Dnyanasadhana College, Thane.

Department of Chemistry
M.Sc. Analytical Chemistry
Sem-I
UNIT- 3.2
Solvent extraction
Dr.G.R.Bhgaure

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 3.2 Solvent extraction
Recapitulation, factors affecting the
solvent extraction of inorganic species,
Separation Of Metal Ions As Chelate,
concept of [pH]1/2 and its significance, ion
association, solvation with suitable examples,
Craig’s counter current extraction:
principles, apparatus and applications,
 Use of crown ethers in solvent extraction.

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 Terms
 Chelates: When bidentate or polydentate ligand is attached
through two or more doner atoms to the same central metal ion
forming a ring structure ,the resulting complex is called as chelate
and the ligand is called as chelating ligand.
 Chelation: The process of formation of chelate is called as Chelation.
 Partition: Transfer of solute from one phase to other phase is called
as partition.
 Distribution coefficient: It is an equilibrium constant obtained by
applying law of mass action to the equilibrium reaction.
 Solute(aq.)- --- Solute(org.)
< --------

 [Solute] (org)
 D=---------------------
 Solute(aq.)
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 Dielectric constant: The capacity of solvent to separate
the oppositely charged particle of solute is called as
called as Dielectric constant.
 .Ex. Water is having High Dielectric constant
(DH20=78.5) ,if any solute is added in water the amount
of work required to separate the charged particle is less.
 Similarly if any solute is added in acetic acid the amount
of work required to separate the charged particle is
more.
 Ion Pair: An neutral species formed by electrostatic
interaction of a cation and an anion in a solvent of low
dielectric constant which does not encourages
separation of ions as does water.

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5
 Solvent extraction
 Solvent extraction is based on the principle that
when a solute is brought in contact with two
immiscible solvents, one of which is invariably
water and the other organic, the solute distributes
itself in a fixed ratio in the two solvents.
 The technique finds application in separation, purification and
enrichment.
 There is another important aspect of solvent extraction in the
form of extractive Spectrophotometry.
 The absorbance of coloured metal complexes, particularly metal
chelates, extracted in the organic phase is measured.
 It is also used to concentrate the metal, separate it from
interferences and develop the absorbing system in a single step.
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 Solvent extraction
Application

Separate The Metal

Extractive Concentrate from interferences and
Spectrophotometry. the metal,. develop the absorbing
system in a single step

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 Criteria For Selecting Organic Solvent For Solvent
Extraction
i) The organic solvent should be immiscible with
the aqueous phase.
ii) It should have good stability. This will amount to
the fact that the organic phase should be capable of
withstanding many recycling operations in a solvent
extraction circuit without degeneration.
iii) A difference in densities of the contacting phases is
essential and should be as great as possible.
iv) Solvent should have low viscosity . Hence, low
viscosity is a desirable property. Dissolution of the
Extractant in low viscosity diluents modifies this
property to a favorable degree.
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v) The interfacial tension should be high for
rapid coalescence.
vi) The solvent should cause no corrosion
difficulties with common materials of
construction to reduce the cost of equipment.
vii) The solvent should have low toxicity, high
boiling and flash points. These mainly avoid
environmental pollution and fire hazards.
viii) It should have high metal loading capacity.
ix) It should be easily stripped of the loaded
metal.
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 Factors Influencing Extraction
a) pH
b) Molarity of the Acid
c) Metal Ion Concentration
d) Presence of Salting out Agents
e) Presence of Masking (Sequestering) Agent
f) Concentration of the Extractant
g) Nature of Diluents

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 pH
a) pH
• In solvent extraction the equilibrium pH i.e., the pH attained
after the two phases have been contacted to equilibrium is an
important which affect on separation of extracting species.
• The pH will be of great significance in extraction systems
listed in the classification scheme under “Extraction by
compound formation”.
• The extraction by chelating agents,
• Extraction by carboxylic and sulphonic acids and acidic
organophosphorus compounds .
• All the above process are susceptible to pH variation.
• The effect of pH on extraction can been seen from the
following diagram.
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0 1 2 3 4 5 6 7 8 9 10
Qualitative extraction curves for metal dithizonates

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 Molarity of the Acid
• The study of the effect of Molarity of the acid
on extraction is carried out on the extraction of
metals by salvation or ion – pair formation.
• These investigations are mainly related to the
mineral acids and that too mostly to HCl and
HNO3.

