Distribution ratio (D) 33
Dithizone 60
Effect of Metal Ion Concentration 80
Extraction isotherms 80
Loading curves 80
Electrodialysis 19,22
Electromigration 20
Capillary electrophoresis 20, 22
Electrochromatography 20, 22
Electrophoresis 20, 22
Slab electrophoresis 20
Equilibrium processes 20
Adsorption 21
Adsorption chromatography (column and planar) 22
Affinity chromatography 22
Chromatography 21
Dialysis 22
Distillation 21
Electrodyalysis 22
Exclusion (gel permeation) chromatography 22
Foam fractionation 21
Fractional crystallization 22
Gas-liquid chromatography 21
Gas-solid chromatography 21
High pressure liquid chromatography 21
Ion exchange chromatography 22
Liquid-liquid column chromatography 21
Liquid-liquid planar chromatography 21
Liquid-liquid extraction 21
permeable barriers 22
Precipitation 21
Rate processes 20
Reverse Osmosis 22
Sublimation 21
Ultrafiltration 22
Extraction by Compound Formation 40
Carboxylic Acids 44
Carboxylic and Sulphonic Acids 42
Chelating Agents 40
Cyanex 272 42
Cyanex 301 42
DEHPA 42
Extraction 44
Masking agents 41
Metal ions 44
Naphthenic acid 43
OPPA 42
Organophosphorus Compounds 41
Sulphonic acids 44
Versatic acid 43

99
Classical Methods Extraction by Crown Ethers 49
Colorometric method 50
Cryptands 50
Extraction of metals 49
Extraction by Ion Pair Formation 48
HMWA 48
Liquid anion exchangers 48, 67
Extraction by Ion Pair Formation 67
Extraction of anionic metal complexes 67
Extraction of Anionic Metal Complexes 69
Extraction of permanganate ion 67
Extraction of Tetraphenylarsonium Permanganate 67
Tetraphenylarsonium chloride 67
Liquid anion exchangers 67
Extraction by Solvation 44
Alkylphosphates 45
Alkylthiophosphates 45
Cyanamid reagent 47
Cyanex 923 47
MIBK 45
TIBPS 47
Extraction by Solvation 63
β, β′ – dichlorodiethyl ether 64
Extraction of Fe(III) 64
Extraction by Synergism 72
Antisynergism 74
HTTA 72
TBP 72
Extraction of
Anionic metal complexes 67
Cd (II) 79
Hg (II) 80
Permanganate ion 67
Tetraphynylarsonium permanganate 67
Zn (II) 79
Extraction of Anionic Metal Complexes 69
Extraction of Metal Chelates 59
Dithizone 60
Metal chelates 59
Oxine 60
Extraction by Synergism 72
Extraction Systems 39
Classification of 39
Factors Influencing Extraction 75
Acid Molarity 85
DEHPA 76
pH 75
Field separations 22
Capillary electrophoresis 22
Electrochromatography 22
Electrodeposition 22
Electrophoresis 22
Thermal diffusion 22
Ultracentrifugation 22
Fractional distillation 15
Flash distillation 15
Steam distillation 16
Vacuum distillation 15
Gas-liquid chromatography 17
Gel filtration 19

100
Gel permeation 19 Solvent Extraction-II
Gibbs Phase Rule 31
High performance 17
High-pressure liquid chromatography (HPLC) 17
HMWA 48
HTTA 72
Ion Exchange 17
Amphoteric exchangers 17, 18
Anion exchangers 17
Cation exchangers 17
Ion exchanger 17
Liquid anion exchangers 48
Liquid-liquid extraction 16
Descending chromatography 17
High performance 17
High-pressure liquid chromatography (HPLC) 17
Liquid-liquid partition chromatography 17
(HPTLC) 17
Liquid-liquid extraction 16,17,30
Extractive spectrophotometry 31
Masking Agents 41, 82, 89
Metal chelates 59
Metal Ion Extraction Equilibria 58
Extraction equilibria 59
Slope analysis 59
MIBK 45
Modifiers 53
DEHPA 53
Molarity 77
Aliquat 336 80
Extraction of Cd(II) 79
Extraction of Hg(II) 80
Extraction of metals by solvation 77
Extraction of Zn(II )79
Ion – pair formation 77
Percent extraction 77
Molecular Geometry 19
Molecular sieves 19
Multiple Extractions 37
Discontinuous countercurrent 37
Fractional distillation 37
Pseudo countercurrent 37
Naphthenic acid 43
Nernst distribution law 32
Distribution coefficient (K´) 32
Extraction coefficient 32
Thermodynamic partition coefficient 32
OPPA 42
Organophosphorus Compounds 41
Oxine 60
Paper chromatography 17
Partition 16
Gas-liquid chromatography 16
Liquid-liquid extraction 16
Liquid-liquid partition chromatography 16
Percentage Extraction (% E) 35
Permeable barrier 19
pH of the Aqueous Phase 85
Planar chromatography 17

101
Classical Methods Rate processes 22
Radiotracers 82
Reproducibility 23, 24
Reversed phase chromatography 17
Reverse osmosis 19,22
Salting Out Agents 81
Masking agents 82
Sequestering agents 82
Scaling up and economics 25
Selective Stripping 90
Selectivity 23
Semi –permeable membranes 19
Applications off 19
Charged membranes19
Homogenous membranes 19
Microporous membranes 19
Thin membranes 19
Separation 10
Objectives 11
Separation Factor ( β ) 36, 84
Separation Method 14
Classification of 14, 20
Equilibrium processes 20
Criteria for selection
Rate process 22
Size exclusion chromatography 19
Slope analysis 59
Solvent extraction 16,30
Solubility 16
Azeotrophic distillation 16
Stripping 84
Sulphonic acids 44
Surface Activity 18
Adsorption 18
Affinity chromatography 18
Gas- solid adsorption chromatography 18
Liquid-solid adsorption chromatography 18
TBP 72
Thin layer chromatography 17
TIBPS 47
Two-dimensional chromatography 17
Ultrafiltration 19,22
Versatic acid 43
Volatility 15
Azeotropic distillation 15
Distillation 15
Flash distillation 15
Fractional distillation 15
Steam distillation 15
Vacuum distillation 15
Vaporization 15
Yield, Speed and Convenience 24

102