Question 12.

18:

Give a brief description of the principles of the following techniques taking an example in each
case.

(a) Crystallisation (b) Distillation (c) Chromatography

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(a) Crystallisation

Crystallisation is one of the most commonly used techniques for the purification of solid organic
compounds.

Principle: It is based on the difference in the solubilites of the compound and the impurities in a
given solvent. The impure compound gets dissolved in the solvent in which it is sparingly
soluble at room temperature, but appreciably soluble at higher temperature. The solution is
concentrated to obtain a nearly saturated solution. On cooling the solution, the pure compound
crystallises out and is removed by filtration.

For example, pure aspirin is obtained by recrystallising crude aspirin. Approximately 2 – 4 g of

(b) Distillation

This method is used to separate volatile liquids from non-volatile impurities or a mixture of those
liquids that have a sufficient difference in their boiling points.

Principle: It is based on the fact that liquids having different boiling points vapourise at different
temperatures. The vapours are then cooled and the liquids so formed are collected separately.

For example, a mixture of chloroform (b.p = 334 K) and aniline (b.p = 457 K) can be separated
by the method of distillation. The mixture is taken in a round bottom flask fitted with a
condenser. It is then heated. Chloroform, being more volatile, vaporizes first and passes into the
condenser. In the condenser, the vapours condense and chloroform trickles down. In the round
bottom flask, aniline is left behind.

(c) Chromatography

It is one of the most useful methods for the separation and purification of organic compounds.
Principle: It is based on the difference in movement of individual components of a mixture
through the stationary phase under the influence of mobile phase.

For example, a mixture of red and blue ink can be separated by chromatography. A drop of the
mixture is placed on the chromatogram. The component of the ink, which is less adsorbed on the
chromatogram, moves with the mobile phase while the less adsorbed component remains almost
stationary.

Question 12.19:

Describe the method, which can be used to separate two compounds with different solubilities in
a solvent S.

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Fractional crystallisation is the method used for separating two compounds with different
solubilities in a solvent S. The process of fractional crystallisation is carried out in four steps.

(a) Preparation of the solution: The powdered mixture is taken in a flask and the solvent is
added to it slowly and stirred simultaneously. The solvent is added till the solute is just dissolved
in the solvent. This saturated solution is then heated.

(b) Filtration of the solution: The hot saturated solution is then filtered through a filter paper in
a China dish.

(c) Fractional crystallisation: The solution in the China dish is now allowed to cool. The less
soluble compound crystallises first, while the more soluble compound remains in the solution.
After separating these crystals from the mother liquor, the latter is concentrated once again. The
hot solution is allowed to cool and consequently, the crystals of the more soluble compound are
obtained.

(d) Isolation and drying: These crystals are separated from the mother liquor by filtration.
Finally, the crystals are dried.
Question 12.20:

What is the difference between distillation, distillation under reduced pressure and steam
distillation ?

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The differences among distillation, distillation under reduced pressure,

and steam distillation are given in the following table.

Distillation Distillation under Steam distillation

1. It is used for the purification This method is used to It is used to purify an organic
of compounds that are purify a liquid that tends to compound, which is steam
associated with non-volatile decompose on boiling. volatile and immiscible in
impurities or those liquids, Under the conditions of water. On passing steam, the
which do not decompose on reduced pressure, the liquid compound gets heated up and
boiling. In other words, will boil at a low the steam gets condensed to
distillation is used to separate temperature than its boiling water. After some time, the
volatile liquids from non- point and will, therefore, mixture of water and liquid
volatile impurities or a not decompose. starts to boil and passes
mixture of those liquids that through the condenser. This
have sufficient difference in condensed mixture of water
boiling points. and liquid is then separated by
using a separating funnel.

2. Mixture of petrol and Glycerol is purified by this A mixture of water and aniline
kerosene is separated by this method. It boils with is separated by steam
method. decomposition at a distillation.
temperature of 593 K. At a
reduced pressure, it boils at
453 K without
decomposition.
Question 12.21:

Discuss the chemistry of Lassaigne’s test.

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Lassaigne’s test

This test is employed to detect the presence of nitrogen, sulphur, halogens, and phosphorous in
an organic compound. These elements are present in the covalent form in an organic compound.
These are converted into the ionic form by fusing the compound with sodium metal.

The cyanide, sulphide, and halide of sodium formed are extracted from the fused mass by boiling
it in distilled water. The extract so obtained is called Lassaigne’s extract. This Lassaigne’s
extract is then tested for the presence of nitrogen, sulphur, halogens, and phosphorous.

