PURIFICATION OF CHARACTERIZATION OF

ORGANIC COMPOUND

PURIFICATION OF ORGANIC COMPOUND

A large number of methods are available for the purification of substances. The choice of method,
however depends on the nature of substance (whether solid or liquid) and the type of impurities
Present on it. The following methods are commonly used for this purpose
(A)simple Crystallization
(B)Fractional Crystallization
(C) Sublimation
(D)Simple Distillation
(E) Fractional Distillation
(F) Distillation under reduced pressure
(G)Steam Distillation
(H)Azeotropic Distillation
(I) Chromatography
(J)Differential extraction
(K) Chemical methods

Simple crystallization
This method is based on the differences in the solubility of the organic compound and its impurities
in a solvent

PREPARATION OF THE SOLUTION

Organic substance is powdered and is dissolved in a suitable solvent by heating. The amount of
solvent should be just sufficient to dissolve the whole of the solid on heating.

Choice of Solvent
The Choice of solvent is very important in the crystallization process. The main conditions of the
solvent are on heating.

• The organic substance should dissolve in the solvent upon heating and it should get separated on
cooling.

• The solvent should not dissolve the impurities.

• The solvent should not react chemically with the substance.

Filtration of the solution
The hot saturated solution is filtered preferably through a fluted filter paper placed in a glass funnel.
The use of the fluted filter paper makes the filtration rapid. The jacketer of the hot water funnel is
heated from outside and this keeps the solution hot in the glass funnel. This will prevent the
formation of crystals during filtration.

EXAMPLE: Naphthalene and urea can be separated by H2O as solvent

Crystallization
The hot filtration is allowed to cool slowly and undisturbed in a breaker or in a crystallizing dish. After
some time crystals of the pure compound are formed.

EXAMPLE:
(i) Sugar mixed with common salt
(Solvent is Ethanol)
(ii) C6H5COOH mix with Naphthalene
(Solvent is hot water)

Separation of crystals
The crystals formed are separated from the mother liquor filtration. The filtration is normally done by
the use of Buchner funnel and a section pump. The enables the filtration under reduced pressure
and is therefore, quite fast.

Drying of crystals
The crystals are dried by pressing between the folds of filter paper and then placed in a steam of air
oven for some time. The crystals are finally dried over sulphuric acid or calcium chloride in a
desiccator.

FRACTIONAL CRYSTALLIZATION
The process of separation of different components of a mixture by repeated crystallizations is called
Fractional crystallization.
• The mixture is dissolved in a solvent in which the two components have different solubilities.
• When a hot saturated solution of this mixture is allowed to cool, the less soluble component
crystallizes out first while the more soluble substance remains in solution (mother liquor).
• The mother liquor left after crystallization of the less soluble component is again concentrated
and then allowed to cool when the crystals of the more soluble component are obtained.
• The two components thus separated are recrystallized from the same or different solvent to yield
both the components of the mixture in pure form.
• Fractional crystallization can be used to separated a mixture of KClO3

EXAMPLE:
Na2SO4(Less Soluble)+Na2Cr2O7(More stable .

Sublimation
Certain organic solids on heating directly change from solid to vapor state without passing through
liquid state, such substances are sublimable and this process is called sublimation.
 Solid heat Vapour

The sublimation process is used for the separation of sublimation volatile compounds from non-
sublimation impurities. The process is generally used for the purification of camphor, Napthalene,
Anthracene , Benzoic acid ,NH4cl,HgCl2,solid SO2,iodineand salicyclic acid containing non-volatile
impurities.

Simple Distillation (More than 400c)

Includes two steps

• Vapourisation

• Condensation

• This method is used for the purification of liquid which boil without decomposition and contain
non-volatile impurities. The simple distillation involves its boiling point so that it is converted into
vapor. On cooling the vapor, pure liquid is obtained.
• The distillate contains pure liquid while the impurities are left behind in the distillation flask,e.g.,
ether from ethyl alcohol
• EXAMPLE:(i)C6H6(B.P.T 800c)&Aniline(B.P.T 1840c)
• (ii)Ether(B.P.T 350c)&Toluene(B.P.T 1100c)

Fractional Distillation (Less than 400C)

This process is used to separate a mixture of two or more miscible liquids which have boiling
points close to each other. The fractionating column is a long tube provided with obstructions to
the passage of the vapor moving upwards and liquid moving downwards. This method may be
used to separate a mixture of acetone (B.P.T. 3300K) and methyl alcohol (B.P.T. 3380K)
.
EXAMPLE: PETROLEUM & COALTAR.

