Methods of purification:
Sublimation.
Crystallization.
Distillation.
Differential extraction
Chromatography.
Sublimation:
solid is directly converted into vapour without undergoing a liquid state.
Sublimable compound is separated from non-sublimable impurity
Eg, Purification of I2 , camphor, Naphthalene & NaCl, ammonium chloride , dry
ice etc.
I2(s)<---->I2(g),
Crystallization:
Difference in solubility of organic compound and impurities in a
solvent.
Impure compound is added to solvent in which it is sparingly soluble at
room temperature and highly soluble at high temperature.
Solution is concentrated to make saturated solution and then cooled
down.
Pure compound crystallizes and separated by filtration.
The filtrate (mother liquor) contains impurities and small quantity of the
compound. To extract the compound, repeated crystallization is carried
out.
Impurity, which imparts colour to the solution are removed by adsorbing
an activated charcoal.
Eg. Purification of sugar, purification of Potash Alum, water and sugar,
benzoic acid and naphthalene etc.
Distillation:
process of separating liquids having difference in boiling point.
Or
Process of separating volatile liquid from non-volatile liquids
Four types:
Simple distillation
Fractional distillation
Distillation under reduced pressure
Steam distillation
Simple distillation:
used for liquids have large difference in their boiling points ( BP difference
should be more than 20°C
Eg. Chloroform(334k) and aniline (457k), propanol and propanone
Fractional distillation
used for liquids have small difference in their boiling points.
Vapors of liquid with high boiling point condense before vapours of liquid
with lower boiling point.
Eg. Oil products are separated from crude oil in the petroleum industry
crude naphtha ( a mixture of paraffin's, olefins, aromatic compounds,
naphthalene, having slight difference in their BP.
Vacuum distillation/Distillation under reduced pressure
Used for liquids having very high boiling point and decompose at below
their boiling point.
Such liquids are boiled at temperature lower than their normal bp by
reducing the pressure on their surface
Ex: separation of glycerol from spent lye in soap industries, mixture of
glycerol and sugar etc.
Steam Distillation
Used for liquid which is steam volatile and insoluble in water.
Eg. Nitrobenzene , water and aniline , chloro toluene, o-nitro phenol and
p-nitro phenol
Differential extraction:
Principle:
Organic compound is more soluble in nonpolar solvent than polar
solvent.
When organic compound is present in water, the solution is mixed with
organic solvent in which organic compound is more soluble.
Note: organic solvent and water should be immiscible.
Thus, water and organic solvent form two different layers in the
mixture.
By distillation or evaporation method, both layers are separated.
If organic compound is less soluble in organic solvent, then large
quantity of solvent is used to extract even a small quantity of
organic compound.
Ex: H2O and toluene
Chromatography: Chroma (Greek word ) means color.
Chromatography is technique extensively used to
separate mixtures into their components,
purify compounds
to test the purity of compounds.
First used to separate colored substances obtained from plants.
It consists of two phases.
Stationary phase: A mixture of substances (solid or liquid) as absorbent is applied
onto a stationary phase.
Mobile phase: a mixture of solvents or gases is allowed to move slowly over the
stationary phase
Note: Different components of a mixture have different degree of adsorption on the
stationary phase.
Solvent
rise up
the
plate
through
Capillary
action
Gradually, components A, B, C ..of the mixture get adsorbed on the adsorbent to
different degrees at different level of the plate.
Adsorption chromatography:
Adsorbents are used alumina or silica gel coated on stationary phase.
It is of two types based on the principle of differential adsorption on
stationary phase.
Stationary phase: solid, mobile phase: solvents / gas
(a) Column chromatography,
(b) Thin layer chromatography.
Column Chromatography:
A column of adsorbent material (stationary phase) is packed in a
glass tube.
A mixture of different components is placed at the top of glass
tube.
Then, appropriate solvent (mobile phase) is allowed to flow down
the column slowly.
Different components of mixture are adsorbed on the adsorbent to
different degrees.
The most readily adsorbed substances are retained near the top
and others come down to various distances in the column
In chromatography technique, purification of compound depends on the
solubility of components, not on the physical state of compounds.
Thin layer chromatography (TLC): used to isolate non-volatile mixtures
Ex: p- nitrophenol and picric acid
A thin layer (about 0.2mm thick) of an adsorbent (silica gel or alumina) is spread
over a glass plate of suitable size. The plate is known as thin layer
chromatography plate or chromaplate.
Mixture of different components is applied about 2 cm above the end of TLC
plate.
Then, TLC plate is placed in closed jar containing eluant (a mixture of suitable
solvents as mobile phase).
When eluant rises up the plate, along with eluant, different components of
mixture also rise up the plate and get adsorbed to different degrees.
Spots of colorful components are visible on TLC plate
but the spots of colorless components which are not visible on the plate, can be
detected by putting the plate under UV light, by placing the plate in a covered jar
containing a few crystals of iodine.
Spots of components which adsorb iodine, appear as brown spot on the plate.
Sometimes, a suitable reagent is sprayed over the plate to detect the spots of
colorless components.
For example, amino acids may be detected by spraying the plate with ninhydrin
solution
The relative adsorption of each component of the mixture is expressed in terms of
its retardation factor i.e. Rf value
Rf value can't be more than 1.
Its value is dependent on the mobile phase and on the type of
chromatography.
Rf value directly proportional to the distance travelled by a component
from base line and inversely proportional to the rate of adsorption of the
component.
Since component having higher Rf value have less rate of adsorption, will
separate out first from the mixture
Components having lower Rf value, have high rate of adsorption, will
separate out last from the mixture.
Partition chromatography:
It is based on continuous differential portioning of components of a mixture
between stationary and mobile phase , also known as paper chromatography.
In Paper chromatography, chromatography paper is used which contains water in
it and acts as stationary phase.
polar solvent binds to the paper chromatography plate.
When nonpolar solvent rises up the plate, based on the solubility, components of
mixture also rise up the plate along with solvent.
Polar components dissolve in polar solvent and non-polar components dissolve in
nonpolar solvents.