(a) Test for nitrogen

Chemistry of the test

In the Lassaigne’s test for nitrogen in an organic compound, the sodium fusion extract is boiled
with iron (II) sulphate and then acidified with sulphuric acid. In the process, sodium cyanide first
reacts with iron (II) sulphate and forms sodium hexacyanoferrate (II). Then, on heating with
sulphuric acid, some iron (II) gets oxidised to form iron (III) hexacyanoferrate (II), which is
Prussian blue in colour. The chemical equations involved in the reaction can be represented as

(b) Test for sulphur

Chemistry of the test

In the Lassaigne’s test for sulphur in an organic compound, the sodium fusion extract is acidified
with acetic acid and then lead acetate is added to it. The precipitation of lead sulphide, which is
black in colour, indicates the presence of sulphur in the compound.

Chemistry of the test

The sodium fusion extract is treated with sodium nitroprusside. Appearance of violet colour also
indicates the presence of sulphur in the compound.

If in an organic compound, both nitrogen and sulphur are present, then instead of NaCN,
formation of NaSCN takes place.

Na + C + N + S → NaSCN

This NaSCN (sodium thiocyanate) gives a blood red colour. Prussian colour is not formed due to
the absence of free cyanide ions.
(c) Test for halogens

Chemistry of the test

In the Lassaigne’s test for halogens in an organic compound, the sodium fusion extract is
acidified with nitric acid and then treated with silver nitrate.

If nitrogen and sulphur both are present in the organic compound, then the Lassaigne’s extract is
boiled to expel nitrogen and sulphur, which would otherwise interfere in the test for halogens.

Question 12.23:

Discuss the principle of estimation of halogens, sulphur and phosphorus present in an organic
compound.

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Estimation of halogens

Halogens are estimated by the Carius method. In this method, a known quantity of organic
compound is heated with fuming nitric acid in the presence of silver nitrate, contained in a hard
glass tube called the Carius tube, taken in a furnace. Carbon and hydrogen that are present in the
compound are oxidized to form CO2 and H2O respectively and the halogen present in the
compound is converted to the form of AgX. This AgX is then filtered, washed, dried, and
weighed.

Let the mass of organic compound be m g.

Mass of AgX formed = m1 g

1 mol of Agx contains 1 mol of X.

Therefore,

Mass of halogen in m1 g of AgX

Estimation of Sulphur

In this method, a known quantity of organic compound is heated with either fuming nitric acid or
sodium peroxide in a hard glass tube called the Carius tube. Sulphur, present in the compound, is
oxidized to form sulphuric acid. On addition of excess of barium chloride to it, the precipitation
of barium sulphate takes place. This precipitate is then filtered, washed, dried, and weighed.

Let the mass of organic compound be m g.

Mass of BaSO4 formed = m1 g

1 mol of BaSO4 = 233 g BaSO4 = 32 g of Sulphur

Therefore, m1 g of BaSO4 contains

Estimation of phosphorus

In this method, a known quantity of organic compound is heated with fuming nitric acid.
Phosphorus, present in the compound, is oxidized to form phosphoric acid. By adding ammonia
and ammonium molybdate to the solution, phosphorus can be precipitated as ammonium
phosphomolybdate.
Phosphorus can also be estimated by precipitating it as MgNH4PO4 by adding magnesia mixture,
which on ignition yields Mg2P2O7.

Let the mass of organic compound be m g.

Mass of ammonium phosphomolybdate formed = m1 g

Molar mass of ammonium phosphomolybdate = 1877 g

If P is estimated as Mg2P2O7,

Question 12.24:

Explain the principle of paper chromatography.

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In paper chromatography, chromatography paper is used. This paper contains water trapped in it,
which acts as the stationary phase. On the base of this chromatography paper, the solution of the
mixture is spotted. The paper strip is then suspended in a suitable solvent, which acts as the
mobile phase. This solvent rises up the chromatography paper by capillary action and in the
procedure, it flows over the spot. The components are selectively retained on the paper
(according to their differing partition in these two phases). The spots of different components
travel with the mobile phase to different heights. The paper so obtained (shown in the given
figure) is known as a chromatogram.
Question 12.25:

Why is nitric acid added to sodium extract before adding silver nitrate for testing halogens?

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While testing the Lassaigne’s extract for the presence of halogens, it is first boiled with dilute
nitric acid. This is done to decompose NaCN to HCN and Na2S to H2S and to expel these gases.
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

Question 12.26:

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

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Nitrogen, sulphur, and halogens are covalently bonded in organic compounds. For their
detection, they have to be first converted to ionic form. This is done by fusing the organic
compound with sodium metal. This is called “Lassaigne’s test”. The chemical equations involved
in the test are

Carbon, nitrogen, sulphur, and halogen come from organic compounds.

Question 12.27:

Name a suitable technique of separation of the components from a mixture of calcium sulphate
and camphor.

