Purification of organic compounds

A large number of methods are available for the purification of substances. The choice of
method, however, depends upon the nature of substance (whether solid or liquid) and the type of
impurities present in it. Following methods are commonly used for this purpose,
1. Simple crystallisation

2. Fractional crystallisation

3. Sublimation

4. Simple distillation

5. Fractional distillation

6. Distillation under reduced pressure

7. Steam distillation
 Purification of solid substances.
 Simple Crystallisation
This is the most common method used to purify organic solids. It is based upon the fact that
whenever a crystal is formed, it tends to leave out the impurities. For crystallisation, a suitable
solvent is one (a) which dissolves more of the substance at higher temperature than at room
temperature (b) in which impurities are either insoluble or dissolve to an extent that they remain
in solution (in the mother liquor) upon crystallisation, (c) which is not highly inflammable and
(d) which does not react chemically with the compound to be crystallized. The most commonly
used solvents for crystallisation are: water, alcohol, ether, chloroform, carbon- tetrachloride,
acetone, benzene, petroleum ether etc.
Examples :
1. Sugar having an impurity of common salt can be crystallized from hot ethanol since sugar
dissolves in hot ethanol but common salt does not.
2. A mixture of benzoic acid and naphthalene can be separated from hot water in which
benzoic acid dissolves but naphthalene does not.

Simple crystallization of Benzoic acid:

Equipment / Materials:
hot plate 125-mL Erlenmeyer flask ice stirring rod spatula
Büchner funnel impure benzoic acid weighing paper digital scales rubber tubing (hose) benzoic
acid boiling stones (chips) filter paper
25 mL graguated cylinder 50 mL beaker Mel-temp apparatus

Experimental Procedures
Using a weighing paper, weigh out about 1.00 g of “impure Benzoic acid for recrystallization”
and transfer it to a 125-ml Erlenmeyer flask. Add about 20 ml distilled water, using a graduated
cylinder, to the flask and bring the mixture to the boiling point by heating on a hot plate, while
stirring the mixture and boiling gently to dissolve benzoic acid completely. (Fig 1)

Remove the flask from the hot plate and examine the solution. If there are particles of benzoic
acid still undissolved, then add an additional amount of hot or cold water in small increments and
resume heating the solution. The objective is to dissolve the entire solid in only as much as hot or
near boiling solvent (water) as is necessary. Do not add too much water or the solution will not
be saturated and the yield of purified benzoic acid will be reduced. Keep adding water in small
amounts (several drops at a time from a Pasteur pipette) until all of the benzoic acid is dissolved
and the solution is boiling.
If the solution is completely clear (though not necessarily colorless) and no solid benzoic acid is
visible, then add additional 10-15 ml water to the mixture and place the Erlenmeyer flask on a
countertop where it will not be disturbed and cover with an upside-down small beaker (to
prevent dust contamination). Allowing the flask to cool slowly will give the best-shaped crystals
after about 5-10 minutes. If crystallization does not occur after 10 minutes, scrape the sides of
the flask above the level of the solution with the sharp end of a glass rod hard enough to audibly
scratch the interior surface of the flask. This may dislodge some undetectable, small crystals that
will drop into the solution and "seed" the solution, helping to induce crystallization. A seed
crystal can serve as a nucleation point for the crystallization process. Cooling the solution in an
ice bath may also help at this point.When the crystals have formed completely (may required ice
bath), collect your solid chemical by setting up a vacuum (suction) filtration on a properly fitted
filter paper in a clean Büchner funnel apparatus as described by your instructor. (Fig 2)

Pour the chilled mixture into the Buchner funnel. The water should filter quickly - if not, check
for vacuum leaks. Get all the crystals out of the flask using a spatula or stirring rod. Rinsing with
1 or 2 mLs of cold water helps get the crystals out of the flask, and rinsing helps remove

impurities.
Let the aspirator run for a few minutes to start air-drying the crystals. Then use a spatula to lift
the filter paper and crystals out of the Buchner funnel, then press them as dry as possible on a
large clean paper towel (hand dry), allow them to dry completely, and transfer the dry sample to
a pre-weigh weighing paper. Determine the weigh the DRY crystals of recovered benzoic acid.

