Purification & Characterization of Organic Compounds:

1. Purification of Organic Compounds

2. Qualitative Analysis of Organic Compounds
3. Quantitative Analysis of Organic Compounds
1. Purification of Organic Compounds:
Methods of
Purification

Differential/Solvent
Crystallization Sublimation Distillation Chromatography
Extraction

Simple Simple Adsorption Partition

Fractional Fractional Column Paper

Vaccum Thin Layer

Steam
[A] Crystallization:
❑ Simple Crystallization:
This method is used for the separation of solid organic compounds from impurities based on differences
in solubilities.
Examples:
(i) Sugar mixed with common salt can be purified with ethanol.
(ii) Phthalic acid mixed with naphthalene can be purified with hot water.
(iii) Benzoic acid mixed with naphthalene can be purified with hot water.

Q. What is mother liquor?

The filtrate is called mother liquor.

Q. How to separate impurities which show colour?

By adding activated charcoal which adsorbs those colorful impurities.

Q. What to do when organic compound and mixed impurity have similar solubility?
Do crystallization multiple times.
❑ Fractional Crystallization:
This method is used for the separation of a mixture of two compounds which are soluble in
the same solvent but their solubilities are different.
[B] Sublimation:
Some solid substances change from solid to vapour state without passing through the liquid
state.
The purification technique based on the above principle is known as sublimation and is used to
separate sublimable compounds from non-sublimable impurities.
[C] Distillation:
❑ Simple Distillation:
This important method is used to separate:
(i) volatile liquids from non-volatile impurities and
(ii) the liquids having sufficient difference in their boiling points.
Liquids having different boiling points vaporise at different temperatures. The vapours are
cooled and the liquids so formed are collected separately.
Examples:
(i) Chloroform (b.p 334 K) and aniline (b.p. 457 K).
(ii) Ether and Toluene
(iii) Hexane and Toluene
(iv) Benzene and Aniline
❑ Fractional Distillation:
If the difference in boiling points of two liquids is not much, simple distillation cannot be used to
separate them. The technique of fractional distillation is used in such cases.
Examples:
(i) Methanol (b.p. 328 K) and propanone (b.p. 329 K).
(ii) Benzene and Toluene.
How it works?
Vapours of the liquid with higher boiling point condense before the vapours of the liquid with
lower boiling point.
The vapours rising up in the fractionating column become richer in more volatile component. By
the time the vapours reach to the top of the fractionating column, these are rich in the more
volatile component.
A fractionating column provides many surfaces for heat exchange between the ascending vapours
and the descending condensed liquid. Some of the condensing liquid in the fractionating column
obtains heat from the ascending vapours and revaporises. The vapours thus become richer in low
boiling component.
The vapours of low boiling component ascend to the top of the column. On reaching the top, the
vapours become pure in low boiling component and pass through the condenser and the pure liquid is
collected in a receiver.
After a series of successive distillations, the remaining liquid in the distillation flask gets
enriched in high boiling component. Each successive condensation and vaporisation unit in the
fractionating column is called a theoretical plate.
Application in petrochemical industry:
❑ Vaccum Distillation/ Distillation under reduced pressure:
This method is used to purify liquids having very high boiling points and those, which decompose
at or below their boiling points.
Such liquids are made to boil at a temperature lower than their normal boiling points by
reducing the pressure on their surface.
A liquid boils at a temperature at which its vapour pressure is equal to the external pressure.
The pressure is reduced with the help of a water pump or vacuum pump.
Examples:
(i) Glycerol can be separated from spent-lye in soap industry by using this technique.
❑ Steam Distillation:
This technique is applied to separate substances which are steam volatile and are immiscible
with water.
In steam distillation, steam from a steam generator is passed through a heated flask containing
the liquid to be distilled.
The mixture of steam and the volatile organic compound is condensed and collected. The
compound is later separated from water using a separating funnel.
In steam distillation, the liquid boils when the sum of vapour pressures due to the organic liquid
(p1) and that due to water (p2) becomes equal to the atmospheric pressure (p), i.e. p =p1+ p2. Since
p1 is lower than p, the organic liquid vaporises at a lower temperature than its boiling point.
Examples:
Thus, if one of the substances in the mixture is water and the other is a water-insoluble
substance, then the mixture will boil close to but below, 373K. A mixture of water and the substance
is obtained which can be separated by using a separating funnel. Aniline is separated by this
technique from an aniline–water mixture.
[D] Differential Extraction:
When an organic compound (non-volatile) is present in an aqueous medium, it is separated by
shaking it with an organic solvent in which it is more soluble than in water.
The organic solvent and the aqueous solution should be immiscible with each other so that they
form two distinct layers which can be separated by a separatory funnel.
The organic solvent is later removed by distillation or by evaporation to get back the compound.
Differential extraction is carried out in a separatory funnel. If the organic compound is less
soluble in the organic solvent, a very large quantity of solvent would be required to extract even a
very small quantity of the compound. The technique of continuous extraction is employed in such
cases. In this technique same solvent is repeatedly used for extraction of the compound.
Examples:
Benzoic acid can be extracted from water using benzene.
[E] Chromatography:
Chromatography is an important technique extensively used to separate mixtures into their
components, purify compounds and also to test the purity of compounds.
In this technique, the mixture of substances is applied onto a stationary phase, which may be a
solid or a liquid. A pure solvent, a mixture of solvents, or a gas is allowed to move slowly over the
stationary phase.
The components of the mixture get gradually separated from one another. The moving phase is
called the mobile phase.
❑ Column Chromatography:
Column chromatography involves the separation of a
mixture over a column of adsorbent (stationary phase)
packed in a glass tube. The column is fitted with a
stopcock at its lower end.
The mixture adsorbed on adsorbent is placed on the
top of the adsorbent column packed in a glass tube.
An appropriate eluant which is a liquid or a
mixture of liquids is allowed to flow down the column
slowly.
Depending upon the degree to which the compounds
are adsorbed, complete separation takes place. The
most readily adsorbed substances are retained near the
top and others come down to various distances in the
column.
❑ Thin Layer Chromatography:
Thin layer chromatography (TLC) involves the separation/identification of substances of a
mixture over a thin layer of an adsorbent coated on glass plate based on their polarity.
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.
The solution of the mixture to be separated is applied as a small spot about 2 cm above one end
of the TLC plate. The glass plate is then placed in a closed jar containing the eluant(solvent).
As the eluant rises up the plate, the components of the mixture move up along with the eluant
to different distances depending on their polarity(non-polar compounds rise up faster than polar
compounds). The relative adsorption of each component of the mixture is expressed in terms of its
retardation factor i.e. Rf value.
The spots of coloured compounds are visible on TLC plate due to their original colour. The spots
of colourless compounds, which are invisible to the eye but fluoresce in ultraviolet light, can be
detected by putting the plate under ultraviolet light. Another detection technique is to place the
plate in a covered jar containing a few crystals of iodine. Spots of compounds, which adsorb iodine,
will show up as brown spots. Sometimes an appropriate reagent may also be sprayed on the plate.
For example, amino acids may be detected by spraying the plate with ninhydrin solution.
Let’s do one experiment.

