Discipline Specific Elective DSE 1 CHD 101

Basic Topics in Analytical Chemistry 3+1=4 Credit

Unit 5. Solvent Extraction (4 hours)

 Solvent extraction or liquid-liquid extraction is a process based on the distribution of

a solute between two immiscible liquid phases.
 In this technique a solution is brought into contact with a second solvent essentially
immiscible with the first solution. So as to bring about the transfer of one or more
solutes into the second or the extracting solvent.
 This method is simple, convenient and easy to perform.
 This technique is applicable for trace as well as large amount of materials. Separation
of inorganic as well as organic substance is possible.

Basic Principle.

The distribution or the partition of a solute between two immiscible solvents is governed by
the Nernst’s Distribution Law.

According to this law, a solute ‘A’ will distribute itself between two immiscible liquids in
such a way that the ratio of concentrations at equilibrium is constant at a particular
temperature and for a given two phase system of liquids; ‘K’ is constant for a solute.

K = Partition coefficient or Distribution coefficient.

C1 = Concentration of solute in solvent 1.

C2 = Concentration of solute in solvent 2.

Nernst’s Distribution Law is valid only if the solute exists in the same molecular state in both
solvents.

In many cases, the solute may undergo dissociation or association in one or both solvents.

Instead of using partition coefficient or distribution coefficient. Distribution Ratio ‘D’ is

used. (‘D’ is used instead of ‘K’)

For example; Benzoic acid is slightly dissociated in water but is associated into a dimer in
benzene.

1. Dissociation in Water.

C6H5COOH C6H5COO- + H+
 2. Association in Benzene

2C6H5COOH (C6H5COOH)2

Consider a solute ‘A’

D = Distribution Ratio.

Distribution ratio is the ratio of the concentration of all the species (or forms) of the solute in
each phase.

The ratio ‘D’ is:

1) Dimensionless or has no units.

2) At a given temperature, for a solute and a given pair of solvents. ‘D’ is constant
independent of the total amount of the solute.
3) D and K are related to each other. When the value of K and D is large, the solute will
tend towards quantitative distribution in Solvent 1.

In solvent extraction most often a solute is extracted from an aqueous solution into an
immiscible organic solvent.

Selection of Solvent:

1) An organic liquid used for solvent extraction must be a good solvent for the solute to
be extracted (i.e. ‘K’ and ‘D’ value must be in favour of the solvent).
2) After being shaken with an aqueous solution, the organic liquid must quickly settle
out as a separate layer. For this, the specific gravity or density should be substantially
greater or considerably lesser than 1.

Efficiency of Extraction

When a solute is to be extracted from an aqueous solution using an organic solvent, the
efficiency of the extraction is greater when

(i) Distribution ratio ‘D’ or the distribution coefficient ‘K’ is in favour of the organic
solvent or greater than unity. So that the concentration in organic layer is
appreciably greater than that in the aqueous layer at equilibrium.
(ii) Extractions are carried out with small volumes of a given quantity of solvent
several times rather than carrying out a single extraction with the entire amount of
solvent.
Mathematical derivation for ‘n’ (Number of extractions)

Let ‘V’dm3 of the aqueous solution contain ‘W’g of solute and let ‘V0’dm3 of the
organic solvent be used for the extraction everytime.
Let ‘W1’g be the weight of the solute unextracted at the end of the first
extraction (left in the aqueous layer).
The expression for W1 can be obtained as follows:
The Distribution Ratio is defined as

( )

( )

( ) ----------------------- (1)

If the extraction is continued with the remaining solute namely ‘W1’g in ‘V’dm3
of aqueous layer and with the same volume of organic solvent i.e. ‘V 0’ for a
second time and the amount of solute unextracted is now ‘W2 ’g.

( ) ---------------------- (2)
Substituting equation (1) in equation (2)
( )( )

( ) ----------------------- (3)
In general for ‘n’ number of extractions with ‘V0’dm3 organic solvent each time the amount
‘Wn’ remaining unextracted will be given by the relation.

( ) -------------------- (4)

‘Wn’ represents the amount of solute in grams unextracted after ‘n’ extractions. Thus lesser is
‘Wn’ greater is the efficiency of the extraction.

Comparison between single extraction and ‘n’ number of extractions

For a single extraction using the entire volume of organic solvent i.e. nV 0.

Let the amount of solute left unextracted in aqueous layer be ‘W´n’.

‘W’ be the actual weight of the solute taken in aqueous phase for extraction.

