Solvent Extraction

Unit-1
 Syllabus
• Unit 1: Solvent extraction
Distribution constant and distribution ratio and
their importance in solvent extraction; synergistic
extraction; extraction by solvation; chelation,
Extraction equilibria for solvation, extraction of
metal by Ion pair formation; Efficiency and
Selectivity of extraction; Extraction system;
Methods of extraction and their applications in
analytical chemistry.
 Introduction
• It is a method of separation techniques in which a solution (usually aqueous) is
brought in contact with a second solvent (usually organic) immiscible with the
first in order to bring about a transfer of solute into the second solvent. This
occurs through a partitioning process, which involves the distribution of a
solute b/w immiscible liquid phases. This technique is also called partitioning
or liquid-liquid extraction.
• It is a method to separate compounds based on their relative solubilities in two
different immiscible liquids, usually water and an organic solvent. It is an
extraction of a substance from one liquid into another liquid phase.
Solvent Extraction, consists of transferring one (or more)
solute(s) contained in a feed solution to another immiscible
liquid (solvent). The solvent that is enriched in solute(s) is
called Extract & the feed solution that is depleted of solute(s)
is called Raffinate.
 When shaken, with two immiscible solvents, the compound will
distribute itself between the two solvents. Normally one solvent is
water and the other solvent is a water-immiscible organic solvent.
Most organic compounds are more soluble in organic solvents, while
some organic compounds are more soluble in water.

Ether is the most common solvent used for extraction. Other common solvents used are
hexane, benzene, chloroform, acetone, carbon tetra chloride etc.
• For example, the mixture of carboxylic acid and phenol can be
separated into individual components by dissolving the mixture in
ether and extracting with dilute sodium carbonate solution so that
carboxylic acid is almost completely transferred to aqueous phase.
• From a mixture of sugar in vegetable oil, sugar can be separated by
shaking the mixture with water.
• Solvent extraction is used for the preparation, purification,
enrichment, separation and analysis of compounds. It is simple,
rapid and is applicable at tracer and microgram concentration level.
 Principle of solvent extraction
• When a solute (liq or solid) is added to heterogeneous system of two immiscible
liquids (in both of which the solute is soluble), the solute distributes b/w the two
liquids. This distribution is governed by Nernst distribution law.
(a) The distribution of solute, A, b/w two immiscible solvents (aq. and organic) is an
eqm process; Aaq ↔ Aorg
(b) At a constant temperature, the ratio of concentrations of a solute in each solvent is
always constant provided its molecular state is the same in both liquids. This
constant is known as the distribution (or partition) coefficient, represented by the
term, KD.
For a solute A distributed between two immiscible phases a and b, the Nernst
Distribution (or Partition) Law states that

KD = [A]org/[A]aq
Where, a= organic solvent and b= aqueous solvent

The greater the distribution ratio is in favour of the organic solvent, the greater will be
the amount extracted in any one operation.
 Limitations of Nernst distribution law
The conditions to be satisfied for the application of the
Nernst’s distribution law are:
• Constant temperature: Temperature has to be maintained
• Same molecular state: not applicable where the solute
undegoes association or dissociation in one of the solvents
• Equilibrium concentration: concentrations of the solute are
noted after the equilibrium is established
• Dilute solutions: Concentration of the solute in the solvents
must be low. The law does not hold for high concentration.
• Non-miscibility of the solvents: The solvents are non-
miscible or only slightly soluble in each other.
 Importance of Distribution ratio in Solvent Extraction or
The Concept of Distribution Ratio

The solute that is distributed between two phases undergoes dissociation or

association on one or both the phases.
Ex. The extraction of benzoic acid from an aqueous solution by addition of
organic solvent like ether. Benzoic acid is slightly ionized in aqueous
solution as follows:
C6H5COOH ↔ C6H5COO- + H+
The ionization constant Ka is given as
Ka = [H+] [C6H5COO- ]
[C6H5COOH]
When aqueous solution of the acid is shaken with immiscible solvent like
ether. The distribution coefficient KD is given by the relation
KD = [C6H5COOH]ether
[C6H5COOH]aq
• However, part of benzoic acid in aqueous layer exists as C6H5COO-
depending on the magnitude of Ka and pH of the aqueous layer.

