PURIFICATION OF ORGANIC COMPOUNDS

Sublimation

• Some solids can directly pass to the vapour state without going through the liquid phase.
The purification technique which exploits this property is called sublimation. It is helpful
in separating sublimable compounds from non-sublimable ones.
• To purify camphor, naphthalene, anthracene and benzoic acid

Crystallization

• A solvent is chosen, where the compound to be purified is sparingly soluble at a lower

temperature and soluble at a higher temperature.

• The solution is filtered first and insoluble impurities are removed on filter paper

• The solution is heated to get a saturated solution when volatile impurities also go away.

• Then on cooling, the crystals of the compounds are formed which settles down and
mother liquor remains over it

• Mother liquor is decanted off and crystals are dried

• For example, crystals of benzoic acid can be crystallized with water.

• Benzoic acid is sparingly soluble in cold water and soluble in hot water.

• Sugar mixed with common salt using ethanol as solvent can be purified

• Phthalic acid mixed with naphthalene can be purified with hot water

Distillation

• The mixture of liquids can be separated by the difference in their boiling points.

• The boiling point is defined as the temperature at which the vapour pressure of the liquid
is equal to the atmospheric pressure.

• The mixture is taken in the RB flask and boiled.

 • The component with a lower boiling point, evaporates faster

• A condenser is used to fasten the process of condensation.

• For example, a mixture of chloroform and aniline can be separated by distillation.

• The boiling point of chloroform is 60°C, and that of aniline is 189°C.

• Therefore, distillation can be used to separate a mixture of chloroform and aniline.

Fractional Distillation

• When the difference between the boiling points of the liquids is very small then we use
fractional distillation.

• Since the vapours of such liquids might condense together, therefore a fractionating
column is fixed to the mouth of the RB.

• Column provides surface area to the vapours for heat exchange.

• Lower boiling point substances rises to higher levels and higher boiling point substances
condensing and falls back down the column.

• 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
theoretical plate

• This process is used for separating mixtures like water and ethanol, or in production of
gasoline from crude oil.

Mixture of acetone and methyl alcohol

Ethyl alcohol and methylated spirit
Distiillation of petroleum crude alcohol and coaltar
Mixture of benzene and toluene

Vacuum Distillation

• The liquids will boil at a temperature lesser than their boiling points if atmospheric
pressure is low

• This is achieved by using a vacuum pump by which the atmospheric pressure is reduced,

• The liquids boil faster, and hence the whole process of distillation is made fast.
 • This method is used when compounds have very high boiling point which waste a lot of
energy and sometimes compounds might get decomposed before their boiling point is
reached. Therefore, we need vacuum distillation in such cases.

• Glycerol is purified by this method. It boils with decomposition at a temperature of 593

K. At a reduced pressure, it boils at 453 K without decomposition.

• Separation of glycerol from spentlye in soap industry

Steam Distillation

• Here steam is passed into the flask containing the liquids to be separated.
• Liquid is steam volatile and immiscible in water
• The principle here is that the liquids will boil faster because vapour pressure of water
helps in equalizing the atmospheric pressure.
• Total pressure = vapour pressure of water+ vapour pressure of liquid components
• In the absence of steam, the process of boiling would have been continued until it
equalizes the atmospheric pressure but very slow.
• Now, with the addition of steam, this process is expedited.
• Aniline is separated by this technique from aniline – water mixture
• Chloro toluene, aniline and nitro benzene
• Isolation of essential oil from flowers
Differential Extraction
• It is a method employed to separate any organic component from an aqueous solution.

• The principle behind the separation is the different solubilities of organic compounds in
an aqueous medium and organic solvent chosen.

• The aqueous solution containing the organic substance is shaken with a suitable solvent
that is immiscible in water but can easily dissolve the organic substance

• Organic solvent used must be immiscible with an aqueous solution

• After shaking organic compound distribute itself in solvent also.

• Mixture kept undisturbed and two different layers are formed i.e. the aqueous layer and
the solvent layer.

• The aqueous layer contains the organic compound

• The layer containing organic substance is separated by a separating funnel leaving

behind the impurities in the aqueous layer.
Chromatography is an important technique extensively used to separate mixtures into
their components, purify compounds

Two of these are: (a) Adsorption chromatography, and (b) Partition chromatography.

Adsorption Chromatography: Adsorption chromatography is based on the fact that

different compounds are adsorbed on an adsorbent to different degrees. Commonly used
adsorbents are silica gel and alumina.

Following are two main types of chromatographic techniques based on the principle of
differential adsorption.

