Solvent Extraction
Solvent extraction is a method used to separate and collect metal ions from a water-
based solution. It works by mixing the solution with an oil-based liquid that has a special
chemical (called an extractant) which grabs the metal ions. The metals move into the oil
layer, which can then be separated from the water. After that, the metals are removed
from the oil by a process called stripping, giving a cleaner water solution full of metals.
This method is often used to extract metals like copper, uranium, cobalt, and rare earth
elements.
Uses:
1. Production of metals
2. Nuclear reprocessing
3. Processing of perfumes
4. Production of vegetable oil
5. Production of biodiesel
Principle of Solvent Extraction:
Solvent extraction involves two steps
a) Extraction
b) Stripping
a. Extraction: In this step, metal ions are moved from a water-based solution into(মেধ )
an oil-based liquid (organic solvent) that contains a special chemical called an
extractant. After mixing well, the metal ions form a bond with the extractant and move
into the organic layer, leaving unwanted materials behind in the water.
b. Stripping: After separating the two layers, the metal-rich organic solvent is treated
with a new water-based solution (usually an acid or base). This makes the metals leave
the organic layer and move back into the fresh water solution. Stripping also cleans the
organic solvent so it can be used again. In short:
Extraction moves metals into the organic solvent.
Stripping moves metals back into a fresh water solution.
Solvent extraction and stripping is a simultaneous process given below:
The difference between extraction and stripping giving below:
Process Solvent Extraction Stripping
Direction Aqueous to Organic Organic to Aqueous
Purpose Extract target metal into organic Recover metal from organic
phase phase
Input Metal solution (aqueous) + organic Loaded organic + fresh aqueous
extractant (acid/base)
Output Loaded organic phase (metal Aqueous solution (metal
complex) recovered)
End goal Metal separation and concentration Metal recovery and solvent
regeneration
Requirements ( েয়াজন ) of an ideal extractant
a) Selectivity
b) High extraction capacity
c) Easily stripped
d) Separate easily from water
i) Density is appreciably different
ii) Low viscosity
iii) High surface tension
e) Safe to handle
i) Nontoxic
ii) Nonflammable
iii) Nonvolatile
f) Stability
g) Availability
h) Easy to recover and use
Extractants:
The transfer of metal ion from aqueous phase to organic phase is obtained by the
addition of certain compounds in the system. These compounds are known as
extractants. They are simple organic compounds. They should be insoluble in aqueous
phase or slightly soluble in aqueous phase.
Name of some extractants:
There are three types of extractant
a) Acidic extractants,
b) Basic extractants and
c) Neutral extractants.
Acidic extractants,
Stearic acid,
Naphthenic acid
Di (2 ethylhexyl) phosphoric acid (D2EHPA),
Dialkylthiophoshinic acid (Cyanex 302),
Dialkyldithiophosphinic acid (Cyanex 301),
Basic extractants:
Tri-n-octyamine (TOA),
Tribenzylamine
Armeen
Primen JMT
Tri-iso-octylamine (TIOA)
Neutral extractants:
Tributyl phosphate (TBP),
Tri-n-octylphosphine oxide (TOPO),
Alizarin,
Morin,
Methyl-iso-butyl ketone (MIBK),
Diluents: Some compounds are added to the extractants to improve the extractive
properties of extractants. These compounds are called diluents. Diluents have no
extractive capacity.
Example: Kerosene, CHCl3, C6H5Cl etc.
Modifier: A modifier added chemical, to the organic solvent during liquid-liquid
extraction to help the two layers separate easily and to prevent the formation of a third
unwanted layer. Modifiers are usually higher alcohols (like those with 6 to 12 carbon
atoms).
Distribution co-efficient:
Concentration of metal ion in ognaic phase
𝐷=
Concentration of metal ion in aqueous phase
Synergism: When some compounds are added to the extractant then the extracting
power of extractant is increased. This phenomena is called synergism.
In the extraction of uranyl ions (UO₂²⁺) from acidic solutions, di(2-ethylhexyl) phosphoric
acid (D2EHPA) is often used as the primary extractant.
Solvent Loading
Solvent loading refers to the maximum amount of metal ions (or other solutes) that an
organic solvent (extractant) can carry or "load" during extraction.
