Unit 3 Solvent Extraction Techniques

UNIT 3

SOLVENT EXTRACTION
TECHNIQUE

Structure
3.1 Introduction 3.5 Mechanism of Extraction:
Extraction by Solvation and
Expected Learning Outcomes
Chelation
3.2 Principle
3.6 Summary
3.3 Classification
3.7 Terminal Questions
3.4 Efficiency of Solvent
3.8 Answers
Extraction Technique

3.1 INTRODUCTION
As you know that in this course, you will be studying a variety of analytical
methods. And, the substance to be analysed may be a mixture or an impure
substance. Hence, the separation of a mixture into its pure components or the
separation of a pure substance from an impure one is also an important part of
the process of analysis.

Solvent extraction technique is one such method of separation. And as you

progress to know more about it during the study, you will realise that this
technique is very convenient, simple and quick to use. In analytical chemistry,
this technique can be used for purposes of preparation, purification,
enrichment, separation in all scales of working from microanalysis to large
scale production.

In this unit, we will begin our discussion with the general principle of this
technique and then the classification of different types of solvent extraction
techniques. The efficiency of solvent extraction will also be explained. Finally,
the mechanism of extraction, i.e. extraction by solvation and chelation will be
elaborated.

The applications of solvent extraction will be dealt in the next unit, i.e. Unit 4. 49
Block 1 Qualitative and Quantitative Aspects of Analysis

Expected Learning Outcomes

After studying this unit, you should be able to:

 explain the term extraction;

 list various types of extractions;

 describe liquid-liquid extraction and its importance;

 discuss the principle of liquid-liquid extraction;

 explain the efficiency of extraction technique;

 differentiate between distribution coefficient and distribution ratio and

discuss the mechanism of extraction, i.e. extraction by solvation and
chelation.

3.2 PRINCIPLE
Any substance whether organic or inorganic, can be separated using the
extraction technique because it distributes or partitions itself between two
immiscible phases differently. Thus, when a substance S, present in phase 1,
generally aqueous, is brought in equilibrium with phase 2, the organic phase, it
Nernst (1891) defined
distributes itself between the two phases, i.e.
the partition isotherm,
“A solute will S (phase 1) S (phase 2)
distribute itself
Such a distribution is governed by the distribution law, about which you have
between two
already studied in the Unit 3 on phase equilibrium in the earlier course,
essentially immiscible
BCHCT-135.
solvents in such a
way that the ratio of You also know that for such equilibrium, at any given temperature, the ratio of
the concentration of activities or concentrations of solute S in the two phases is constant. This is
the solute in the two shown below:
phases, after
equilibration has been [S]phase 2 [as ]phase 2
  constant  K eq  KD … (3.1)
achieved, at a [S]phase 1 [as ]phase 1
particular
temperature, is The equilibrium constant is called the distribution coefficient, KD or partition
constant, provided coefficient.
the solute has the
It is the distribution coefficient, whose value decides the mobility of substance
same molecular
S from phase 1 to phase 2. If the value of KD is sufficiently large, only then
weight in each
such a complete mobility or transfer of substance to phase 2 will take place.
phase”.
However, if this value is small, then the substance will remain in phase 1 only.

Also, when we are considering the distribution coefficient here, we are

assuming that the substance S is present in both the phases in one form only,
i.e., it is neither ionising (nor dissociating) nor associating in either of the
phases. We will keep the discussion simple here and take such a situation
later at appropriate place. So till then, keep this factor also in your mind.

It is also important to know that the ratio of distribution of a substance, S, in

50 two phases (i.e. KD) does not depend on the total quantity of S.
Unit 3 Solvent Extraction Techniques

After understanding about the distribution coefficient, let us now study about
the classification of extraction technique.