( )

( )

( ) ----------------------- (5)

From equation (4) for ‘n’ number of extractions the weight of the solute left unextracted is
given by

( ) -------------------- (4)

Dividing the terms inside the bracket by ‘V’ we get

( )

Let

( )

( )
------------------------------- (6)
Similarly for equation (5)

( )

( )

Let

( )

------------------------- (7)
( )

( ) ( )

Hence from the given relations it is clear that multistep extraction using several small
portions of a given organic solvent is more efficient than a single extraction with a large
volume of the organic solvent.

Expression for Percentage Extraction

The expression for a single extraction with ‘W1 ’g of solute left in the aqueous layer is given
by

( )

V = Volume of aqueous solvent

V0 = Volume of organic solvent

W = Total weight of solute taken in aqueous layer.

The amount extracted (W-W1) will correspond to

( )

( )

The fraction will correspond to ‘x’

Now dividing the R.H.S by V0 we get

Percentage Extraction

‘E’ or percentage extraction depends both on the distribution ratio as well as on the
volume ratio of the two phases.

In general for ‘n’ extractions, the fraction ‘x’ that is extracted is given by the expression

( )

* ( ) +
Complexing Agents in Solvent Extraction

‘Like dissolves like’. Organic solvents dissolve organic solutes or in other words covalent
solvents dissolve covalent solutes more readily than inorganic solutes. Similarly inorganic
solute dissolves more readily in water than in organic solvents.

Inorganic salts in aqueous medium mainly consist of ions.

In the extraction of metal ions from the aqueous solution using an organic solvent, it is
necessary to decrease the solubility of metal ions in water and increase it in organic solvent.
If the migration of the metal ions from aqueous solution to organic extractant is desired in
large quantity.

The larger solubility of metal ions in water is due to the association of water molecules with
the charged metal ions (Hydration). The stability of hydrated metal ions is due to the
liberation energy of hydration. If the charge on the metal ion is neutralized by one way or the
other, solubility of metal ions in water can be reduced substantially and its solubility in
organic solvent gets increased automatically.

Extraction of metals by Chelation

The charge on the metal ions can be neutralized using an appropriate complexing or chelating
agent which converts the metal ions into neutral metal complexes. Larger the size of the
complex and more hydrophobic it is in nature, more efficient will be its extraction in organic
solvent.

Example: The reagent 8-hydroxyquinoline (oxime) forms neutral, water insoluble,

Chloroform or Carbontetrachloride soluble complex with metal ions like copper,
aluminium,etc.

Aluminium ions in solution are usually converted into the hydroxyquinolate by the addition
of 8-hydroxyquinoline. The chelate thus formed is extracted by using benzene or Chloroform.
It is possible in this way to extract only aluminium at pH=5.8 in the prsesnce of iron, nickel
and vanadium.
 ( ) ( ) ( ) ( )

HQ = 8-Hydroxyquinoline and subscripts indicate the solvent.

The equilibrium is seen to be dependent on [H+]. Hence the pH control is necessary.

Other complexing agents or masking agents that are often used are dimethyl glyoxime,
acetylacetone, cupferron α-nitroso, ß-naphthol and dithiozone.

 Acetylacetone forms well established chelates with more than sixty metal ions.
 Dimethyl glyoxime is used for the extraction of nickel and palladium.
 Dithiozone can be used for the extraction of Mn, Fe, Co, Ni, Cu, Zn, Pd, Ag, Cd, Pb.

Separation Factor ‘ß’

If a solution contains (two or more solutes) say A and B, it is often observed that when
conditions are such that ‘A’ is extracted, some amount of B is also extracted.

The extent of separation can be found by a quantity called the separation factor ‘ß’

[ ]
[ ]
[ ]
[ ]

 In cases where one of the distribution ratio, say DA is large and DB is small, an almost
complete extraction of A is possible i.e. the separation of A from B is almost
complete.
 In solvent extraction one tries to make ‘ß’ as large as possible by an appropriate
choice of extractant and by adjusting the volume ratio.
 For example, When DA= 10 and DB = 0.1, the separation factor ‘ß’ will be 100. A
single extraction in such a case will remove about 91% A and 9% B.
 The separation effect increases with the magnitude of the separation factor.
Types of Extractions:

1) Batch extraction

2) Continuous extraction

1) Batch Extraction

This is one of the simplest and widely used methods of extraction.