Distillation Under Reduced Pressure (vacuum

Distillation)
Certain liquids have a tendency to decompose at a temperature below their boiling points. Such
liquids cannot be purified by ordinary distillation. Therefore, vacuum distillation is used for liquids
which decompose at a temperature below their normal boiling points.
For Example, glycerol boils with decomposition at 5630K,Cane Juice, glycerol from spent lye.

Steam Distillation
The process of steam distillation is used for the separation and purification of liquid which is
appreciably volatile in steam, from non-volatile components of a mixture. Thus, the process of steam
distillations is used to purify the substances which:
• Are volatile in steam but are not miscible with water
• Possess sufficiently high vapor pressureat the boiling point temperature of water (1000C)
• Contain non-volatile impurities.

The process of steam distillation can be applied for the separated of a mixture of O-nitrophenol
& P-nitrophenol. In this process water vapor carry along with them vapor of O-nitrophenol which
is more volatile and they get condensed in the receiver. P-nitro phenol with higher B.P remains in
the distillation flask.
The method can also be used for the purification of impure sample of aniline
EXAMPLE: Chloro -toluene & Aniline & nitro benzene, Turpentine oil.

Azeotropic Distillation

Azeotropic mixture is a mixture having constant boiling point. For example, Mixture of ethanol
and water in the ratio of 95.87 :4.12i9a ratio present in rectified spirit). It boils at 78.13 0C.

• A special type of distillation (azeotropic distillation) is used for separating the constituents of an
azeotropic mixture.
• The process is based on the fact that dehydrating agents such as C6H6, CCl4, diethyl ether depress
the partial pressure of one of the original components. As a result, the boiling point of that is
raised sufficiently and thus the other component will distil over.

Chromatography
• Russian botanist Tswett in 1906
• This is a modern method used for the separation of mixtures into its components, purification of
compounds, and also to test the purity of components.
Principle of chromatography
The technique of chromatography is based on the difference in the rates at which the
components of a mixture move through a porous medium(Called stationary phase ) under the
influence of some solvent or gas ( called moving phase ). Thus this technique consists of two
phases: one of these is a stationary phase of large surface area while the second is a moving
phase which is allowed to move slowly over the stationary phase. The stationary phase is either a
solid or a liquid while the moving phase may be a liquid or a gas.

Types of chromatography
Depending on the nature of the stationary and the mobile phases, the different types of
chromatographic techniques commonly used an follows:
 Type of chromatography Mobile/Stationary phases Uses
Absorption of column Liquid/Solid Large scale separations
chromatography
Thin-Layer Liquid/Solid Qualitative analysis
chromatography (identification and
characterization of organic
compounds)
High performance liquid Liquid/Solid Qualitative and Quantitative
chromatography analysis
Gas-liquid chromatography Gas/liquid Qualitative and Quantitative
(GLC) analysis
Paper or partition Liquid/Liquid Qualitative and Quantitative
chromatography analysis of polar organic
compounds (sugars, alpha-
amino acids and inorganic
compounds)

• Rf value (Retention Factor) or Retardation factor

The movement of the substance relative to the solvent is expressed in terms its retention factor
(Rf Value). This gives the relative absorption of each components of mixture.

Rf=Distance moved by the substance from the base line (x)

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

* It is constant for a given substance (component) under a given set of conditions. Therefore, it is
possible to identify the various components by the determining R f Values.

* Differential Extraction
* This method is used for the separation of an organic compound (solid or liquid) from its
aqueous solution by shaking with a suitable solvent [e.g., ether, benzene, chloroform, carbon
tetrachloride) in a separating funnel.
*The solvent selected should be immiscible with water but should dissolve the organic
compound to an appreciable extent.
* Applied to non-volatile compounds
Ex: C6H5COOH Extracted from its H2O Solution Using C6H6.