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Prof Derick Carboo

Department of Chemistry
University of Ghana,
Legon
E-mail: dcarboo@ug.edu.gh
dcarboo45@gmail.com


INTRODUCTION
Analytical measurements always seek to measure only one
component at a time, sometimes in presence of other species.
When the other species do not interfere with the measurement
there is no problem. This is however not always the case and the
need arises to either separate the analyte from the interferent , or
the interferent from the analyte of interest
There are various methods to realize this:
1. MASKING: react interfering species with a reagent to render it
inactive
2. PRECIPITATION : React it with reagents that form solid
compound with it, so it can be filtered and removed
3. SEPARATION: Another method is to separate it spatially by, for
example, distillation, extraction, diffusion, sublimation,
adsorption, chromatography etc.


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ANALYTICAL SEPARATION
The goal of an analytical separation is to remove either the
analyte or the interfering species from the sample matrix.
To achieve a separation there must be at least one significant
difference between the chemical or physical properties of the
analyte and interferent.
Separation processes can be generally seen in two groups:
Mechanical separation, e.g. filtration (based on size of
particles), decantation (based on densities of the phases) etc.
Molecular separation in which the separation of molecular
aggregates is based on differences in mass, structure and
charge distribution.
The basis of molecular separation can be spontaneous
equilibrium processes in which the substance to be separated
are distributed in two phases solid liquid, liquid liquid etc.
It can also be irreversible non-equilibrium processes e.g.
diffusion

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SEPARATION EFFICIENCY
Relying on chemical or physical properties for
presents a fundamental problem: A separation
that completely removes an interfering species
may result in the partial loss of analyte. Altering
the separation to minimize the loss of analyte,
however, may leave some of the interferent
behind
A separations efficiency is given by two factors:
The completeness of recovery of the desired
solute i.e. recovery factor
the extent of separation of the solute from other
undesirable substances, i.e. separation factor.


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SEPARATION EFFICIENCY
The analyte recovery factor :
R
A
= Q
A
/(Q
A
)
O


(Q
A
)
O
= Quantity of A in the original sample
Q
A
= quantity of A remaining after the separation

The recovery of the interfering species I is also defined :
R
I
= Q
I
/(Q
I
)
O


(Q
I
)
O
= Quantity of Interferent in the original sample
Q
I
= quantity of Interferent remaining after the separation

A recovery of 1.00 means none of the analyte was lost during the separation.

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REQUIRED RECOVERY FACTOR
Recovery factor can be expressed in percentage.
The values of R
A
required in quantitative analysis
depends on the relative amount of A in sample.
A is major component R
A
> 0.999
A is minor component (0.1 1%) > 0.99
A is trace component ( < 0.01%) R
A
> 0.99
A is trace component (0.001 0.0001%) R
A
> 0.95

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SEPARATION FACTOR
The separation factor S
B/A
defines the extent of separation of
two constituents A and B.
For the solute B (for example) it is given by
Q
B
/Q
A
= S
B/A
.( Q
B
)
O

( Q
A
)
O

S
B/A
= R
B
/R
A



The separation factor depends on the original ratio of B to A
i.e. (Q
B
)
O
/( Q
A
)
O

It also depends on the permissible value of Q
B
/Q
A
which is
determined by extent of interference of B in extraction of A,
and the accuracy desired.


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LIQUID-LIQUID EXTRACTION

The term distribution is understood to mean the partitioning of
substances between two phases. Example I
2
distributes itself
between H
2
O and HCCl
3
(a water immiscible solvent):
I
2(aq)
I
2(org)

This is an equilibrium process in which the substance distributing
itself exists in the same form in both phases. The process can
be treated by the law of mass action.
The most important phase system considered here is liquid
liquid extraction systems of use in inorganic analysis.
This is mainly water/organic solvent systems but there are other
less popular systems such as in the liquid-liquid extraction of
metals in fire assay procedures. Here the ore sample is fused with
mixture of flux, reducing agent and lead oxide, The molten
metals Au, Ag and Pt are extracted by the molten lead from the
slag.

