RECRYSTALLISATION

INTRODUCTION:

Various organic compounds and inorganic compounds are present in their crude form
containing a number of impurities. These compounds can be purified by technique -
Recrystallization. Recrystallization is a technique used to purify chemicals.

The terms "crystallization" and "recrystallization" are two different processes

Crystallization refers to the formation of a new, insoluble product by a chemical reaction; this
product then precipitates out of the reaction solution as an amorphous solid containing many
trapped impurities.

Recrystallization does not involve a chemical reaction; the crude product is simply dissolved
into solution, and then the conditions are changed to allow crystals to re-form. Recrystallization
produces a more pure final product.

PRINCIPLE

Basic principle of recrystallization involved the selection of a proper solvent for the given
system of compound in which the required compound is soluble at elevated temperatures but
insoluble at low temperature.

In recrystallization mixing of an impure solid compound with a hot solvent done initially to form
a saturated solution or nearly saturated solution.

The solution is then allowed to cool down. As the solution cools down, the solubility of the
desired compound decreases, and pure crystals grow from solution, leaving impurities behind
in the solution. After separation of pure compound in crystalline form, the saturated solution
left behind is called mother liquor.

a) Rapid cooling favors small crystals, and the rate of cooling determines the size and quality of
the crystals: b) Slow cooling favors the growth of large and generally purer crystals The rate of
recrystallization is usually greatest at about 50 °C below the melting point of the substance, the
maximum formation of crystals occurs at about 100 °C below the melting point.

MATERIALS REQUIRED

(A) Apparatus required:

For recrystallization, simple apparatus are required Beaker, funnel, water bath, heating mantle,
glass rod, measuring cylinder, tripod stand fluted filter paper, Buchner funnel and others as in
need.

In recrystallization the filter paper must be carefully fitted into the funnel so the upper portion
beds tightly against the glass.

To prepare the filter paper for use, the dry paper is usually folded exactly in half and exactly
again in quarters. The folded paper is then opened so that a 60° cone is formed with three
thicknesses of paper on one side and a single thickness on the other, the paper is then adjusted
to fit the funnel. The paper is placed in the funnel, moistened thoroughly with water, pressed
down tightly to the sides of the funnel, then filled with water. If the paper fits properly, the
stem of the funnel will remain filled with liquid during the filtration.

In majorly filtration is achieved more rapidly using a fluted filter paper in recrystallization

(B) Chemicals required:

For recrystallization, chemicals required are solvents for the given compound.

SOLVENTS:

Choosing solvent is a crucial step (the compound should be soluble in the hot solvent and as
insoluble as possible in the cold solvent).

There are many factors that determine an appropriate solvent that is.

Solvent should be:

1) Unreactive.

2) Inexpensive, and
3) Have low toxicity.

It is also important that the solvent have a relatively low boiling point (b.p. often < 100°C) as it's
best if the solvent readily evaporates from the solid once recovered.

Table: Solvent- Boiling Point ("C)

Diethyl ether 35

Methylene Chloride 40

Acetone 56

Methanol 65

Hexanes 69

Ethyl acetate 77

Ethanol 78

Methylated spirit 78.5

Water 100

Toluene 111

Glacial acetic acid 118

B) Solvent Properties:

List of solvents, their properties and their boiling point are given below.

1) Diethyl ether:

Diethyl ether is commonly use as organic compound solvent but in major, diethyl ether is not
use due to its very low boiling point. high volatility and hazardous nature.

2) Methylene Chloride:
Methylene chloride is an organic solvent and used as re-crystallization solvent in the extraction
of several pharmaceutical compounds and in the production of many antibiotics and vitamins. It
has no flash point under normal use conditions and can be used to reduce the flammability of
other substances, decreasing the chance of in-fire or explosion.

Direct exposure can harm the eyes, skin, liver, and heart. It can cause drowsiness, dizziness,
numbness and tingling limbs, and nausea and loss of consciousness.

3) Acetone

Acetone tends to be a good solvent at all temperatures also miscible with water at every
concentration and thus a good organic solvent.

Direct exposure can cause drying and cracking of the skin with redness, irritate the eyes, nose

and throat.

4) Methanol/Ethanol/Methylated spirit:

Methylated spirit contains 95% ethanol and 5% methanol. These alcohols are majorly use for
recrystallization processes.

They have good dissolving ability for many organics, but is also infinitely co-soluble with water
Addition of water can rapidly reduce the solubility of many organics and thus induce
recrystallization.

Alcohols can cause dangerous fire hazards, thus do not bring them near to fire. Ingestion can
cause drowsiness, nausea and vomiting, and unconsciousness. It can also affect concentration
and vision.

5) Hexanes:

Hexanes offers poor solubility in the cold solvent, but good to middling solubility in the hot
solvent thus they are best for organic solutes to be recrystallized.

