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SOLVENT EXTRACTION
Solvent extraction is defined as the extraction or isolation of a desired
component or substance by extracting it with the help of a solvent having
maximum affinity (solubility) from the other immiscible liquid. For example,
if we have a mixture of resorcinol and benzoic acid, both are soluble in ether
one possibility is to add NaHCO3 in it, it will give sodium salts of both the
compounds

These both give sodium salts and these salts are soluble in HCl, so it is
a problem and hence need to separate them by solvent extraction with either
and water.
PARTITION COEFFICENT OR DISTRIBUTION LAW:
When a substance is dissolved in two immiscible solvents there is a
definite ratio of the concentration of that substance in one solvent to the
concentration of the substance in the second solvent, at a definite temperature
or mathematically Kd i.e. Distribution coefficient or partition coefficient is
equal to C1/C2.
Kd or KD = C1/C2
Kd = Distribution constant
D = Distribution Ratio
This law is called distribution law or partition law and the constant is
called distribution or partition constant or coefficient. The major factors which
affects the distribution law
1 Temperature effect
2 Solvent effect
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Temperature effect:
Temperature effect is the way that by the increase of temperature it
increases the solubility of both the solvents and their ratio change. So
the value of Kd change.
Solvation effect:
Solvation effect change the value of Kd.
Polymerization (Dimer):
When we add solute in solvent it changes by various reactions, for
example by dimerization as benzoic acid in benzene, benzoic acid form dimer
in benzene

Kd is generally taken for aqueous solution. One solvent is organic

Kd =C1/C2 is the ratio for the very simple reaction if there is no side
effect. But there are some side effects for example if the solvents are benzene
and H2O and we add benzoic acid in this then the side effect are that in water
benzoic acid ionizes and in benzene dimers are formed so we require some
other way to avoid these side effects for this we have a distribution ratio D.
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If there is no side reaction in the solvent then

D = Kd = C1/C2 = Vo/Va
Vo = Volume of organic phase
Va = Volume of aqueous phase
One organic and one aqueous solvent is taken due to its immiscibility.
Sometimes the volume of aqueous phase is above and organic phase is below
and in some case the organic phase is above and aqueous phase is below. But
in formula Vo is always above and Va is always below.
The difference in Kd and D is that in case of D the concentration of all
types of species in organic phase divided by concentration of all types of
species in aqueous phase. Concentration expressed on either in
volume/volume or in milli moles/milli moles. If it is volume by volumeit is
denoted by Dc and if it is in the form of millimoles it is denoted by Dm.
Units of Extraction:
The extraction is always expressed in terms of %age
% Extraction = 100[1 – 1/1(Dm+1)n] For millimoles
% Extraction = 100Dc/[Dc + (Va/Vo)]n For Volume by Volume
n = is the number of extractions
If Vo = Va then
%E = 100 Dc/[Dc + (1)n
METHODS OF EXTRACTIONS:
Suppose there is 20 ml aqueous solution containing X millimoles of
solute, extraction is with 20 ml of organic phase.
There are two methods of extraction
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1 One method is that these equal amounts are shaken together

and then separate. The other method is that in which solvent is divided into four
parts then it is shaken in four installments with the other solvent having solute
dissolved in it. In other words the “%age extraction depends upon the number of
extractions, larger is the number of extraction more will be the %age of extraction
provided the time and temperature of the extractions must be the same.
NATURE OR TYPES OF EXTRACTION:
There are methods of extraction
1 Single short or Batch Method
2 Continuous Method
3 Multiple Extractions or Crag’s Method
Batch Method:
It is an ordinary simple method usually used in labs. In this method the
amount of the aqueous phase containing the specie is taken in a
separating funnel to it added the whole amount or total volume of the
extracting solvent then both are shaken profusely and after giving them
rest the two immiscible layers are physically distinct from their organic
layer or organic phase whether it form the upper or lower layer is
separated from the aqueous layer is by draining from the separating
funnel. The amount of the specie is recovered by evaporating the
solvent, the sample or specie is weighed and calculated by usual
measurement is done by using conventional / analytical method.
Apparatus: Common glass separating funnel, it is Squibed pear shape
funnel or Squibed funnel.
Continuous Method:
In continuous flow method the amount of the desired component is
extracted with the help of extracting solvent in a way that it is added
continuously as fresh installments in repeated or continuous manner.