• Hence quantitative separation may not be achieved. However in solvent

extraction, the primary interest is the fraction of the total solute i.e.
transferred into either of the two phases and association and dissociation is
immaterial. A different term called the distribution ratio D has been
introduced which takes account of the solute in all its forms in the two
phases.

• It is defined as the ratio of the concentration of the species of the solute in

each phase. It is given by

• D = [C6H5COOH]ether
[C6H5COOH]aq + [C6H5COO-]aq …………(1)
 Relation between D and KD
• KD- Distribution or Partition coefficient
• D- Distribution Ratio

Ka = [H+] [C6H5COO- ]
[C6H5COOH] ………………………. (2)

• [C6H5COO-] = Ka [C6H5COOH] / [H+] ……………………….(3)

[C6H5COOH]ether
KD = [C6H5COOH]aq

[C6H5COOH]ether = KD [C6H5COOH]aq ………………………. (4)

Substituting equation 3 and 4 in eq. 1, we get

D= KD [H+] ………………………. (5)

[H+] + Ka
 Conclusion from eq. 5 D= KD [H+]
[H+] +Ka
From eq. (5), it is clear that
(a) When [H+]aq >> Ka, D is nearly equal to KD.

(b) If KD is large, Benzoic acid will be extracted into ether layer and D is
maximum under these conditions.

(c) When [H+] << Ka, then D reduces to KD [H+]aq , which will be very
Ka
small and benzoic acid will remain in the aqueous layer.

(d) Equation predicts that the extraction efficiency (D) will be independent of
original concentration of the solute. This is one of the attractive feature of
the solvent extraction. This method is applicable to tracer levels and to the
macro levels provided there are no side reactions.
 Percent of Extraction (E%)
The more commonly used term for expressing the extraction efficiency by analytical
chemist is the percent extraction “E”, which is related to “D” as

Where V represent solvent volume and the other quantities remain as previously
defined.
The percent extraction may be seen to vary with the volume ratio of the two phases as
well as with D.
• If Vaq and Vorg represents the volume of aqueous and organic
phases respectively in litre and E moles of solute A, out of 100
moles of A, is present in organic phase and (100-E) moles of A
in aqueous phase. Then
• D=[C]org/[C]aq
= E/Vorg/(100-E)/Vaq
=E/Vorg x Vaq/(100-E)
100 D Vorg= E (DVorg+Vaq)
100 D = E (D+Vaq/Vorg)
E= 100D ...…..(6)
D+Vaq/Vorg
From equation it is clear that fraction extracted (E) can be
increased by decreasing the ratio Vaq/Vorg i.e by increasing the
volume of organic phase.
If Vaq=Vorg, then E= 100D/ D+1
 Separation Factor
• If a solution contains two or more solute say, A and B, it is often observed
that when A is extracted some amount of B is also extracted. The extent of
separation can be found by a quantity called the separation factor β that is
related to the distribution ratio of A and B by the equation

β = [Aorg]/[Aaq] = DA
[Borg]/[Baq] DB

From this equation it is clear that in order to make β large, we need to

make an appropriate choice of extractant and adjust the volume ratio.
When DA= 10 and DB= 0.1, the separation factor β will be 100. Hence we
conclude that when DA is large and DB is small, almost complete extraction
of A takes place.
• When DA and DB are close to each other, both A and B are
extracted at the same. In this case β can be increased by
adjusting the volume ratio given by Bush Densen Equation