 Fractional Crystallisation
The process of separation of different components of a mixture by repeated crystallisations is
called fractional crystallisation. 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 crystallises out first while the more soluble substance
remains in solution. The mother liquor left after crystallisation 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 crystallisation can be used to separate a mixture of (less soluble) and KCl (more
soluble).

 Sublimation

Certain organic solids on heating directly change from solid to vapour state without passing
through a liquid state, such substances are called sublimable and this process is called
sublimation.

The sublimation process is used for the separation of sublimable volatile compounds from non
sublimable impurities. The process is generally used for the purification of Benzoic acid.

 Sublimation of Benzoic acid

Chemical and Apparatus
Beaker , funnel, hotplate, glass rod, filter paper, cold water or ice,
benzoic acid
Procedure of experimental
1. Place a mixture of 1 gm. of one of the sublimed substances
(impurity benzoic acid ) in a 200 ml. beaker, covered
with a filter paper and funnel above it surrounding by cold water or ice .
2. The beaker is placed on a hotplate or a low flame.
3. The sublimed substance (i, e. the benzoic acid) will collect on the bottom of the cold
funnel and on the side walls of the beaker in pure, crystallic form .

 Purification of liquid substances.

 Boiling point Definition

The boiling point of an organic liquid is the temperature at which its vapour pressure equals the
atmospheric pressure over the liquid or it is the temperature at which the vapour and liquid phases are
in equilibrium at agiven pressure. the boiling point is considered as a criterion of purity of a
compound and is useful for identification of organic compounds.
Similar to the melting point the boiling point may be sharp or may vary over a temperature range.
Pure liquids have sharp boiling points while mixtures show a boiling point range.
The atmospheric pressure plays an important role in determination of the boiling point correctly.
Reduction of the pressure leads to a decrease or a depression in the boiling point and vice versa.
 Simple Distillation

Distillation is the joint process of vapourisation and condensation. This method is used for the
purification of liquids which boil without decomposition and contain non-volatile
impurities. This method can also be used for separating liquids having sufficient difference in
their boiling points. This method can be used to separate a mixture of
1. chloroform (b. p. 334 K) and aniline (b. p. 457 K)

 Fractional Distillation
This process is used to separate a mixture of two or more miscible liquids which have boiling
points close to each other. Since in this process, the distillate is collected in fractions under
different temperatures, it is known as fractional distillation. This process is carried out by using
fractionating columns. Fractionating column is a special type of long glass tube provided with
obstructions to the passage of the vapour upwards and that of liquid downwards. This method
may be used to separate a mixture of acetone (b. p. 330 K) and methyl alcohol (b. p. 338 K) or a
mixture of benzene and toluene. One of the technological applications of fractional distillation is
to separate different fractions of crude oil in petroleum industry into various useful fractions
such as gasoline, kerosene oil, diesel oil, lubricating oil etc.
  Distillation under Reduced Pressure(vacuum distillation).
This method is used for the purification of high boiling liquids and liquids which decompose at
or below their boiling points.

The crude liquid is heated in distillation flask fitted with a water condenser, receiver and vacuum
pump. As the pressure is reduced, the liquid begins to boil at a much lower temperature than its
normal boiling point. The vapour is condensed by water condenser and the pure liquid collects in
the receiver.
Glycerol which decomposes at its boiling point (563 K) under atmospheric pressure can be
distilled without decomposition at 453 K under 12 mm of Hg. Similarly, sugarcane juice is
concentrated in sugar industry by evaporation under reduced pressure which saves a lot of fuel.
  Steam Distillation
This method is applicable for the separation and purification of those organic compounds (solids
or liquids) which (a) are insoluble in water (b) are volatile in steam (c) possess a high vapour
pressure (10-15 mm Hg) at 373 K and (d) contain non-volatile impurities.
Aniline (b. p. 457 K) can be purified by steam distillation since it boils at a temperature of 371.5
K in presence of steam. Other compounds which can be purified by steam distillation are:
nitrobenzene, bromobenzene, o-nitrophenol, salicylaldehyde, o-hydroxyacetophenone, essential
oils, turpentine oil etc.