3.3 CLASSIFICATION
Before taking up the classification of solvent extraction, let us first understand
the term extraction. When the substance to be purified or isolated is present in Liquid-liquid
one phase, and a second phase is use to obtain it, then we say that it has extraction is used in
been extracted into the second phase. many analytical
separations and this
As two phases are involved in the extraction, depending upon their physical procedure was used
states, various types of extractions are possible. from earliest times in
technology for the
The physical state of the phase in which the sample or substance to be
preparation of
extracted is present is written first and then the physical state of phase used
essential oils, drugs,
for extraction is written to denote a particular type of extraction. A hyphen is
dye stuffs and
used in between the two phases in this representation. For example, if we
perfumes.
extract a substance initially present in the solid phase by using a liquid
phase, then we represent it as solid-liquid extraction.

The most familiar type of extraction to you may be liquid-liquid extraction

wherein the substance to be separated or extracted is present in the liquid
phase and it is extracted by using a second liquid phase.

The extraction of a substance in a laboratory using a separatory funnel is the

most familiar and commonly used form of liquid-liquid extraction. In this
technique, a solute present in phase 1 (say water) is extracted by using the
phase 2 (an organic liquid say ether or ethyl acetate).Please note here that the
two phases are immiscible with each other.

This is shown below in Fig. 3.1. For performing this extraction, the two liquid
phases are taken in the separatory funnel and are vigorously shaken. The
vigorous shaking increases the surface area between the phases allowing
their increased interaction. Then, the contents of the separatory funnel are
allowed to rest for sometime so that the two phases get separated.

Phase 2
Phase 1

a) b)
Fig. 3.1: Liquid-liquid extraction using a separatory funnel:
a) A separatory funnel and b) Separation of two phases 51
Block 1 Qualitative and Quantitative Aspects of Analysis

Can you now guess which phase will be at bottom? Yes, the denser phase will
be at the bottom in the separatory funnel. Then, by opening the stop cock, the
two phases can be separated one by one in different containers.

A solute present in an aqueous solution is extracted in the second phase

which is generally organic liquid. Thus, the solute has been extracted from the
aqueous phase using a solvent. Hence, such an extraction is also called
solvent extraction.

But has all of the substance has got extracted into the organic phase or phase
2? We will find the answer to this question in the forth coming sections.

Let us now understand the efficiency of the solvent extraction technique.

SAQ 1
In the following types of extractions, identify the phase from which the
substance to be extracted is present:
(i) Liquid-Solid (ii) Solid- Liquid (iii) Liquid- Liquid

3.4 EFFICIENCY OF SOLVENT EXTRACTION

TECHNIQUE
The distribution of a species in two phases is not governed by a simple
equilibrium as discussed in the previous section. In fact, while evaluating the
efficiency of the solvent extraction, we have to consider thetotal
concentration of the substance in each of the phases.

Thus, we need to use another term distribution ratio, D. The distribution ratio
is shown below in Eq. 3.2;

[Sphase 2 ]total
D … (3.2)
[Sphase 1]total

If phase 2 is an organic solvent and phase 1 is aqueous medium, then for

such a system, wecan write the distribution ratio, Das shown below:

Total conc. of S in organic phase

D … (3.3)
Total conc. of S in aqueous phase

For simple systems about which we discussed in the previous section, the
distribution ratio and the distribution coefficient are identical.

But for some more complex systems in which the solute or the substance
exists in more than one form in any one of the phases, the distribution ratio
and the distribution coefficient are not the same.

We can understand this with the example of the distribution of a weak acid
between water and an organic solvent. Weak acids partially ionise in aqueous
phase and hence, for a weak acid, HA, we can write the following ionisation in
the aqueous medium:
+ -
52 HA H + A
Unit 3 Solvent Extraction Techniques

Thus, the concentration of HA in aqueous phase is taken to be the

concentration of all the species of the substance HA, i.e. the concentration of
undissociated form of HA, i.e. [HA]aq and the concentration of conjugate base
or anion of HA, i.e., A-, represented as [A-]aq.

Then, according to Eq. 3.3, we can write

Total conc. of S in organic phase

D
Total conc. of S in aqueous phase

[HA]org
D … (3.4)
[HA]aq  [A - ]aq

Looking at Eq. 3.4, you can now appreciate that in such situations, distribution
ratio, D is different from the distribution coefficient, KD given by Eq. 3.1.

