CHAPTER 6

CONVENTIONAL SEPARATION
TECHNIQUES

Content
6.1 Distillation, precipitation, crystallization
6.2 Solvent extraction
Solid - Liquid extraction
Liquid- Liquid extraction
6.3 Planar and Column Chromatography

Distillation
Distillation is used to purify a
compound by separating it from a
non-volatile or less-volatile material.
When different compounds in a
mixture have different boiling points,
they separate into individual
components when the mixture is
carefully distilled.

Ex : Distillation of petroleum

Precipitation
Precipitation is the formation of a solid
in a solution during a chemical reaction.
Precipitation reactions can be used for
inorganic analysis.

Crystallization

Crystallization is a technique which chemists use to purify solid

compounds.
Crystallization is based on the principles of solubility
Compounds (solutes) tend to be more soluble in hot liquids (solvents)
than they are in cold liquids.
If a saturated hot solution is allowed to cool, the solute is no longer
soluble in the solvent and forms crystals of pure compound.
Impurities are excluded from the growing crystals and the pure solid
crystals can be separated from the dissolved impurities by filtration

Solvent extraction
Organic and inorganic substances
distribute themselves between two
immiscible liquids, each of them very
differently.
These differences have been used for
separation of chemical species.

Liquid-liquid extraction is a useful method to separate components

(compounds) of a mixture

Let's see an example.

Suppose that you have a mixture of sugar in vegetable oil (it tastes
sweet!) and you want to separate the sugar from the oil. You
observe that the sugar particles are too tiny to filter and you
suspect that the sugar is partially dissolved in the vegetable oil.

HOW TO SEPARATE
THE SUGAR
FROM OIL??????
What will you do?

How about shaking the mixture

with water
Will it separate the sugar from the
oil?
Sugar is much more soluble in
water than in vegetable oil, and,
as you know, water is immiscible
(=not soluble) with oil.
Did you see the result?The water
phase is the bottom layer andthe oil
phase is the top layer, because
water is denser than oil.
*You have not shaken the mixture
yet, so sugar is still in the oil phase.

By shaking the layers (phases) well, you

increase the contact area between the
two phases.The sugar will move to the
phase in which it is most soluble: the
water layer

Now the water phase tastes

sweet,because the sugar is moved to
the water phase upon shaking.**You
extracted sugar from the oil with
water.**In this example,water was
the extraction solvent ;the original
oil-sugar mixture was the solution to
be extracted; and sugar was the
compound extracted from one phase
to another. Separating the two layers
accomplishes the separation of the
sugar from the vegetable oil

Did you get it? .....the concept of LIQUID-LIQUID EXTRACTION?

Liquid-liquid extraction is based on the transfer of a solute
substance from one liquid phase into another liquid phase according
to the solubility. Extraction becomes a very useful tool if you choose
a suitable extraction solvent.You can use extraction to separate a
substance selectively from a mixture, or to remove unwanted
impurities from a solution.In the practical use, usually one phase is a
water or water-based (aqueous) solution and the other an organic
solvent which is immiscible with water.
The success of this method depends upon the difference in solubility
of a compound in various solvents. For a given compound, solubility
differences between solvents is quantified as the "distribution
coefficient"

Partition Coefficient Kp (Distribution Coefficient Kd)

When a compound is shaken in a separator funnel with two immiscible
solvents, the compound will distribute itself between the two solvents.
Normally one solvent is water
and the other solvent is a
water-immiscible organic
solvent.
Most organic compounds are
more soluble in organic solvents,
while some organic compounds
are more soluble in water.

Here is the universal rule:

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.

(when solvent1 and solvent2 are immiscible liquids

For example,Suppose the
compound has a distribution
coefficient K = 2 between
solvent1 and solvent2
By convention the organic
solvent is (1) and waater is
(2)

The ratio of A in the two phases will be constant,(K)

at an given temperature.
K =

a A org
a A aq

A org
A aq

Where a is unit activity and A in molar concentration.

K is equilibrium constant and also known as
distribution coefficient (KD)
If KD is large, > 1, the solute tends to distribute
quantitatively in the organic solvent

Generally the value of KD will be the value

of the ratio of the solubility of A in each
solvent.
The distribution coefficients are useful
because they permit us to calculate the
concentration of an analyte remaining in a
solution after a certain number of
extractions.
They also provide guidance as to the most
efficient way to perform an extractive
separation

The concentration of A remaining in aqueous solution

after i extractions with an organic solvent ([A]i ) is
given by the following equation:
[A]i =

Vaq

V K V
aq
org D

i
[A]o

Where,
[A]i
is the concentration of A remaining in the aqueous
Vaq
volume of aqueous solution
[A]o original concentration of aqueous solution
i
number of extraction portion of the organic solvent
Vorg volume of organic solvent

sol

Example 1
The distribution coefficient for iodine between
an organic solvent and water is 85.
a) Write the distribution coefficient expression
b) Find the concentration of I2 remaining in
the aqueous layer after extraction of 50 mL of
0.001M I2 with the following quantities of
organic solvent
i) 50 mL ii) two 25 mL iii) three 10 mL portions

KD =

[I 2 ]org
[I 2 ]aq

= 85

i) [I2] =

50

x 0.001 = 1.16 x 10-5 M

(50x85) 50

ii) 5.28 x 10-7 M

iii) 5.29 x 10-10 M

Increase in extraction
efficiency by extracting in
smaller portions

SMALLER PORTION = SMALLER VALUE IN AQUEOUS PHASE

SO, HIGH EFFICIENCY

If you extract twice with 1/2 the volume, the extraction is more
efficient than if you extract once with a full volume. Likewise,
extraction three times with 1/3 the volume is even more efficient.
four times with 1/4 the volume is more efficient.five times with 1/5
the volume is more efficientad infinitum
The greater the number of small extractions, the greater the
quantity of solute removed. However for maximum efficiency the
rule of thumb is to extract three times with 1/3 volume

Separatory Funnel Extraction Procedure

Separatory funnels are designed to facilitate the mixing of immiscible liquids

Application -separating Metal Ions as

Chelates
Many organic chelating agents are weak
acids (HQ) that react with metal ions to
give uncharged complexes (MQ2) that
are very soluble in organic solvents, such
as ethers, hydrocarbons, ketones and
chlorinated species (including chloroform
and carbon tetrachloride).
Most metal cations on the other hand, are
nearly insoluble in organic solvent.
Separation between many metal ions can
be done at different pH

Example :
Metal cation, Zn2+ is extracted with an
organic solution containing chelating agent
(Q).

Example :

% extracted

Explain how an aqueous sample consisting of Cu2+ , Pb2+

and Cd2+ can be separated into its component parts by
adjusting the pH of the solution

Plot of extraction efficiency for (i) Cu2+, (ii) Pb2+ and (iii) Cd2+.

Answer :
The pH of solution adjusted to less than 1 (very acidic)
for extraction of Cu2+ and to around pH 8 to extract Pb2+
and to pH >12 to extract Cd2+

Liquid-liquid extraction advantages :

1. Able to extract large quantity of sample.
2. Widely applied to both organic and inorganic
samples extraction.

Liquid-liquid extraction disadvantages:

1. Limited to water immiscible samples.
2. Formation of emulsion may takes place during
shaking.
3. Large volume of solvent used create waste
disposal problem.
4. Extraction process takes time.