EXTRACTION

Dr. Nabil Bader

Liquid-Liquid extraction
Liquid-Liquid extraction is a mass transfer
operation in which a liquid solution (the
feed) is contacted with an immiscible or
nearly immiscible liquid (solvent) that
exhibits preferential affinity or selectivity
towards one or more of the components in
the feed.
• liquid-liquid extraction (or more briefly, solvent extraction) is
a useful method to separate components (compounds) of a
mixture. The success of this method depends upon the
difference in solubility of a compound in various solvents.

• In the practical use, usually one phase is a water or

water-based (aqueous) solution and the other an
organic solvent (i.e. vegoil) which is immiscible with
water.
• . Solvent extraction is used in nuclear reprocessing, ore
processing, the production of fine organic compounds,
the processing of perfumes and other industries.
Distribution ratio

• In solvent extraction a distribution ratio is oftein

quoted as a measure of how well extracted a species
is.
• The distribution ratio (D) is equal to the concentration
of a solute in the organic phase divided by its
concentration in the aqueous phase.
• Depending on the system the distribution ratio can be
a function of temperature, the concentration of
chemical species in the system and a large number of
other parameters
Sometimes the distribution ratio is referred to the partition coefficent
which is oftein expressed as the log.
Terms:
• Solvent is the term for the organic layer
• Diluent is the term for an inert liquid used to dissolve
an extractant, and to dilute the system.
• Extractant is the term for a metal extraction agent
• Raffinate is the term for the aqueous layer after a
solute has been extracted from it
• Scrubbing is the term for the back extraction of an
unwanted solute from the organic phase
• Stripping is the term for the back extraction from the
organic phase
Ideal Extraction Solvents:
• Immiscibility.
• Dissolves the compound to be extracted.
• Does not dissolve impurities.
• Volatile.
• Not toxic, not flammable.

Unfortunately, few solvents are known to meet both criteria...

• Some solvents are not toxic but flammable (e.g.,
diethyl ether, hydrocarbons--petroleum ether,
hexanes).
• Some are not flammable but toxic (e.g.,
dichloromethane, chloroform).
• Some solvents are both toxic and flammable (e.g.,
benzene).
 Common extraction solvents

Density1 bp
Name Formula Comments
(g / mL) (oC)

LIGHTER THAN WATER:

diethyl ether (CH3CH2)2O 0.7 35 highly flammable, toxic
petroleum ether - ~0.7 30 - 60 flammable
hexanes - ~0.7 >60 flammable

benzene C6H6 0.9 80 flammable, toxic, carcinogenic

toluene C6H5CH3 0.9 111 flammable

ethyl acetate C4H8O2 0.9 78 flammable, irritant

HEAVIER THAN WATER:

methylene chloride CH2Cl2 1.3 41 toxic

(dichloromethane)

chloroform CHCl3 1.5 61 toxic

carbon CCl4 1.6 77 toxic, cancer suspect agent
tetrachloride

1
The density of water is 1.0 g / mL; that of saturated aqueous sodium
chloride solution is 1.2 g / mL.
Distribution coefficient "K"

When a compound is shaken in a separatory funnel with two

immiscible solvents, the compound will distribute itself between
the two solvents.
At a certain temperature, the ratio of concentrations of a solute in
each solvent is always constant.

And this ratio is called the

distribution coefficient, K.
Suppose the compound has a distribution coefficient K = 2
between solvent1 and solvent2.

1) If there are 30 particles of compound , these are distributed

between equal volumes of solvent1 and solvent2...
(2) If there are 300 particles of compound , the same distribution ratio is
observed in solvents 1 and 2,

No matter how much solute there is, the distribution

coefficient K remains constant, equal to 2.
Let's see a second example.
Let's look again at Figure 2. There are 300 particles of compound
distributed between 100 mL each of solvents 1 and 2.
When you double the volume of solvent2 (i.e., 200 mL of solvent2
and 100 mL of solvent1),
the 300 particles of compound distribute as shown:
Compare the results observed in Figures 2 and 3.
Solvent2 is the extraction solvent, i.e., the solvent used to
remove (extract) compound from solvent1.
In Figure 2, 200 of the possible 300 particles are extracted into
solvent2,
whereas in Figure 3, 240 of the possible 300 particles are
extracted into solvent2.

If you use a larger amount of extraction solvent, more solute

is extracted.

But -- what happens if you extract twice with 100 mL of

solvent2 ?
The greater
the number of
small
extractions,
the greater
the quantity
of solute
removed.
it is more efficient
to carry out two
extractions with 1/2
volume of
extraction solvent
than one large
volume.
Why do you shake it?
Shaking allows greater
area of contact
between the two
immiscible liquids,
resulting in faster
equilibration of the
solute substance(s)
between the two
liquids.
* Factors affecting extraction:
• 􀂾􀂾 Interaction between solvent and analyte
• 􀂾􀂾 Distribution coefficient:
• KD = (mi/V)Solvent /(mi/V)Matrix
Where: mi – mass of analyte and V – volume of solvent
• 􀂾􀂾 Volume of solvent vs. multiple extraction
• Temperature
Soxhlet Extractor

• 1 – solvent flask
• 2 – extractor
• 3 – solvent collector
• 4 - condenser
Solvent Selection

• High affinity for the analytes of interest

• Low affinity for the solid matrix
• High volatility, easily be removed to
concentrate the analytes of interest

The sample must be stable at the boiling point of the extracting

solvent
Soxhlet Extraction
• Non- and semivolatile organic compounds from solid samples
• Simple, low cost
• Time consuming (16-24 hrs, 4-6cycles/hr)
• Consumes large amount of solvent
Supercritical Fluid Extraction
SFE
• What is Supercritical Fluid?
By controlling
temperature and
pressure every
substance can be
set into a
supercritical state
Supercritical Fluid Properties
• Heavy like liquid, penetration power of gas
• Good solvating power
• High diffusivity
• Low viscosity
• Minimal surface tension
• Effective and selective solvents
Critical Properties of Selected Substances
CO2
• Available with high purity at low cost
• Environmental friendly
• Low Tc and moderate Pc
• CO2 is non-polar, has no permanent dipole moment
• Addition of polar organic solvent or modifier
Why SFE is not a universal technique?

• Solvation power of CO2

• SFE is matrix dependent technique
• Fairly expensive technique
• Difficult to use