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 Effect of Metal Ion Concentration
 The effect of the metal ion concentration on the distribution
ratio of the metal is negligible.
 This will mean that both tracer and macro amounts of metals
may be expected to extracted to the same extent under
similar equilibrium conditions provided the solubility of the
extracting species in the organic phase is not exceeded.
 The relationship between M(aq.) and M (org.) with the increasing
metal ion concentration is used to find the loading capacity
of the extractant.
 These plots known as loading curves or extraction isotherms
for the extraction of Ti (IV), V (IV), Fe (III), Cu (II) and Zn (II) in
toluene solution of Cyanex 923 are shown in Fig. 3.8.

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[Metal
ion]
---------Fe (III)
(organic)
-1
--------Ti (IV)

-2
---------V (IV)

-3

-3 -2 -1
[Metal ion ] (aq)

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 In all these plots, the linear part of the curve means
that the extracting species does not change with the
increasing metal ion concentrations, thereafter, at a
certain point,
 The loading condition sets in and no further increase
in the metal content of the organic phase is observed.
 From this, the amount of the metal ion that can be
loaded on a particular amount of the extractant can
be calculated and the results expressed in terms of
molar ratio.
 Sometimes from this, you can infer the
Stoichiometry of the extracted species.

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 Presence of Salting out Agents

 When inorganic salts are added more and more

amount of solute transfer to organic phase this is
called as salting and inorganic substances are
called as Salting out Agents
 The salting out effect is explained on the activity of
the distributing species and strong ability of these
ions to bind water ( hydration) thereby depleting
aqueous phase of the water molecules to compete.
 The magnitude of enhancement in extraction by the
added salt depends upon the charge and ionic size of
the cation for a given anion.

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• Aluminium and ferric salts are stronger salting
out agents than ammonium salts but
analytically, the ammonium salts are more
convenient because it is easier to remove them
in the aqueous phase by repeated evaporation
with HNO3 and HCl.
• Generally, large amounts of these salts are
added.

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 Presence of Masking (Sequestering ) Agents
 The substances which can form complex with a particular metal ion to
prevent from taking part in their usual reactions are called Masking agents
also known as sequestering agents.
 They are mainly used to prevent particular metals from taking part in their
usual reactions and therefore, the interference of the undesirable elements
is removed without the actual separation step.
 The masked metal forms a water soluble complex most often negatively
charged.
 In solvent extraction, the masking agents are used to prevent certain metal
ions from forming extractable complexes and thus, they increase the
selectivity.
 The use of masking agents like cyanide, tartarate, citrate, fluoride and
EDTA is restricted largely to metal chelate extraction systems. In highly
acidic solutions encountered in many extraction systems, most of the
masking agents do not function effectively.

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 Concentration of the Extractant

 Extraction increases with the increasing

Extractant concentration.
 Invariably, a straight line is obtained in the
plots of log [Extractant] vs log D.
 The slope of the straight line corresponds to
the number of Extractant molecules involved
in the formation of the extracting species.

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Log

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Liquid -Liquid Extractions Involving Metal Chelates
OR
Separation Of Metal Ions As Chelate,
Principle: One of the most common applications of a liquid–
liquid extraction is the selective extraction of metal ions using a
chelating agent.
 During the process of Chelation chelating agent undergoes
ionization, the ionisable proton is displaced by the metal ion
when the chelate is formed, and the charge on the organic
compound neutralizes the charge on the metal ion.
 Due formation of chelates size of the complex increases, this
complex becomes hydrophobic in nature because of this more
and more solute transferred in organic solvent.
 As most of the chelating agents are less ionize in water
for these reasons the chelating agent is added to the
organic solvent instead of the aqueous phase.
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 Factors affecting chelate formation
a) Basic strength of chelating group
b) Electronegativity of donor group
c) Ring size
d) Nature of central metal ion
e) Resonance and steric effect

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 Basic strength of chelating group
• The stability of chelate complex formed with
the given metal ion generally increases with
basic strength of the donating agent as
measured by the pKa values. pKa values
decides the stability of the chelate complex .

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 Electronegativity of donor group

• Electronegativity of basic group (donor group)

in the reagent is also important .For transition
elements atoms of low electronegativity tends
to form stronger bond.
• For.Ex. Dithiozone with sulphur as doner atom
forms a better chelate than diphenyl
carbazone with oxygen atom as doner atom.

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 Ring Size
 Size of chelate complex is also important.
 5 or 6 membered ring chelates are more
stable as they have minimum steric hindrance
and no strains. The functional group of ligand
must be situated that they permit the
formation of stable ring. The chelate stability
increases with no. of rings

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 Nature of central metal ion
 For metal ions charge to size ratio i.e. ionic
radius decides the stability of the complex.
 As this ratio increases more stable complex is
formed.