Remember that the distribution coefficient is equilibrium constant and its value
is constant for the distribution of a solute between two phases at a constant
temperature. However, the value of distribution ratio depends upon the
concentrations of different forms of the species present in the two phases.

The distribution ratio, as explained above is just a ratio of concentrations and

does not depend on the volume ratio of the phases. However, the fraction of
the substance extracted or the extent of extraction depends on the volume
ratios of the two phases used in the extraction.

We will illustrate the efficiency of the extraction by calculating the fraction of

the substance transferred from phase 1 to phase 2 is the next unit, i.e. Unit 4
in its Sec. 4.3 on Qualitative and Quantitative aspects of Solvent Extraction.

SAQ 2
Which one of the two is larger for a given system involving ionisation of the
substance to be extracted in the aqueous phase-distribution constant or
distribution ratio?

We will now discuss the mechanism of extraction. But before proceeding to

study of mechanism, answer the following SAQ.

3.5 MECHANISM OF EXTRACTION: EXTRACTION

BY SOLVATION AND CHELATION
It is important to understand here that the general aspects of solvent extraction
discussed so far are equally valid for inorganic and organic compounds.
Solvent extraction is a much cleaner way of separating inorganic species as
compared to the precipitation methods which involve precipitation followed by
filtration and washing of the precipitate.

The use of solvent extraction involves the concept of ‘like dissolves like’. Thus,
a substance, whether organic or inorganic, will move to the organic phase
when its solubility is higher in the organic phase as compared to the aqueous
phase (or medium). 53
Block 1 Qualitative and Quantitative Aspects of Analysis

The uncharged organic molecules will tend to dissolve in the organic phase
while the anions arising from their ionisation will be charge species and would
remain in the polar aqueous phase.

The inorganic species such as metal ions, would like to remain in the aqueous
phase as these are charged species. To make them extracted to the organic
phase, their charge has to be neutralised so that these behave like the organic
species. Two of such approaches are as follows:

(i) Extraction by solvation and

Cyanex 923 is a liquid(ii) Extraction by chelation
phosphine oxide usedLet us first understand extraction by solvation and then will discuss extraction
by chelation.
as a solvent (i) Extraction by Solvation
extraction reagent. It Neutral inorganic molecules or complexes can be solvated using
is particularly effective electron donor extractants. The solvation increases their solubility in
the organic phase. Such electron donor reagents are of the following

in the separation and two types:

(a) Reagents containing oxygen linked to carbon, e.g., ethers, esters,
purification of various alcohols and ketones.
metal ions from (b) Reagents in which oxygen or sulphur is linked to phosphorous, e.g.
alkylphosphates or alkyl thiophosphates.
aqueous solutions. Some examples of such reagents which are extensively used are as follows:
For example, it can be Trialkylphosphate Dialkyl alkylphosphonate
used to remove OR OR
cadmium impurities RO  P = O RO  P = O

from phosphoric acid OR OR

or to recover metals Example: Tri-n-butyl phosphate

(TBP)
Example: Dibutyl butylphosphonate
(TBBP)

like chromium through Alkyl dialkylphosphinate Trialkylphosphine oxide

liquid-liquid extraction OR
R

RP=O
processe RP=O
R
R
Example: Butyl dibutyl phosphinate Example: Tri-n-octylphosphine oxide
(TOPO)

Note that the first three of the above compounds are esters while the last
compound is a phosphine derivative. In the last century, another very useful
extractant, cyanex 923 was introduced which was a mixture of four
54 trialkylkylphosphine oxides.
Unit 3 Solvent Extraction Techniques

Similar to the above reagents containing P=O, reagents with P=S are also
possible. These are esters of alkylthiophosphoric, alkylthiophoshonic,
alkylthiophosphinic esters and triakylphoshphine sulphides.

You can yourself try writing their structures as given in SAQ below:

Some examples of these reagents are namely cyanamid reagent,

triisobutylphoshinesulphide (TIBPS) and cyanex 471 X.