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LIQUID-LIQUID EXTRACTION :PARTITION (DISTRIBUTION)COEFFICIENT


A substance A partitions itself between an aqueous and an
immiscible organic solvent.
A
aq
A
org

If a
aq
and a
org
are the activities of A in the two phases
K
o
D
= a
org
/a
aq

where K
o
D
is activity partition coefficient.
Assumptions:
1) amount of A does not affect the solubility of the
solvents in each other, and
2) A has the same form in both solvents.
At a specific ionic strength of the aqueous phase and
sufficiently low concentration of A in the organic phase
(10
-2
M), K
D
is partition coefficient based on
concentration.
K
D
= [A]
org
/ [A]
aq
(Nernst
Equation)


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LIQUID-LIQUID EXTRACTION

K
D
will be close to K
o
D
at low (0.2 0.3 M)
electrolyte concentration.
Usually the partition coefficient of an unionized (non-
electrolyte) substance varies with the concentration of
an indifferent electrolyte in the water phase.
In general the solubility decreases in the water
with increase in salt concentration. This effect is
utilized in salting-out. In rare cases there can also be
salting-in when the opposite dependence is the case.
The partition law is useful in liquid-liquid extraction
procedures in which a solution (usually aqueous) is
brought into contact with a second immiscible solvent
(usually organic) to bring about a transfer of the one or
more solutes into the second solvent







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Liquid-liquid extraction is a very useful technique for
separating inorganic solutes from aqueous solutions for
analysis.
Because most inorganic solutes have little affinity to
organic solvents, there is need to convert them to
complexes which are capable of being extracted into
organic solvents.
These include neutral metal chelates , ion-association
complexes , coordination complexes, etc.

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EXTRACTION COEFFICIENT
In analytical work the partition law in the form of the Nernst
equation cannot always be applied because in most cases the solute
may have more than one form in each of the solvents.
Processes like solvation, association, complexation, acid-base reactions
etc. may lead to different species.
Example: the extraction of I
2
from acidic iodide solution with CCl
4

provides a good illustration . In the I
2
-H
2
O system, iodine undergoes
hydrolysis in the water and is therefore present as I
2
, I
3
-
, higher
polyiodides, hydrolytic products etc.
In such a case it is useful to define an extraction coefficient, E.
E = E [A]
org
/E[A]
aq

which gives the ratio of the concentrations of ALL the forms of A in the
two phases. E[A] is the stiochiometric or analytical concentration
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In the case of I
2

K
D
= [I
2
]
CCl4
/ [I
2
]
aq
= 89.9
Iodine hydrolyses in water.
2 [I
2
]
CCl4

E = ________________
[I
2
]
aq
+ 3 [I
3
-
]
aq
+ [I
-
]
aq


E can be obtained from K
D
and the

equilibrium constant K
hydro
for the I
2
-
hydrolysis
K
hydro
= [I
3
-
]
aq
[I
-
]
aq
= 0.00130
[I
3
-
]
aq


In practice a suitable oxidizing agent will be used to keep the
concentrations of [I
3
-
]
aq
and [I
-
]
aq
close to zero. The
extraction coefficient may or may not be constant with
respect to concentration of the solute.
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SIMPLE EXTRACTION

Partition coefficients are employed to determine the optimal
conditions for the extraction of one solute from one solvent into
another.

1) When one of the solutes has high K
D
(about 10) and the other
very small K
D
(0.1 0.001), simple extraction can be used to
separate them.
Simple extraction is done in separatory funnel. The extractable
part increases as K
D
increases and also as V
II
increases.

2) When K
D
of the desired substance is low, continuous or
exhaustive extraction can be used. This entails drops of the
organic solvent passing through the aqueous continuously in a
cycle.
Apparatus: two types one for less dense water immiscible and
the other for heavier solvents.



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CALCULATION OF FRACTION REMAINING AFTER n-EXTRACTIONS

K
D
can be used to calculate the amount of solute remaining in the
solution after a number of extractions.