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 Resonance and steric effect
 The stability of chelate structure is enhanced
by the contribution of resonance structures of
the chelate rings.
 Thus copper acetyl acelanto complex has
greater stability than copper chelate of
salicyldoxime.

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 Separation Of Metal
Ions
As Chelate,

8-Hydroxyquinoline 1-Nitroso-2- Cupferron

(Oxine) Dimethylglyoxime. (ammonium salt of N-
naphthol
nitroso-N-
phenylhydroxylamine).

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Examples of metal
chelates extractions

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 • 8-Hydroxyquinoline (oxine)
• Oxine is a versatile organic reagent and forms chelates with
many metallic ions. The chelates of doubly and triply charged
metal ions have the general formula
• M (C9H6ON)2 , M (C9H6ON)3 , M (C9H6ON)4.
• Oxine is generally used as a 1 per cent (0.07 M) solution in
chloroform, but concentrations as high as 10 per cent are
advantageous in some cases (e.g. for strontium).
• 8-Hydroxyquinoline, having both a phenolic hydroxyl group
and a basic nitrogen atom, is amphoteric in aqueous solution;
it is completely extracted from aqueous solution by
chloroform at pH < 5 and pH > 9; the distribution coefficient
of the neutral compound between chloroform and water is 720
at 18 OC.
• The usefulness of this sensitive reagent has been extended by
the use of masking agents (cyanide, EDTA, citrate, tartrate,
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etc.) and by control of pH
 Dimethylglyoxime.
 Dimethylglyoxime: The complexes with nickel
and with palladium are soluble in chloroform. The
optimum pH range for extraction of the nickel
complex is 4-12 in the presence of tartrate and
 7-12 in the presence of citrate (solubility 35-50
ug Ni mL-' at room temperature); if the amount of
cobalt exceeds 5 mg some cobalt may be
extracted from alkaline solution. Palladium(I1)
may be extracted out of ca 1M-sulphuric acid
solution.

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 1-Nitroso-2-naphthol.
• 1-Nitroso-2-naphthol reagent forms
extractable complexes (chloroform) with
• Co(III) in an acid medium and
• with Fe(II) in a basic medium.

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 Cupferron (ammonium salt of
N-nitroso-N-phenylhydroxylamine).
 The reagent is used in cold aqueous solution
(about 6 percent). Metal cupferrates are soluble
 in diethyl ether and in chloroform, and so the
reagent finds wide application in solvent-
extraction separation schemes.
 Ex. Fe(III), Ti, and Cu may be extracted from 1.2
M HC1 solution by chloroform: numerous other
elements may be extracted largely in acidic
solution.
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 Extraction by Solvation
• In case of extraction by solvation the solvent it self participate in the extraction
of complex.
• The basic character of oxygen atom enables the incorporation of the solvent
molecule in the coordination sphere of metal ion to form solvated complex
which is extractable.
• Ex.Fe(III) forms chelate complex of composition H[FeCl4] in HCl solution which
can be extracted with verity of solvent possessing doner O atom such as diethyl
ether, ethyl acetate, butyl acetate etc. The amount of metal extracted depends
upon concentration of acid and passes through max. amount of 6M HCl.
• Fe3+ HCl [HFeCl4] this complex formed is extracted by water molecule i.e. in
aq.phase. Hence solvent like diethyl ether is added to water are replaced .Hence
it passes into organic phase. The ability of oxygenated solvent complex with
water molecule for acidic metal ion depends on electron donating ability that is
bacicity of ‘O’ or any other doner atom.
• Such bacicity in turn depends on steric availability of electrons. The comparative
strength of water may be reduced by using high concentration, which by mass
action to shift equilibrium .
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 Crown ethers
• Crown ethers are cyclic  chemical compounds that consist of
a ring containing several ether groups.
 Crown ethers find the application to form stable complexes
with a number of metal ions, particularly the alkali metal ions.
 These crown ethers are macrocyclic compounds containing
9-60 atoms, including 3-20 oxygen atoms, in the ring.
 Complexation is considered to result mainly from electrostatic
ion-dipole attraction between the metal ion situated in the
cavity of the ring and the oxygen atoms surrounding it.
 The ion-pair extraction of Na+, K+ and Ca2+ with some organic
counter-ions and dicyclohexyl-18-crown-6 as complex-
forming reagent has been described.

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 Crown ethers
•

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 The first number in a crown ether's name refers to the
number of atoms in the cycle, and the Second Number
refers to the number of oxygen atom.