[1] Column chromatography: Column chromatography involves 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 is placed on the top of the adsorbent column

• An eluant is allowed to flow down the column slowly.

• The most adsorbed substances are retained near the top and others come down
to the column

[2] Thin Layer Chromatography:

• It involves separation of substances of a mixture over a thin layer of an adsorbent

coated on glass plate.
• A thin layer of silica gel or alumina is spread over a glass plate called as
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

• As the eluant rises up the plate, the components of the mixture move up along
with the eluant to depending on their adsorption extent

• Retention factor is calculated by Rf = Distance moved by the substance from base

line (x)/ Distance moved by the solvent from base line (y)

• The spots of coloured compounds are visible on TLC plate

• The spots of colourless compounds, can be detected by putting the plate under
ultraviolet light by iodine and spraying some chemicals

• To separate ortho and para nitroaniline

• To separate blue and red dye

• To separate and purify plant pigments and other natural products

 QUESTION-ANSWERS

Q.1 By mistake, an alcohol (boiling point 97°C) was mixed with a hydrocarbon
(boiling point 68°C). Suggest a suitable method to separate the two compounds.
Explain the reason for your choice.

• A mixture of alcohol and hydrocarbon can be separated by simple distillation because both
components have a large difference in their boiling points. When the temperature is raised to
the boiling point of the low boiling liquid i.e., hydrocarbon, the vapours will consist only of the
hydrocarbon without any contamination of alcohol as their boiling points are far apart. These
vapours can be condensed back to get the hydrocarbon.
Question 2. Describe the method, which can be used to separate two compounds with
different solubilities in a solvent

Answer: Fractional crystallisation is used for this purpose. A hot saturated solution of these two
compounds is allowed to cool, the less soluble compound crystallises out while the more
soluble remains in the solution. The crystals are separated from the mother liquor and the
mother liquor is again concentrated and the hot solution again allowed to cool when the
crystals of the second compound are obtained. These are again filtered and dried.

Question 3. What is the difference between distillation, distillation under reduced pressure
and steam distillation?
Answer:

• Distillation is used in case of volatile liquid mixed with non-volatile impurities or top
separate two liquids in a mixture having different boiling points.
•
Distillation under reduced pressure: This method is used to purify such liquids which
have very high boiling points and which decompose at or below their boiling points.
•
Steam distillation is used to purify steam volatile liquids associated with water
immiscible impuritites.

Question 4. Why is nitric acid added to sodium extract before adding silver nitrate for
testinghalogens?
This is done to decompose NaCN to HCN and Na2S to H2S. These are gases which can be expel
led. That is, if any nitrogen and sulphur are present in the form of NaCN and Na2S, then they are
removed. The chemical equations involved in the reaction are represented as
NaCN+HNO3→NaNO3+HCN
Na2S+2HNO3→2NaNO3+H2S

Question5. Explain the reason for the fusion of an organic compound with metallic sodium for
testing nitrogen, sulphur and halogens.

Answer: Organic compound is fused with sodium metal so as to convert organic compounds into
NaCN, Na2S, NaX and Na3PO4. Since these are ionic compounds and become more reactive and
thus can be easily tested by suitable reagents.

Question 6. Name a suitable technique of separation of the components from a mixture of

calcium sulphate and camphor.

Answer: Sublimation. Because camphor can sublime whereas CaSO4 does not.

Question 7. Explain, why an organic liquid vaporises at a temperature below its boiling point
in its steam distillation ?

Answer: It is because in steam distillation the sum of vapour pressure of organic compound and
steam becomes equal to atmospheric pressure rapidly

Question [Link] CCl4 give white precipitate of AgCl on heating it with silver nitrate? Give reason
for your answer.

Answer: No. CCl4 is a completely non-polar covalent compound whereas AgNO3 is ionic in
nature. Therefore they are not expected to react and thus a white ppt. of silver chloride will not
be formed.

Question 9. Why is it necessary to use acetic acid and not sulphric acid for acidification of
sodium extract for testing sulphur by lead acetate test?

Answer: For testing sulphur sodium extract (Lassaignes extract) is acidified with acetic acid
because lead acetate react with sulphuric acid
 .

Question 10. The best and latest technique for isolation, purification and separation of organic
compounds is: (a) Crystallisation (b) Distillation
(c) Sublimation (d) Chromatography.

Answer: (d) is the correct answer

Question 11 Paper chromatography is an example of

a) Partition chromatography

b) Adsorption chromatography

Ans. Paper chromatography is partition chromatography

***Important note:::::::TLC is used for quick identification of components before scaling up

to a column chromatography for larger scale purification.