_
n
= [V
II
/(V
I
K
D
+ V
II
) ]
n
C

_
n
= amount in millimoles of substance in V
II
(aqueous phase)
n = number of extraction
K
D
= partition coefficient
C = starting amount of solute in (aqueous) solvent II
V
I
= volume of (organic) solvent I
V
II
= volume of (aqueous) solvent II
_
n
/C = fraction remaining after n extractions
Plotting _
n
/C against n reveals the number of extractions needed for
quantitative removal
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PROBLEMS
1. A solute, B, has a K
D
between water and chloroform of 5.00.
A 50.00-mL sample of a 0.050 M aqueous solution of the solute is
extracted with 15.00 mL of chloroform.
1. Calculate the fraction of B remaining after one extraction.
2. Calculate the fraction remaining after 3 extractions.
3. What volume of chloroform is needed to extract 99.9% of the solute?


2. A solution of OsO
4
in 50ml of H
2
O is to be extracted by CHCl
3
with a
required recovery of 99% of OsO
4
. How may extraction will be needed
with (a) 5mL and (b) 10mL portions of the solvent. K
D
for OsO
4
is 19.1
in CHCl
3
/H
2
O system
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APPLICATION OF SIMPLE EXTRACTION IN INORGANIC SYSTEMS
Types of inorganic extraction systems

1. Systems having simple inorganic molecules in both
organic and aqueous phases.
These substances are non-polar and volatile. The organic
solvent simply dissolves the species, does not react
with it chemically.
The substances prefer the disordered covalent structure of
the organic solvent to the ordered structure of water.
Preferred solvents are non-oxygen containing organic
solvents CHCl
3
, CCl
4
etc.
Examples are I
2
, other halogens, OsO
4
, RuO
4
, AsCl
3
,
GeCl
4
, . SnI
2
, Hg metal

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2. Systems in which uncharged chelate complexes of metals with
organic reagents are extracted into organic phase (Chelation -
Extraction)
Organic ligands such as 8-hydroxyquinoline (oxine), diphenylthiocarbazone
(dithizone), dithiocarbamates, crown ethers, 9,10,phenanthroline etc readily
form neutral chelate complexes with metal ions.
In these complexes the ligands surround (or encapsulate ) the metal ion.
The complex is rendered more lipophilic than hydrophilic and can
therefore be easily extracted into organic phase from water. In some cases
where the coordination requirements of the cation is not fully met by the
ligands, small molecules such as H
2
O or organic solvent may be
incorporated into the chelate system. EDTA, though a very good chelating
agent cannot be used for chelation extraction experiments because its
complexes are not neutral and very soluble in water.
Solvents that are suited for such extraction are non-oxygenated organic
solvents, e.g. CHCl
3
, CH
2
Cl
2
etc.
Extractions involving these chelate complexes are often pH-dependent.
Hence strict pH control allows valuable separations especially in trace
analysis.

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3. Systems in which ION-ASSOCIATION compounds are formed
with organic reagents.
Large anions and cations are poorly solvated due to decreasing
charge density and increasing polarisability. As a result their
salts are ion association compounds (the electrostatic
attraction in ionic compounds is here weak) These compounds
easily precipitate out of water in which they have low
solubility. They may be soluble in organic solvents.
Examples :
Tetraphenlylarsonium perrhenate : [Ph
4
As]
+
[ReO
4
]
-

Cesium tetraphenylborate : Cs
+
[Bph
4
]
-

K
+
and NH
4
+
are also precipitated by tetraphenyl borate anion because the
salts are ion association compounds. For the same reason ClO
4
-
forms
sparingly soluble salt with K and Cs.
Tetraalkylammonium uranyloxinate : [R
4
N]
+
[UO
2
(ox)
3
]
-
etc. Here both
the anion and cation are large, polarisable and poorly solvated.

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4. Systems in which COORDINATION COMPLEXES of
inorganic species with the organic solvent molecules are formed.
In this group the organic solvent molecule coordinates to the inorganic
species. For example many metals form chloroacids in concentrated HCl.
Fe
3+
+ 4Cl
-
[FeCl
4
]
-

The corresponding acid H[FeCl
4
] is readily extracted from water by ether,
ester and ketones such as MIBK (methyl isobutyl ketone) but not CHCl
3
or
CCl
4
etc. This is because these extracting solvents contain basic oxygen
which coordinates strongly to the proton of the chloroacid, thus:



C
O - - -- - --H
+
[FeCl
4
]
-

C


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The ion pair formed has a large cation consisting of the solvated
adduct. This coordinates through the O to the organic solvent
Extractable chloro-complexes are formed by Fe(III), Au(III), Sb(V),
As(III), Ti(III).
Notable cations that cannot be extracted as chlorocomplexes include
Al(III,) Bi(III), Cr(III), Co(II), Fe(II) and Mn(II). In AAS analysis of Au,
a lot of ions (especiallt Fe(III) interfere. One way of solving the problem
is to mask the Fe(III) with either fluoride ions (formation of the soluble
and stable hexafluoroferrate(III) ion) or phosphate and then extraction of
the Au as the AuCl
4
-
.
Another example is the extraction of metals from strong nitric acid
solutions. Tributyl phosphate (TBP) can be used to extract U(VI)
from HNO
3
solution. The bonding ability of TBP rests on the
basicity and steric availability of the phosphoryl group PO.
Kerosine is used to dilute the TBP. The method has economical
application in the reprocessing of spent fuel from nuclear reactors.
Here uranium as UO
2
(NO
3
)
2
is extracted and separated from Pb(II)
and Th(III). Under the same condition Fe(III), Bi(III) also extract.
TBP can also be used to extract Fe(III) from both dilute and
concentrated HCl


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EXAMPLES OF SOLVENT EXTRACTION EQUILIBRIA
A) Partition of a weak acid between water and an immiscible organic solvent
HX is a weak acid such as 8-hydroxyquinoline (oxine), acetylacetone
(acac) etc. Suitable organic solvents include chloroform, ether, MIBK,
ethylacetate etc.
If we make the following assumptions:
The acid is monomeric in both solvents, i.e does not dimerise, react to
form new species etc.
the anion of the acid does not penetrate the organic phase i.e. there is
no dissociation of the acid in organic phase
The following equilibria can be expressed:
For the partitioning of the weak acid between the organic and aqueous
phases,
For the partitioning of the weak acid between the organic and aqueous phases,
[HX]
org

K
D
= --------------- (i)
[HX]
aq


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The extraction coeficient
[HX]
org

E = ------------------ (ii)
[HX]
aq
+ [ X
-
]
aq


and the dissociation of the acid (in water)

[H
3
O
+
]
aq
[ X
-
]
aq

K
a
= ---------------------- (iii)
[HX]
aq



K
a
[HX]
aq

Rearranging (iii) gives : [ X
-
]
aq
=

-------------------
[H
3
O
+
]
aq


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Substitution in (ii)
[HX]
org

E = -------------------------------------------
[HX]
aq
+ (K
a
[HX]
aq
/[H
3
O
+
]
aq
)

[HX]
org

E = ----------------------------------- (iv)
[HX]
aq
( 1 + (K
a
/[H
3
O
+
]
aq
)

From (I) [HX]
org
= K
D
[HX]
aq

K
D

therefore E = ------------------------- (v)
1 + ( K
a
/[H
3
O
+
]
aq
)

This relationship shows the dependence of the extraction coefficient E on
the distribution coefficient K
D
of the weak acid, its ionisation constant
K
a
and the pH of the aqueous phase.

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B) Extraction of a metal as a chelate compound
Chelating agents that can be used to extract metal ions froms aqueous
solutions into organic phase include: 8-hydroxyquinoline,
Diphenyldithiocarbamate (Dithizone), Cupferron etc. but not EDTA
because the EDTA-chelate is not nuetral
Examples of Reactions:
M
n+

aa
+ nHX M(X)
n
+ nH
+

Cu
2+
aq
+ 2HOx

Cu(Ox)
2
+ 2H
+


With HX as the ligand (which is usually a weak organic acid) the
extraction coefficient for the extraction of the metal chelate is given by
E C
Morg

E = --------------- (vi)
EC
Maq


where E C is the total metal concentration in each of the solvents
regardless of the form in which it is.


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Assumptions:
1. the only metal in the organic phase is MX
n
i.e. only the
chelate exists in the organic phase.
Therefore C
Morg
= [MX
n
]
org .