Direct exposure or skin contact can cause a skin rash, dryness and redness. It can imitate the
nose, throat and lungs mucosal lining. Further exposure can cause headache, nausea, vomiting,
dizziness, lightheadedness and unconsciousness

6) Water:

Water is used for recrystallization of organic compounds majorly because it is an extremely

polar liquid, cheap with good recrystallization properties.
Water forms hydrogen bonding with organic molecules and at 100°C, the temperature weakens
the intermolecular attractions of organic compounds, forcing them to fall apart.

Upon cooling, bonds between organic compound reform and thus recrystallization takes place.

7) Glacial Acetic acid

Glacial acetic acid is frequently use for recrystallization of organic compounds.

But it is corrosive to tissues and can cause moderate to severe burns. Exposure to the vapors of
acetic acid causes eye, skin, mucous membrane, and upper respiratory tract irritation.

Majorly for organic compounds - WATER or ALCOHOL/WATER combination is use as solvent.

other than this many organic solvents are also use for recrystallization.

For inorganic compounds - ETHANOL is generally used Take care that the amount of ethanol or
other solvent is not so large that the impurities are also precipitated.

PROCEDURE

1) Clean and dry all the apparatus.

2) Using a conical flask, a known weight of the solid is dissolved in a volume of solvent sufficient
to give a saturated or nearly saturated solution at the boiling point.

3) The hot solution is filtered through a fluted filter paper placed in a short-stemmed funnel,
and the filtrate collected in a beaker: this process will remove any insoluble material present. If
the substance crystallizes out in the funnel, it should be filtered through a heated or jacketed
funnel.

4) The clear hot filtrate is cooled rapidly by immersion in a dish of cold water or in a mixture of

ice and water, according to the solubility of the solid, the solution should be constantly stirred
in order to promote the formation of small crystals and to prevent the trapping of mother
liquor.

5) The solid is then separated from the mother liquor by filtration by filter paper or directly by
using Buchner funnel.
6) When all the liquid has been filtered, the solid is pressed down on the funnel with a wide
glass stopper, sucked as dry as possible, then washed with small portions of the original solvent
to remove the adhering mother liquor.

7) The recrystallized solid is dried in an oven above the laboratory temperature with the
exclusion of dust

8) The dried solid is preserved in glass-stoppered bottles (best) or in sample bags. When the
solid is removed from the funnel, take great care to avoid introducing fibers from the filter
paper, or small particles of glass from the glass filter disc.

PRECAUTIONS:

Precautions must be taken care while handling different solvents having different chemical
properties.

Carefully handle the solvents, wear proper gloves, mask and lab coat before working with
chemicals.
Basic recrystallization techniques for the experiments performed are given below:

EXPERIMENT - 1

Aim:

To perform recrystallization of Acetanilide:

Materials Required:

Apparatus required: Beaker, funnel, heating mantle, glass rod, measuring cylinder, tripod stand,
fluted filter paper, Buchner funnel and others as in need.

Chemicals Required: Glacial Acetic acid. Distilled water, Crude sample of acetanilide

Procedure:

Take a 250ml beaker and add a mixture of one volume of acetic acid and two volumes of water

(about 100mL).

Now heat the solution and add the crude acetanilide in slightly hot solution mixture, with
constant stirring, until the crude sample gets solubilize Filter the solution using Fluted filter
paper, and let the crystals set.

After pure crystal formation, wash and dry them using water and filter paper or air dry the
crystals.

Result:

Pure Acetanilide obtained as Colorless to white crystalline flakes with melting point 114.3°C.

Precautions:
Carefully handle acetanilide and glacial acetic acid, wear proper gloves, mask and lab coat

before working with chemicals.

Acetanilide can causes skin eye and respiratory imitation. It is harmful if get swallowed.

Glacial acetic acid is corrosive to tissues and can cause moderate to severe burns. Exposure to
the vapors of acetic acid causes eye, skin, mucous membrane, and upper respiratory tract
irritation.
EXPERIMENT -2

Aim:

To perform recrystallization of p-Nitro acetanilide

Materials Required:

Apparatus required: Beaker, funnel, water bath, glass rod, measuring cylinder, tripod stand.
fluted filter paper, Buchner funnel and others as in need.

Chemicals Required: Ethanol or methylated spirit, Distilled water, Crude sample of p-nitro
acetanilide

Procedure:

Take a 250ml Beaker, and add the crude p-nitro acetanilide into it (should be dry).

Now add 50ml of Ethanol or methylated spirit to it, the whole mixture should be up to 100ml in
total volume.

Now heat the mixture slowly until it is mixed properly and evaporate the mixture up to 70ml of
is remained.

Filter the solution using filter paper, and allow it to stand and let the crystals set under low
temperature. For this, ice bath or direct refrigeration can be done.

After pure crystal formation, dry them using filter paper or air dry the crystals.

Result:

Pure p-Nitro acetanilide obtained as white to yellowish crystalline solid with melting point -215
°C.