Example:
In the solvent extraction of uranium(VI) from aqueous sulfuric acid using tri-n-butyl
phosphate (TBP) in kerosene, the organic phase can load a certain maximum
concentration of uranyl ions (UO₂²⁺). The loading capacity depends on:
Concentration of TBP
Temperature
Acid concentration
Reaction:
UO22+ + 2NO3− + 2TBP ⇌ UO2(NO3)2⋅2TBP (organic phase)
Third Phase Formation
Third phase formation refers to the undesirable phenomenon in solvent extraction. Third
phase formation where the organic phase separates into two immiscible organic layers.
It creates:
A heavy organic layer (full of metal)
A light organic layer (with little extractant and metal)
This makes separation harder, reduces efficiency, and causes problems in industrial processes.
For example:
When nitric acid is very strong (above 6–8 M) or there’s a lot of uranium, the organic phase
splits into:
A heavy uranium-rich layer
lighter layer with little uranium
How to prevent third phase formation:
Keep acid levels under control
Don’t overload the solvent
Use modified or mixed solvents
Clean or refresh the organic phase
Adjust the temperature
Mechanism of Solvent Extraction:
A) Ion-pair transfer mechanism:
In this process, a metal complex moves from water into an organic solvent as part of a
neutral ion pair.
The extractant (like diethyl ether, written as R–O–R) reacts with the acidic
metal complex HFeCl₄.
The oxygen in the ether uses its lone pair of electrons, to lightly bond with
a proton (H⁺) of HFeCl₄, forming a protonated ether (R–OH⁺).
This creates an ion pair made of (R₂O⋅H⁺) and (FeCl₄⁻).
This ion pair is neutral and dissolves easily in the organic solvent, helping
to extract the Fe(III) complex without forming strong covalent bonds.
C2H5 C2H5
O + HFeCl4 O. HFeCl4
C2H5 C2H5
.
.
B) Ion exchange mechanism
a. Cation exchange mechanism
O O O
2RO-P-OH + UO22- 2RO-P-O- UO2-O-P- +2H2+
OR
OH OH
OH
b. Anion exchange mechanism
RNH2 + HCl → RNH3Cl-
RNH3Cl- + A- → RNH3+ A- + Cl-
C) Chelate extraction mechanism
Engineering Aspects of Solvent Extraction
Percent extraction:
Percent extraction shows how effectively a solvent removes a metal or
substance during solvent extraction.
It tells us what percentage of the material moves from the water phase
into the organic phase.
The formula for percent extraction is easy to understand and doesn't
need complex derivation.
The expression for percent extraction, P, is shown as:
where D is the distribution coefficient, Va is the volume of the aqueous phase, and Vo is
the volume of organic phase.
Separation factor:
Separation factor tells us how well two metal ions (like X and Y) are separated
from each other during solvent extraction.
When you have two metals in a solution and want to extract them, the separation
factor shows how much better one metal is extracted compared to the other.
The formula is:
DX = distribution ratio of metal X
DY = distribution ratio of metal Y
Multiple extractions:
Multiple extractions expression may be derived by considering a certain volume, Va, of
the aqueous phase containing ma grams of solute and a certain volume, Vo, of the
organic phase. With first extraction concluded, the weight of solute left in the aqueous
phase is considered to be m1. The equilibrium concentration in aqueous phase is then
equal to ma/Va and the equilibrium concentration in organic phase is equal to (ma –
m1)/Vo. The process so far permits the following expression for first extraction stage:
Rearrangement of the expression above leads finally to:
A second extraction is considered, and in that case the weight of the solute left in the
aqueous phase is taken to be m2. Like those while on first extraction, the equilibrium
concentration in aqueous phase is equal to m2/Va and the equilibrium concentration in
organic phase is equal to (m1 – m2)/Vo. The expression for D in the second extraction
process carried out is as follows:
Rearrangement of the above expression, like the preceding case of the first extraction,
leads the final expression to:
It is thus possible to record the expression for mn, the weight of solute left behind in the
aqueous phase after n extractions. Such an expression is:
Replacing weight by concentration terms,
where Cn is concentration after n extractions and Ci is initial
concentration in aqueous phase.