12-crown-4
18-crown-6 Dibenzo-18-crown-6
15-crown-5
diaza-18-crown-6
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 Affinity for Cations
 Crown ethers strongly bind certain cations,
forming complexes. The oxygen atoms are well situated
to coordinate with a cation located at the interior of the
ring, whereas the exterior of the ring is hydrophobic. The
resulting cations often form salts that are soluble in
nonpolar solvents, and for this reason crown ethers are
useful in phase transfer catalyst.
 The denticity of the polyether influences the affinity of
the crown ether for various cations.
 For example, 18-crown-6 has high affinity for potassium
cation, 15-crown-5 for sodium cation, and 12-crown-4
for lithium cation. The high affinity of 18-crown-6 for
potassium ions contributes to its toxicity.
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 Affinity for amines
 Apart from its high affinity for potassium cations, 18-
crown-6 can also bind to protonated amines and form
very stable complexes in both solution and the gas phase.
 Some amino acids, such as lysine, contain a
primary amine  on their side chains.
 Those protonated amino groups can bind to the cavity of
18-crown-6 and form stable complexes in the gas phase.
Hydrogen-bonds are formed between the three hydrogen
atoms of protonated amines and three oxygen atoms of
18-crown-6.
 These hydrogen-bonds make the complex a stable adduct.

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• Concept of [pH]1/2 and its
significance, ion association,
solvation with suitable examples

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 2. Extraction by ION ASSOCIATION
COMPLEXES
 An alternative to the formation of neutral metal
chelates for solvent extraction is that in which the
species of analytical interest associates with
oppositely charged ions to form a neutral
extractable species.
 Such complexes may form clusters with
increasing concentration which are larger than just
simple ion pairs, particularly in organic solvents of
low dielectric constant. The following types of ion
association complexes can be discussed .
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• The ion pair formation is the process in which uncharged species are formed which can be easily
extracted by organic solvents.
• Ion pair formation process can be represented as ;
• A++B- A+B-
---

[A  B-]
K
[A  ] [B - ]

The value of ion pair formation constant is related to dielectric constant.

e2
K 
aK 2T
Where :K= Boltzman constant
a-= empirical parameter
e= charge
T= Temperature
€= dielectric constant
The decrease in die electric constant of aqueous phase by addition of salt fevours the ion pair
formation.
The important step in mechanism of extraction process is distribution of unextractable
species in organic phase.
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Factors affecting extraction by ion pair association
 Salting effect
 Dielectric constant of solvent and temperature
 Size of anion
 Nature of doner atom

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 Salting effect

• Low dielectric constant of a solution fevours

the ion pair association. Hence during
extraction salt is added to aqueous phase
which decreases the dielectric constant of aq.
Phase which in turn facilitate the ion pair
association this effect is called as salting effect

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 Dielectric constant of solvent and
Temperature
• In case of solvents with high dielectric
constant ion association increases with
increase in temperature. While in case of
solvents with low dielectric constant ion pair
formation decreases with increase in
temperature.

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 Size of anion

• The size of anion plays an important role in

ion pair formation. As the size of anion
increases the ion pair formation process also
increases.
• The ion association increases with anion as per
the following order.
• [Na+ NH2-]< [Na+NH-C6H5] < [Na+ N(C6H5)2-]

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 Nature of doner atom

 The extent of ion pair formation also changes

with nature of doner atom.
 [Na+OC6H5] < [Na+NHC6H5] < [Na+SC6H5]
 The order of doner atom for association is
 O<N<S

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 Craig’s counter current extraction:
principles, apparatus and applications,
 Lyman C.Craig
 Counter Current Extraction:
 A solvent extraction technique in which
two immiscible liquids move in opposite
directions in continuous contact with each
other with a resultant separation of solutes.

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 In this extraction process one solvent,
generally lighter one ( low density) moves by
steps through a series of equilibration vessels
in which it comes in contact with stationary
portions of the other heavier portion.
 Solutes separates on the basis of differences in
their partitioning between two solvents

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Apparatus

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The Device of Continuous Countercurrent
Extraction.

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 Craig’s counter current extraction applications

 Craig's extraction process are found in the biochemical

area.
 It is used to separates peptides having molecular weight
500 -5000 .
 Some antibiotics and certain antibiotics are
polypeptides can be separated by this technique.
 Peptide hormones are separated from the posterior lobe
of pituitary gland.
 It is used for isolation and characterization
adrenocorticotrophic hormone from pituitary gland.
 The technique is also used for purification of
pharmaceutical preparation
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 Apparatus for Craig Extraction

Upper phase from Upper phase from

holding tubes holding tubes of
enters when previous cell enters
transfer is here
completed by
restoring
horizontal position

Tube for
Drain temporarily holding
tube upper phase when
capped in vertical position
during during transfer
operation

Junction of upper and

Lower phases when
Equilibration tube cell is rotated clock54to
vertical position
•All the best

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