Vorg = 1
Vaq (DADB)1/2
Methods of solvent extraction
 Methods of solvent extraction
• Batch extraction
• Continuous extraction
• Countercurrent extraction
Batch extraction
 Batch extraction
Batch extraction, the simplest and most commonly used
method, consists of extracting the solute from one
immiscible layer in to other by shaking the two layers
until equilibrium is attained, after which the layers are
allowed to settle before sampling. This is commonly
used on the small scale in chemical laboratories.
The most commonly employed apparatus for performing
a batch extraction is a separatory funnel. The batch
extractions may also be used with advantage when the
distribution ratio is large.
Continuous extraction
 Continuous extraction
The second type, continuous extraction, makes use of a
continuous flow of immiscible solvent through the solution or a
continuous countercurrent flow of both phases. Continuous
extractions are particularly applicable when the distribution ratio
is relatively small. Continuous extraction device operate on the
same general principle, which consist of distilling the extracting
solvent from a boiler flask and condencing it and passing it
continuously through the solution being extracted. The extracting
liquid separates out and flows back into the receiving flask,
where it is again evaporated and recycled while the extracted
solute remains in the receiving flask. When the solvent cannot
easily be distilled, a continuous supply of fresh solvent may be
added from a reservoir.
 Countercurrent extraction
• Also called Craig countercurrent extractor
• Craig method: to separate two species by
solvent extraction if their KDs are not
sufficiently different.
Lyman C. Craig, 1906-1974
• A method of multiple liquid-liquid extractions is countercurrent extraction,
which permits the separation of substances with different distribution
coefficients (ratios).
• A design known as Craig apparatus is used for this purpose. Craig
apparatus consists of a series of glass tubes (r: 0, 1, 2..) that are designed
and arranged such that the lighter liquid phase is transferred from one tube
to the next.
• C:\Users\Sharda\Desktop\Countercurrent Extraction - Craig
Apparatus.html
• The extractant and solution containing
the solute are introduced through A and B
and equilibrated there.
• When two phases are separated the
apparatus is tilted so that the upper layer
or the phase get decanted through C and
is collected in D.
• When the apparatus is again made
vertical the liquid in D passes through E
into the next equilibrium chamber
(similar to B)
 Classification of extraction systems:

1. Extraction by solvation
2. Extraction by chelate formation
3. Extraction by ion pair formation
4. Synergitstic extraction
 Some organic compounds can be
made water-soluble.
• Compounds belonging to the following solubility
classes can be converted to their water-soluble salt
form.
• and

• Organic acids include carboxylic acids (moderately

weak organic acids) and phenols (weak organic
acids).
• Bases include amines
To a first approximation, in dilute solution, KD is
independent of concentration.

• KD pertains to a single species

• Doesn’t include products of side reactions
• Consider the distribution of benzoic acid
between benzene and water
Separating species

Β-naphthol

Benzoic acid
• pH < 2 Both non-ionic, both will transfer to
benzene.

• pH > 5 Benzoic acid is deprotonated and stays

in water
• -naphthol still transfers to benzene

• pH 11 Both dissociate and both stay in water.

Some dimerizes in the organic phase

Each species has own KD

But we are interested in total amount extracted

 Total benzoic in organic phase
D
Total benzoic in aqueous phase
[HBz]org  2[(HBz)2 ]org
D [HBz]aq  [Bz  ]aq

D is the Distribution ratio

• Substitute:

 [HBz] [HBz] org

[Bz ]  K a 
, KD  and
[H ] [HBz] aq
[(HBz) 2 ]  K f [HBz] 2
then

K D (1  2K f [HBz])
D
Ka
1 
[H ]
For a weak acid which doesn’t
dimerize – can simplify:

KD
D
Ka
1 
[H ]
Factors influencing the extraction
efficiency
1. Choice of solvent
2. Acidity of an aquous phase
3. Stripping
4. Use of masking agent
5. Salting out agent
6. Back washing
7. Variation of oxidation state
8. Synergic extraction
9. Use of organic acid media
 Choice of solvent
•The most important consideration in the selection of a solvent for use in a
particular extraction procedure is the extractability of the element of interest.
For subsequent analytical processing a consideration of the solubility of the
solute in particular solvent, the ease of recovery of the solvent or the ease of
recovery of the solute from the solvent is very important. Thus, the boiling point
of the solvent or the ease of stripping by chemical reagents enters into selection
of a solvent when the possibility of a choice existed.
• The degree of miscibility of the two phases, the relative specific gravities,
viscosities and tendency to form emulsion should be considered. From the point
of view of safety, the toxicity and the flammability of the solvent must be
considered.
•Use of a suitable solvent for effective separation is very important. Metal
chelates and many organic molecules, being essentially covalent compounds
do not impose many restrictions on the solvent and the general rules of
solubility are the great use.
•In ion association systems and particularly in oxonium type ions, the role of
solvents is very important. This is due to involvement of solvent in the formation
of extractable species.
 Acidity of Aqueous phase
•The extractability of metal complexes is greatly
influenced by the acidity of an aqueous phase.
• It is necessary to assure optimum concentration of H+
ions for maximum extraction.
• In the case of chelate extraction, the chelating reagent
concentration is maintained constant; the distribution of
the metal in a system is a function of pH.
•For this reason, curves of extractability versus pH at
constant reagent concentration are of great analytical
significance.
•Sometimes it is possible to achieve the desired
characteristics of a solvent by employing a mixed
solvent system.
 Stripping
Stripping is the removal of the extracted solute from the organic phase for further
processing or analysis. In many colorimetric procedures and even radioactive
techniques, the concentration of solute is determined directly in the organic phase.
However, where further separation steps are required, it is necessary to remove the
solute from the organic layer to more stable medium. When organic layer is on the
steam bath, care should be taken, to avoid loss of volatile solute during evaporation.
Addition of acid to water before evaporation helps to break the chelate complexes,
thereby causing the metal ion to enter the aqueous phase. In the process of destroying
the residual organic matter, hydrochloric acid, nitric acid, perchloric acid or aqua regia
is used.
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 masking agent. The metal ion is then back extracted in the stripping aqueous phase.
The conditions employed depends upon 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 and reducing agent changes the
metal ion to be stripped in an oxidation state in which it is not extracted under the
specific conditions.
 Use of masking agents
In the extraction procedures for metal pairs that are difficult to
separate; masking or sequestering agents are introduced to
improve the separation factor. Masking agents are themselves
metal-complexing agents, which serve to prevent a particular
metal from taking part in their usual reaction, and thus to remove
their interference without the necessity of actual separation. In
solvent extraction, masking agents are used to prevent certain
metals from forming extractable complexes and increasing the
selectivity of the method. In extraction of metals the application of
masking agents, which include cyanide, tartarate, citrate, fluoride,
and EDTA. The selection of a particular masking agent largely
depends on the acidity of the system and the complex formation
constants of the metal with both the masking and the extraction
agent. EDTA, which has been proved as most useful masking
agent, forms anionic complexes with a number of metal ions.
 Salting out agents
The term salting-out agent is applied to those electrolytes whose
addition greatly enhances the extractability of complexes. The function
of salting-out agent would be primarily of providing a higher
concentration of complex and thus improve the extraction. Water is
probably bound as a shell of oriented water dipoles around the ion and
thus becoming unavailable as “free solvent”. Addition of salting-out
agents decreases the dielectric constant of the aqueous phase, which
favors the formation of the ion association complexes. Salting-out
agents have been used with great success in separation involving the
halide and thiocynate systems.
In addition to enhancement of the extraction of the metal of interest
using saltingout agents, it is also possible to decrease the extraction of
impurities in the system. Thus, it is necessary to choose an agent that
produces a favorable separation factor between the element of interest
and the impurities. However, it must be remembered that anomalies
sometimes result from specific interaction effects. Aluminium or calcium
salts are strong salting-out agents, whereas ammonium salts are much
weaker but analytically more convenient.
 Backwashing
Backwashing is an auxiliary technique used with batch extractions
to influence quantitative separations of elements. The combined
organic phases from several extractions of the original aqueous
phase contain practically all the desired elements and possibly
some of the impurities that have been extracted to a much smaller
extent. This combined organic phase when shaken with one or
more small portions of a fresh aqueous phase containing the
optimum reagent/ salting agent concentration, acidity, etc., will
result in a redistribution of the impurities in favor of the aqueous
phase since their distribution ratios are low.
Under optimum conditions, most of the elements of interest will
remain in the organic layer, since their distribution ratios are high.
This technique is analogous in many respects to the re-
precipitation step in a gravimetric precipitation procedure. With the
proper conditions, most of the impurities can be removed by this
backwashing operation, with negligible loss of the main
component, thereby attaining a selective operation.
 Variation of oxidation state
The selectivity of an extraction is increased by the modification of
oxidation states of the interfering ions present in solution, in order
to prevent the formation of their extractable metal complexes e.g.
reduction of Cerium(IV) to Cerium(III) prevents extraction of this
element from nitrate media, the extraction of Iron(III) from chloride
solutions can be prevented by reduction to Iron(II), which is not
extractable. Similarly, Antimony(V) may be reduced to the
tetravalent state to suppress its extraction.
Conversely, it is important in the preparation of a solution for
extraction to adjust the proper valence state of metal ion required
for the formation of the complex in order to ensure complete
extraction of that element. Selectivity can also be achieved by
variation of the oxidation state of the co-extracted interfering ions
during the stripping operation.
 Synergic extraction