Multiple Extractions, Counter current or Crag’s Method:

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This method is used industrially or on big scale, it can’t be used in lab.

By this method 99.9% extraction can be done. “In Crag’s method is
consisted a unit contain desired number of Crag’s tube in which the
fresh amounts of extracting solvent is added and the desired component
is extracted in this process the material is transferred from tube to tube
and in each tube the un-extracted material is shaken mechanically with
extracting solvent and ultimately on reaching the 99th tube the total
component is almost extracted by the extracting solvent.
Applications:
1 It is mostly used for the solvent extraction of rare earths and the
metal ion present in minute amounts.
2 It is used as ion association complex technique. In ion association
complex method the desired metal ion is incorporated in some bulky molecules and
it is then associated with some other ion to form in pair. The behavior of ion pair or
that molecule is organic like e.g. tetra phenyl Arsonium molecule (C 6H5)4As+. It
make ion pair with Magnate ion MnO4 as (C6H5)4As+MnO4-.
3 The most important application of extraction is the extraction of
metals by chelation, e.g. formation of 8-hydroxy qunolinate complex of metals. It
mostly reacts with divalent trivalent and tetra valent. They are pH dependent second
example is of EDTA.
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% Extrtaction:
Assume the extraction of a chemical specie from water to an organic
solvent. Then the % extraction of specie ‘c’ extracted into the organic
phase is

dividing the right hand side of the equation by Vo [c]w.

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For the amount remaining in water after extractions in n number of

extractions is

Vw & Vo = Volume of water & volume of solvent

W = Amount of solute remaining
Wa = Initial amount of solute in H2O
Example:
One gm of solute is contained in 100 ml of an aqueous solution. Calculate
the amount remaining in the aqueous phase after
(a) A single extraction with 90 ml of an organic solvent.
(b) A single extraction with 30 ml of an organic solvent.
(c) Three extractions with 30 ml of an organic solvent.
D = 10
(a) Batch Extraction
n = 1
Wa = 1 gm
Vw = 100 ml
Vo = 90 ml
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(b) Batch Method

n = 1
Vw 100 ml
Vo 30 ml
Wa 1 gm
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(c) Multiple Method:

n = 3
Vw = 100 ml
Vo = 30 ml
Wa = 1 gm
D = 10

As ‘C’ is a multiple method lets solve it stepwise.

Ist Step:
n = 1
Vw = 100 ml
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Vo = 30 ml
Wa = 1 gm
D = 10

Now for sec step Wa2 will be Wa2 = W1 = 0.25 gm

n = 1
Vw = 100 ml
Vo = 30 ml
D = 10
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For third step Wa3 = W2 = 0.0625 gm

n = 1
Vw = 100 ml
Vo = 30 ml
D = 10
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Numerical:
20 ml of an aqueous solution of 0.1 M Buteric acid is shaken with 10 ml of ether.
After the layers are separated. It is determined by titration that 0.5 millimoles of
buteric acid remain in aqueous layer . What is the distribution ratio and %
extraction.
20 ml contain buteric acid = 0.1 M
For millimoles it is multiplied by volume
Total concentration = 20 × 0.1 = 2.0 millimoles
Millimoles of buteric acid in ether = [2.0 – 0.5]/10
= 1.5/10 = 0.15 millimoles
(Where 10 is the volume of ether in ml)
Millimoles of buteric acid in aqueous layer = 0.5/20 = 0.025 millimoles
(Where 20 is the volume of aqueous layer)
D = 0.15/0.025 = 6
%E = 100 D / [D + Va / Vo]
%E = 100 × 6/[6 + 20/10]
E = [100 × 6] / 8
= 75 %