A B A+B Unknown

A B A+B U
❑ Partition/Paper Chromatography:
Partition chromatography is based on continuous differential partitioning of components of a
mixture between stationary and mobile phases. Paper chromatography is a type of partition
chromatography. In paper chromatography, a special quality paper known as chromatography paper
is used. Chromatography paper contains water trapped in it, which acts as the stationary phase.
A strip of chromatography paper spotted at the base with the solution of the mixture is
suspended in a suitable solvent or a mixture of solvents. This solvent acts as the mobile phase.
The solvent rises up the paper by capillary action and flows over the spot. The paper selectively
retains different components according to their differing partition in the two phases.
The paper strip so developed is known as a chromatogram.
The spots of the separated coloured compounds are visible at different heights from the
position of the initial spot on the chromatogram.
The spots of the separated colourless compounds may be observed either under ultraviolet light
or by the use of an appropriate spray reagent as discussed under thin layer chromatography.
2. Qualitative Analysis of Organic Compounds:
❑ Detection of C and H:
❑ Detection of Other Elements:
Nitrogen, sulphur and halogens present in an organic compound are detected by “Lassaigne’s
test”.
The elements present in the compound are converted from covalent form into the ionic form by
fusing the compound with sodium metal.

Cyanide, sulphide and halide of sodium so formed on sodium fusion are extracted from the
fused mass by boiling it with distilled water. This extract is known as sodium fusion extract.
By testing this extract, N, S, and X can be detected.
(i) Test for N:
(ii) Test for S:

• If both N & S are present: there is no free CN- ion, so, it does not give Prussian blue
test.

If sodium fusion is carried out with excess of sodium, the thiocyanate decomposes to
yield cyanide and sulphide. These ions give their usual tests.
(iii) Test for X(Cl, Br, I):

• Cl- + AgNO3 = AgCl ↓ (White ppt)

• Br- + AgNO3 = AgBr ↓ (Pale Yellow ppt)

• I- + AgNO3 = AgCI ↓ (Yellow ppt)

If nitrogen or sulphur is also present in the compound, the sodium fusion extract is first
boiled with concentrated nitric acid to decompose cyanide or sulphide of sodium formed during
Lassaigne’s test. These ions would otherwise interfere with the silver nitrate test for halogens.
❑ Detection of P:
The compound is heated with an oxidising agent (sodium peroxide). The phosphorus present in
the compound is oxidised to phosphate. The solution is boiled with nitric acid and then treated
with ammonium molybdate. A yellow colouration or precipitate indicates the presence of
phosphorus.
3. Quantitative Analysis of Organic Compounds:
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