Synergism is defined as the combined action of

two complexing reagents, which is greater than
the sum of the actions of the individual reagents
used alone.
An example of the synergic extraction of Ce(III)
with picrolonic acid and benzo-15-crown-5.
 Use of organic acid media
• Organic acid media are having ability of controlling the
concentration of the complexing ligand.
•This is one of the unique application, as the ease of
adjustment of pH and the wide difference in pH at which
various metal ions form anionic complexes.
•The comparative ease of stripping of the complexes
from the organic phase can be achieved by fully
exploiting the differences in reactivity of various metals
to backwash in the aqueous phase by mineral acid.
•It is known that organic acid media offers better
separation of metals possibly due to high stability of
metal organic acids complexes.
Synergistic extraction
 Synergistic extraction
• The process of extraction is enhanced on account of the use of two
extractants.
Eg. Extraction of Uranium with Tributyl phosphate (TBP) as well as 2-
Thenoyl trifluoroacetone (TTA).
Although either of TBP or TTA are individually capable of extracting
uranium if mixtures of these two extractants are used, enhanced extraction
is achieved.
Hence the phenomenon in which two reagents, when used together, extract
a metal ion with enhanced efficiency compared to their individual action is
known as synergism.
Applications Of Solvent
Extraction
 Solvent Extraction of Metal ions
by Chelation
• Formation of chelate molecule with an organic chelating agent.
• Many of these reagents are weak acids that ionize in water.
• The ionizable proton is displaced by the metal ion when the chelate is
formed and the charge in the organic compound neutralizes the charge in
the metal ion.
• Ex. Diphenyl thio carbazone (Dithizone) which forms a chelate with lead
ion
Conclusion on Extraction of Metal Chelates
Extraction by solvation
 Extraction by solvation
Solute molecules are associated with the solvent molecules this
is known as solvation. In extraction by solvation, solvent
molecules are directly involved in formation of the ion
association complex.

In case of extraction by solvation the extracted species is solvated

with a definite number of solvent molecules.

Using this process it is possible to extract Uranium, Plutonium or

Thorium from acid solutions. One solvent used for this purpose
is the organophosphate tri-n-butyl phosphate.
Distribution ratio can be calculated by:
Extraction by Ion pair
formation
Extraction by Ion pair formation
The extraction will proceed with formation of a neutral
uncharged species which in turn is extracted into
organic phase.
Most of the high molecular weight amines or so called
liquid ion exchanger comes under this group. The
mechanism of extraction by ion pair formation can be
described as follows:

The control of temperature and activity is most important in

accomplishing quantitative separations. In ion pair extraction the
metal may be incorporated with by co-ordination in either the cation
or anion of the extractable ion pair.