Precautions:
Ethanol or methylated spirit can cause dangerous FIRE HAZARD, do not bring it near to fire.

Always use water bath for heating ethanol or spirit. Ingestion can cause drowsiness, nausea and
vomiting, and unconsciousness. It can also affect concentration and vision.

p-Nitro acetanilide can cause mild skin and eye irritation.

 EXPERIMENT-3

Aim:

To perform recrystallization of Benzoic acid:

Materials Required:

Apparatus required: Beaker, funnel, heating mantle, glass rod, measuring cylinder, tripod stand,
fluted filter paper, Buchner funnel and others as in need.

Chemicals Required: Distilled water, Crude sample of benzoic acid.

Procedure:

Take a 50ml Beaker, and add 20-30ml water in it and boil it.

During boiling, add the crude benzoic acid in small quantities to it until it get dissolved with
constant stirring.

After mixing, filter the solution using filter paper, and let the crystals set.

Result :

Pure Benzoic acid is obtained as shiny white crystals with melting point - 122.3°C.

Precautions

Benzoic Acid exposure to skin can cause skin allergy, itching and a skin rash.
EXPERIMENT-4

Aim:

To perform recrystallization of Benzil:

Materials Required:

Apparatus required: Beaker, funnel, water bath, glass rod, measuring cylinder, tripod stand,
fluted filter paper, Buchner funnel and others as in need.

Chemicals Required: Ethanol or methylated spirit, Crude sample of benzil

Procedure:

Take a 100ml Beaker, and add about 50mL of Ethanol or methylated spirit to it.

Now heat it and add crude benzil to it and dissolve it by constant stirring. Reduce the amount
up to 45 mL. Filter the solution using filter paper, and allow it to stand and let the crystals set
under low temperature. After pure crystal formation, dry them using filter paper or air dry the
crystals.

Result:

Benzil obtained as white to pale yellow crystalline solid with melting point-94.8" C

Precautions:

Benzil can cause skin irritation and can cause serious eye damage/eye irritation, prevent direct
exposure of benzil to skin. Ethanol or methylated spirit can cause dangerous FIRE HAZARD, do
not bring it near to fire. Always use water bath for heating ethanol or spirit. Ingestion can cause
drowsiness, nausea and vomiting, and unconsciousness. It can also affect concentration and
vision.
EXPERIMENT-5

Aim:

To perform recrystallization of Dibenzalacetone:

Materials Required:

Apparatus required: Beaker, funnel, water bath, glass rod, measuring cylinder, tripod stand,
fluted filter paper, Buchner funnel and others as in need.

Chemicals Required: Ethanol or methylated spirit, Crude sample of dibenzalacetone

Procedure:

Take a 50ml Beaker, and add about 25mL ethanol or methylated spirit to it.

Now heat it and add crude dibenzalacetone to it and dissolve it by constant stirring. Reduce the
amount up to 20mL

Filter the solution using filter paper, and allow it to stand and let the crystals set under low
temperature.

After pure crystal formation, dry them using filter paper or air dry the crystals.

Result:

Dibenzalacetone obtained as pale yellow crystalline solid with melting point. 110 C.

Precautions:

Dibenzalacetone can cause skin irritation when directly expose to skin and can lead to skin
allergic reactions. Ethanol or methylated spirit can cause dangerous FIRE HAZARD, do not bring
it near to fire. Always use water bath for heating ethanol or spirit. Ingestion can cause
drowsiness, nausea and vomiting, and unconsciousness. It can also affect concentration and
vision.
EXPERIMENT -6

Aim:

To perform recrystallization of 1-phenylazo-2-napthol

Materials Required:

Apparatus required: Beaker, funnel, heating mantle, glass rod, measuring cylinder, tripod stand,
fluted filter paper, Buchner funnel and others as in need.

Chemicals Required: Glacial Acetic acid, Crude sample of 1-phenylazo-2-napthol

Procedure:

Take a 250ml Beaker, and add 80ml of Glacial acetic acid to it and heat it.

Now add the crude 1-phenylazo-2-napthol (should be dry) to it slowly and in small quantities
until it is mixed properly.

Once the whole sample get mixed with acetic acid remove it from heating mantle Filter the
solution using filter paper, and allow it to stand and let the crystals set under low temperature.
For this, water bath or ice bath can be used. After pure crystal formation, filter them using
Buchner funnel and dry them using filter paper or air dry the crystals.

Result:

1-phenylazo-2-napthol (Sudan 1) obtained as orange-red crystalline solid mass with melting

point-131 C.

Precautions

1-phenylazo-2-napthol or Sudan 1 is an azo dye. In major azo dyes are very toxic and
carcinogenic in nature. Sudan 1 is known to cause malignancy, genetic mutation and toxic
effects when came in direct contact with skin or mucous membranes. Handle this dye with
optimum precautions