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The process of sublimation is used to separate a mixture of camphor and calcium sulphate. In
this process, the sublimable compound changes from solid to vapour state without passing
through the liquid state. Camphor is a sublimable compound and calcium sulphate is a non-
sublimable solid. Hence, on heating, camphor will sublime while calcium sulphate will be left
behind.

Question 12.28:

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

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In steam distillation, the organic liquid starts to boil when the sum of vapour pressure due to the
organic liquid (p1) and the vapour pressure due to water (p2) becomes equal to atmospheric
pressure (p), that is, p = p1 + p2

Since p1 < p2, organic liquid will vapourise at a lower temperature than its boiling point.

Question 12.29:

Will CCl4 give white precipitate of AgCl on heating it with silver nitrate? Give reason for your
answer.

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CCl4 will not give the white precipitate of AgCl on heating it with silver nitrate. This is because
the chlorine atoms are covalently bonded to carbon in CCl4. To obtain the precipitate, it should
be present in ionic form and for this, it is necessary to prepare the Lassaigne’s extract of CCl4.

Question 12.30:

Why is a solution of potassium hydroxide used to absorb carbon dioxide evolved during the
estimation of carbon present in an organic compound?

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Carbon dioxide is acidic in nature and potassium hydroxide is a strong base. Hence, carbon
dioxide reacts with potassium hydroxide to form potassium carbonate and water as
Thus, the mass of the U-tube containing KOH increases. This increase in the mass of U-tube
gives the mass of CO2 produced. From its mass, the percentage of carbon in the organic
compound can be estimated.

Question 12.31:

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

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Although the addition of sulphuric acid will precipitate lead sulphate, the addition of acetic acid
will ensure a complete precipitation of sulphur in the form of lead sulphate due to common ion
effect. Hence, it is necessary to use acetic acid for acidification of sodium extract for testing
sulphur by lead acetate test.

Question 12.32:

An organic compound contains 69% carbon and 4.8% hydrogen, the remainder being oxygen.
Calculate the masses of carbon dioxide and water produced when 0.20 g of this substance is
subjected to complete combustion.

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Percentage of carbon in organic compound = 69 %

That is, 100 g of organic compound contains 69 g of carbon.

Molecular mass of carbon dioxide, CO2 = 44 g

That is, 12 g of carbon is contained in 44 g of CO2.

Therefore, 0.138 g of carbon will be contained in = 0.506 g of CO2

Thus, 0.506 g of CO2 will be produced on complete combustion of 0.2 g of organic compound.

Percentage of hydrogen in organic compound is 4.8.

i.e., 100 g of organic compound contains 4.8 g of hydrogen.

Therefore, 0.2 g of organic compound will contain

It is known that molecular mass of water (H2O) is 18 g.

Thus, 2 g of hydrogen is contained in 18 g of water.

∴0.0096 g of hydrogen will be contained in of water

Thus, 0.0864 g of water will be produced on complete combustion of 0.2 g of the organic
compound.

Question 12.33:

A sample of 0.50 g of an organic compound was treated according to Kjeldahl’s method. The
ammonia evolved was absorbed in 50 mL of 0.5 M H2SO4. The residual acid required 60 mL of
0.5 M solution of NaOH for neutralisation. Find the percentage composition of nitrogen in the
compound.

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Given that, total mass of organic compound = 0.50 g

60 mL of 0.5 M NaOH solution H2SO4 = 30 mL of 0.5 M H2SO4

∴Acid consumed in absorption of evolved ammonia is (50–30) mL = 20 mL

Again, 20 mL of 0.5 MH2SO4 = 40 mL of 0.5 MNH3

Also, since 1000 mL of 1 MNH3 contains 14 g of nitrogen,

∴ 40 mL of 0.5 M NH3 will contain = 0.28 g of N

Therefore, percentage of nitrogen in 0.50 g of organic compound = 56 %

Question 12.34:

0.3780 g of an organic chloro compound gave 0.5740 g of silver chloride in Carius estimation.
Calculate the percentage of chlorine present in the compound.

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Given that,

Mass of organic compound is 0.3780 g.

Mass of AgCl formed = 0.5740 g

1 mol of AgCl contains 1 mol of Cl.

Thus, mass of chlorine in 0.5740 g of AgCl

Hence, the percentage of chlorine present in the given organic chloro compound is .

Question 12.35:

In the estimation of sulphur by Carius method, 0.468 g of an organic sulphur compound afforded
0.668 g of barium sulphate. Find out the percentage of sulphur in the given compound.

Total mass of organic compound = 0.468 g [Given]

Mass of barium sulphate formed = 0.668 g [Given]

1 mol of BaSO4 = 233 g of BaSO4 = 32 g of sulphur

Thus, 0.668 g of BaSO4 contains of sulphur = 0.0917 g of sulphur

Therefore, percentage of sulphur = 19.59 %

Hence, the percentage of sulphur in the given compound is 19.59 %.