In this method, a given volume of solution is brought into contact with a given volume of
solvent until equilibrium is attained followed by separation of the liquid layers. Whenever
required the procedure is repeated after the addition of fresh solvent.

The batch extraction process gives rapid and simple separations and is used when the
distribution ratio of the solute of interest is large since a few extractions only will be required
to achieve quantitative separations.

The most commonly used apparatus for performing a batch extraction is a separating funnel
since it is simple to add and withdraw the respective phases using the stopcock.

Method: Two immiscible solvents (generally water and an organic liquid), one of which
initially contains the solute (or solutes) are placed in contact with each other in a separating
funnel. The system is vigorously shaken to bring the two layers in contact. The system is then
left undisturbed for some time. The solute distributes itself between the two liquids. The
extent of this distribution depends upon the distribution ratio ‘D’.

2) Continuous Extraction

Continuous extractions are used when the distribution ratio is relatively small and therefore a
large number of batch extractions would be required to achieve quantitative separation.

Method: The principle of the method consists in distilling the extracting solvent from a
reservoir and condensing it and passing it continuously through the solution being extracted.
The apparatus used depends upon whether the extracting solvent is heavier or lighter than the
phase being extracted i.e. for aqueous solutions, whether the solvent is heavier or lighter than
water as shown in Fig 2 and Fig 3.

In Fig 2, the set up consists of an extraction vessel ‘A’ fitted with a reflux condenser (C) and
a solvent reservoir (R) which is heated.

The aqueous solution containing solute to be extracted and the extracting solvent are allowed
to come into contact in the extraction vessel. The solvent level is adjusted at the level of the
solvent return tube. The solvent reservoir is heated. The vapours pass into the extraction
vessel through ‘B’, go up the condenser, condense and the liquid drops pass downward
through the solution in ‘A’. As they move downwards, they carry down a certain amount of
the solute. The level of solvent in ‘A’ rises and the extracting solvent with some amount of
solute now overflows into the solvent reservoir R. This continuous and the solute in the
extracting solvent accumulates in the reservoir.

Figure 3, Shows the set up when the extracting solvent is lighter than water. Here, the
condensed liquid is forced to move downward by means of a bubbler type funnel F. Since the
extracting liquid is lighter than water, it raises through the aqueous solution extracts some
amount of the solute and overflows into the reservoir.
Problems:

1) 0.1dm3 of water containing 0.1g of iodine is shaken with 0.075dm3 of

Carbontetrachloride (CCl4). The distribution coefficient between CCl4 and water at
room temperature is 85. Calculate the weight of iodine remaining unextracted in the
aqueous layer after
(i) one extraction with 0.075dm3 of CCl4
(ii) Three extractions with 0.025dm3 of CCl4
2) The distribution ratio ‘D’ of an organic solvent and water phases for a given solute is
20 in favour of organic solvent. Calculate the percentage extraction for a volume ratio
of
(i) 1 for a single extraction.
(ii) 10 for two successive extractions.
3
3) 200cm of an aqueous solution containing 1.5g of solute ‘A’ is extracted a number of
times with 20cm3 portions of an organic solvent. Distribution ratio in favour of
organic phase is 60. Calculate the number of extractions required to bring the amount
of the solute in aqueous phase 0.03g.
4) Ninety-six percent of a solute is removed from 100mL of an aqueous solution by
extraction with twice 50mL portions of organic solvent. What is the distribution ratio
of the solute in favour of organic solvents?
5) 200cm3 of an aqueous solution containing 100mg of a solute is treated with an
immiscible organic solvent. The distribution ratio D of the solute in favour of organic
solvent is 22. If 15cm3 of organic solvent is to be used at a time. Calculate the
minimum number of extractions required so that no more than 1mg of solute remains
in the aqueous solution.
6) In a certain solvent extraction the distribution ratio of the solvent in favour of the
organic solvent is 25. Calculate the percentage extraction if a single extraction is
carried out using volume ratio
(i) (ii)
7) 200cm3 portion of an aqueous solution containing 0.05mole of a certain solute is
extracted twice with 25cm3 of ether. Calculate
(i) The amount of solute remaining unextracted
(ii) The percentage Extraction (Given D = 12).
8) 0.05dm3 of a 0.25M solution of Fe3+ is to be equilibrated with 0.005dm3 of ether in
each extraction. How many extractions are necessary so as to bring the concentration
of Fe3+ in the aqueous layer 1×10-5M. The distribution ratio of Fe3+ is 17.6 in favour
of ether.