SAQ 3
Write the general structures of following classes of compounds:

(i) Alkylthiophosphoric ester

(ii) Alkylthiophosphonic ester

(iii) Alkylthiophosphinic ester

(iv) Trialkylphosphine sulphide

Since these oxygenated solvents and organophosphorous esters solvate the

proton and the neural inorganic species, they can be used for the extraction of
the acids and salts. Some such compounds along with their extractants are as
follows:

 Ce(NO3)4 . (ether)2

 HNO3. TBP

 VO2 (NO3). TBP

 H+(TBP)4.ReO-4

(ii) Extraction of Chelation

Extractions by chelation or using chelating agents are a part of the broad

category of extraction by compound formation.

Many chelating agents are weak acids which can ionise in water. They react
with the metal ions to give the chelates which are uncharged complexes.
These are nearly insoluble in water but are highly soluble in organic solvents,
i.e. ethers, hydrocarbons, ketones, chloroform and carbon tetrachloride.

Many chelating agents are having a limited solubility in water or they may get
hydrolysed or may be oxidised by air in their aqueous solutions. Hence,
instead of adding them to the aqueous phase, these chelating agents are
added to the organic phase. The chelates formed are then extracted to the
organic phase.

You can see Fig. 3.1 for these equilibria.

55
Block 1 Qualitative and Quantitative Aspects of Analysis
MLn HL
Organic K D,HL
Aqueous
HL
+
KD, c
H2O

Ka

MLn n+ -
M + n L n
+
+
H3O

Fig. 3.1: Liquid-liquid extraction of metal ion using a chelating agent

In the aqueous phase, the chelating agent complexes with metal ion to form a
stable metal-ligand complex which is then extracted into the organic phase.

The distribution ratio is given as follows:

[Conc. of metal chelate in organic phase] … (3.5)

D
[Conc. of metal ion in aqueous phase
K

[ML n ]org [HL]norg

 
[Mn  ]aq [Hn  ]aq
n

Here, K is a constant containing many terms involved in the equilibria shown in

Fig. 3.1.

Normally, the extractions are carried out using a large excess of the chelating
agent (HL) so that its concentration remains essentially constant during the
extraction.

Some examples of chelating agents are β-diketones, dithizone,

8-hydroxyquinoline,monoximes,dithiocarbamates and hydroxamic acids.

Some other commercial acidic chelating agents are LI X 63,LIX 64 N,

LIX65 N, SME 529, P-5000series ,(hydroxyoxime S), Kelex 100 and Hostarex
DK16 ,LIX 54 ,X 151 (β-diketones).

Extractions with Diphenylthiocarbazone: Diphenylthiocarbazone, or

dithizone, is a useful reagent for separating minute quantities of a dozen or
more metal ions. Its reaction with a divalent cation, such as Pb2+, resulting
formation of a chelate can be written as shown below:

N=N
2+
2 C=S + Pb
+2 H+
HN  HN

Dithizone (green)

56
Unit 3 Solvent Extraction Techniques

Both dithizone and its metal chelates are essentially insoluble in water but
dissolve readily in solvents such as carbon tetrachloride and chloroform.
Solution of the dithizone reagent is deep green, whereas solutions of the metal If a metal M, present
chelates are intensely red, violet, orange, or yellow and provide a sensitive as various species
means for the photometric determination of the separated ions. M1, M2 M3 …., is
partitioned between
The distribution ratio of the various metal dithiionates is described by Eq. 3.5.
an organic and an
Thus, for lead,
aqueous phases,
coca

K
D

r
g

o
[PbDz 2 ] r
g
2
c Dz
then the distribution
   … (3.6)
q

ratio or extraction
a
q

a
q
2  2
[Pb ] [H3 O ]
coefficient, E can be
defined as
From Eq. 3.6, you can see that the distribution ratio, D depends upon the pH
of the aqueous phase. Total metal conc.in
all forms in organic phase
E
Total metal conc.in
Thus, the pH can be changed or adjusted in a useful way to extract or all forms in aqueous phase
separate the metal ions if the equilibrium constants of the metal ions under
consideration are sufficient different. Thus, the selectivity can be achieved by If polynuclear species
controlling the pH. are formed, their
concentrations are
You can see such a selective extraction of metal ions in Fig. 3.2. It shows how multiplied by
the percentages of different metal ions, extracted into a chloroform solution of appropriate
dithizone, change with the pH of the aqueous medium. stoichiometric
coefficients.
100
Cu(II) Sn(II) Pb(II) Cd(II)
80
% extracted

60

40

20

-1 0 1 2 3 4 5 6 7 8 9 10 11 12
pH

Fig. 3.2: Extraction of different metal ions with change in pH of the aqueous
medium.