A large excess of HX will
ensure the formation of almost only MX
n


2. Ignore possible lower complexes such as MX, Mx
n-1
, MX
n-2
,
so that
C
Maq
= [M
n+
]
aq
+ [MX
n
]
aq


The extraction coefficient will be given by

[MX
n
]
org

E = -------------------- (vii)
[M
n+
]
aq
+ [MX
n
]
aq



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Since as is usually the case, the partition of the chelate greatly favours the
organic phase, [MX
n
]
aq
is very small and can be neglected

[MX
n
]
org

E = -------------
[M
n+
]
aq

[MX
n
]
org

Now the partition coefficient K
DMXn
of MX
n
is K
DMXn
= -----------
[MX
n
]
aq


and [MX
n
]
org
= K
DMXn
[MX
n
]
aq
.

Therefore,
K
DMXn
[MX
n
]
aq
.
E = ------------------- (viii)
[M
n+
]
aq


Where K
DMXn
is the partition coefficient of the chelate in the two solvents.


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Now the formation constant of the chelate in the aqueous solution (i.e.
the equilibrium constant of the reaction:
M
n+

aq
+ nX
-

aq
(MX
n
)
aq
is given by

[MX
n
]
aq
. [MX
n
]
aq
.
K
f
= ------------------- and [M
n+
]
aq
= -----------
[M
n+
]
aq
x [X
-
]
n
aq
K
f
[X
-
]
n
aq


Since the chelating agent is a weak acid we can write the K
a
for the
reaction: HX + H
2
O H
3
O
+
+ X
-
aq


[H
3
O
+
]
aq
[X
-
]
a q
K
a
[HX]
aq

K
a
= ------------------ or [X
-
]
a q
= ----------------
[HX]
aq
[H
3
O
+
]
aq


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[Mx
n
]
aq
[H
3
O
+
]
n
aq

Therefore [M
n+
]
aq
= ------------------------
K
f
K
a
n
[HX]
n
aq


and [M
n+
]
aq
[H
3
O
+
]
n
aq

--------- = ---------------------
[MX
n
]
aq
K
f
K
a
n
[HX]
n
aq


Substituting this in (viii)

K
DMXn
K
f
K
a
n
[HX]
n
aq

E = ---------------------------------- (ix)
[H
3
O
+
]
n
aq

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EXTRACTION COEFFICIENT

Also from the distribution of the chelating agent itself in the two phases
we recall (I) K
DHX
= [HX]
org
/ [HX]
aq


and use it to replace [HX]
aq
in (ix).

K
DMXn
K
f
K
a
n
[HX]
n
org

E = ---------------------------------- (x)
K
n
DHX
[H
3
O
+
]
n
aq

In (x):
E = extraction coefficient
K
DMXn
= partition coefficient of the chelate MX
n
in the two solvents
K
DHX
= partition coefficient of the chelating agent HX in the two solvents
K
a
= acid dissociation constant of HX in water
K
f
= formation constant (or equilibrium constant) for the complexation reaction
n = Charge on the metal cation
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EXTRACTION CONSTANT

Equation (x) gives the extraction coefficient of the metal in terms of
the constants K
DMXn
, K
n
DHX
, K
f
, and K
a
all of which are properties of
a particular compound at a certain temperature and can be obtained
from literature
the [H
3
O
+
]
aq
and [HX]
org
which are subject to experimental
manipulation.
We can put all these constants together and call it EXTRACTION CONSTANT,
K
ex

K
DMXn
K
f
K
a
n

K
ex
= ---------------------
K
n
DHX


From which E then becomes:
K
ex
[HX]
n
org

E = ------------------
[H
3
O
+
]
n
aq



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EXTRACTION COEFFICIENT
log E = log K
ex
+ nlog [HX]
org
- nlog [H
3
O
+
]
aq

log E = log K
ex
+ nlog [HX]
org
+ npH

Thus a plot of log E against pH should yield a straight line with n as slope
and (log K
ex
+ nlog [HX]
org
) as intercept on the ordinate.



log E

} log Kex + nlog [HX]org
pH
1. So if n, the charge on the
metal is high the slope will be
steeper.
2. Note that in the final
equation no term involving
the concentration of the
metal appears.
It therefore applies to trace
concentrations as well as to
macro quantities.

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END OF LECTURE ON EXTRACTION

GOOD LUCK
TO ALL !

10/18/2011 Prof Derick Carboo 33