You will study more about the extraction of metal ions from aqueous solution
to the organic phase using different chelating agents in Sec. 4.4 of Unit 4.

3.6 SUMMARY
In this unit, you have learnt the following main points:

 Various types of extractions can be classified as solid-liquid, liquid-solid,

liquid-liquid and gas-liquid extractions.

 Solvent extraction, i.e. liquid-liquid extraction is very commonly used in the

laboratories for purification of organic compounds. It is also an important
technique in industries.

 The liquid-liquid extractions involve partitioning of a substance in two

phases which are immiscible with each other. 57
Block 1 Qualitative and Quantitative Aspects of Analysis

 For the mobility of any substance from the aqueous phase to the organic
phase, its distribution coefficient should be sufficiently large in favour of the
organic phase.

 The efficiency of the extraction also takes into account the distribution of
the substance.

 Extraction by solvation and by chelation are two important mechanisms of

extraction.

 Extraction by solvation can be performed using ethers, esters, alcohols

and ketones which are oxygen containing electron donor extractors. The
other reagents used contain oxygen and sulphur linked to phosphorous
and these are compounds of the type alkylphosphateesters or
alkylthiophosphate esters.

 Extraction of metal ions using chelating agents such as β-diketones,

dithizone and 8-hydroxyquinoline is useful in metal ion separations and it
is it is dependent on the pH of the aqueous phase.

3.7 TERMINAL QUESTIONS

1. What is the principle of liquid-liquid extraction?

2. Explain the process of solvent extraction used in laboratories to purify

organic compounds.

3. Differentiate between the terms-distribution coefficient and distribution

ratio.

4. For which type of systems, the distribution coefficient and distribution ratio
are same?

5. Write the structures of the following:

(i) TBP

(ii) TBBP

(iii) TIBPS

3.8 ANSWERS
Self Assessment Questions

1. (i) Liquid (ii) Solid (iii) Liquid

2. Distribution coefficient, Refer to Eq. 3.4.

OR
3. (i): Alkylthiophosphoric ester  RO  P = S

58 OR
Unit 3 Solvent Extraction Techniques
OR
(ii): Alkylthiophosphonic ester  RO  P = S

R
OR
(iii): Alkylthiophoshinic ester  RP=S

R
(iv): Phosphine sulphide  RP=S

R
Terminal Questions
1. If any substance (solute) is soluble in two immiscible solvents, then it will
distribute or partition itself between the two phases (solvents) in a definite
proportion. In certain cases, a solute dissolved in one phase i.e. aqueous
phase is more or less completely transferred to the second phase which is
often an organic liquid such as chloroform, carbon tetrachloride or
benzene etc.

2. Ref. to Fig. 3.1 and the explanation given in Sec. 3.2.

3. Distribution coefficient is equilibrium constant and it does not depend

upon the quantity of the substance to be extracted.

Distribution ratio is ratio of total concentrations of the substance in the two

phases at a particular temperature.

4. For systems which are simple, i.e. in which the substance to be separated
exists in one form only and it does not associate or dissociate in any of
the phases.
OCH 2CH 2CH 2CH 3

5. (i) TBP  CH 3CH 2CH 2CH 2O  P = O

OCH 2CH 2CH 2CH 3

OCH 2CH 2CH 2CH 3

(ii) TBBP  CH 3CH 2CH 2CH 2O  P = O

CH 2CH 2CH 2CH 3

H3C CH 3
CH
(iii) TIBPS 
CH 2
H3C
CH  CH 2  P = S
H3C
CH 2

CH
H3C CH 3

59