RECRYSTALLIZATION

Abstract
Recrystallization is the simplest and most widely used operation for purifying
organic solids that differ in their solubility at different temperature. In this experiment,
Acetanilide was used as the pure organic compound. Acetylation of Aniline and Acetic
Anhydride yields the crude product or crude Acetanilide. The Acetanilide will undergo
another crystallization process using the preferred Recrystallizing Solvent. The product of
the 2nd crystallization will be the Pure Acetanilide. Determine the Melting Point of the Pure
Acetanilide to confirm its purity. When the acquired melting point is near the theoretical
melting point of Acetanilide then the produced Pure Acetanilide is indeed pure.
Recrystallization is based on the fact that the solubility of a solid in a given solvent
increases with the temperature of the solvent.

Introduction derivative. The largest application of Aniline is for

Organic Compounds are members of the
chemical compounds whose molecules contain
carbon. Organic compounds that came from the
nature, whether solid or liquid, contain impurities
in them. There are different purification methods
that can be used to remove the impurities
present in a compound. For liquids, Distillation
(Experiment 1) is the most common used
purification method. It separates volatile liquids
on the basis of their boiling points. For solids,
Recrystallization is the simplest and most widely
used purification method.
the preparation of Methyl Diphenyl Diisocyanate
(MDI), which is used for the production of
polyutherane. Aniline is a toxic substance that
affects the oxygen inside the blood, resulting the
hemoglobin to transform to methemoglubin that
causes cyanosis. It can also cause skin irritation
when there is skin contact. Chemical facts of
Aniline:
 Molar Mass : 93.13 g/mol
 Density : 1.0217 g/ml
 Melting Point : -6 ˚C

Crystallization is a purification method

usually used by chemist to remove impurities to
solids. Recrystallization is so named because it
involves dissolving a solid that, in most cases,
had originally crystallized from a reaction mixture
or another solution, and then causing it again to
crystallize from solution. During the first
crystallization a crude product will be formed.
This product still have impurities that needs to be
remove that is the reason for doing crystallization
for the 2nd time. The product of Recrystallization Fig.1 Structure of Aniline
will have fewer impurities, close to none, than
the crude product. The level of purity of the Acetanilide is the product of this
product can be checked through its melting point Recrystallization. Acetanilide or N-
range. Looking closely to the crystals, they phenylacetamide (IUPAC name) with a formula of
formed a lattice structure. Lattice is a fixed and C6H5NH(COCH3) is produced by adding Acetic
rigid arrangement of atoms, molecules or ions. Anhydride with Aniline. It is used as an inhibitor
Formation of crystals is due to the difference in in hydrogen peroxide and is used to stabilize
solubility of the solid with the solvent. Solutes or cellulose ester varnishes. Acetanilide has
compounds tend to be more soluble in hot analgesic and antipyretic properties but is not
solvents than they are in cold solvents. that usually used due to its side effects of
cyanosis just like Aniline. Chemical facts of
Aniline is the primary compound used to Acetanilide:
acquire Acetanilide, which is our product. Aniline  Molar Mass : 135.17 g/mol
or Phenylamine(IUPAC name) with a formula of  Density : 1.219 g/cm3
C6H5NH2, is a odorless, oily, poisonous benzene  Melting Point : 114 -116 ˚C

Fig.2 Structure of Acetanilide
Acetic Anhydride is the reagent added to
Aniline to undergo acteylation. Acetylation is the
process of introducing an acetyl functional group
into a compound. Acetic Anhydride or Ethanoic
Anhydride, whose chemical formula is C 4H6O3, is
widely used as reagent in chemical synthesis. It
has a vinegar-like odor and reacts with water to
form Acetic Acid. It is also used in manufacturing
aspirin, formed due to acetylation of Salicylic
Acid. Chemical Facts about Acetic Anhydride:
 Molar Mass : 102.09 g/mol
 Density : 1.082 g/cm3
 Melting Point : -73.1 ˚C
Fig.3 Structure of Acetic Anhydride
Objectives of the Experiment are as
follows:
 Synthesize Acetanilide by acetylation of
Aniline.
 Purify crude Acetanilide product by
Recrystallization.
Experimental
Deposit a corn-grain sized amount of
crude Acetanilide into three (3) different test
tubes. Add distilled water to one test tube,
hexane to another, and methanol to the last.
Shake well and note the solubility of Acetanilide.
After shaking, put them in a water bath for 1-5
minutes, again, note the solubility of Acetanilide
in its respective solvents under heat. Then place
immediately to an ice bath. For the last time,
note the solubility of Acetanilide. This process will
determine the appropriate and the best solvent
that will yield pure Acetanilide through the
acetylation of Aniline and Acetic Anhydride.
In an Erlenmeyer flask, add 2ml of Aniline
with 20ml of distilled Water then slowly add 3ml
of Acetic Anhydride. Put the flask in an ice bath
that will hasten the crystallization of the solution.
When the crystals are fully formed, filter the
solution to obtain the formed crystals, which will
be the crude Acetanilide. After filtering, dry the
crystals by pressing the crystals with filter paper
that will sip the remaining liquid, or leaving the
crystals over-night for the liquid to evaporate on
its own. When the crude Acetanilide is completely
dry, weigh it using the analytical balance. This
process is the first crystallization on the
experiment.
When the crude Acetanilide is completely
dry, add 10ml of the chosen solvent, for our
group we chose Methanol (CH3OH), to it. Put the
solution in a water bath to hasten the reaction.
Note the changes in the solution. If the solution
became colored, put activated charcoal that will
remove the color due to its ability to absorb color
materials. Filter the solution while it is hot and
immediately put the filtrate to an ice bath to
hasten the crystallization of the solution. When
the solution is done crystallizing, filter the
solution and wash the residue or the crystals with
distilled water to completely remove the
impurities remaining in them. Let the crystal dry
just like the crude Acetanilide. The 2nd product
will be the Pure Acetanilide. After drying the pure
Acetanilide, weigh it using the analytical balance.
For the determination of the purity of the
pure Acetanilide find its melting point and
compare it with the theoretical melting point of a
pure Acetanilide. Triturate the crystals using a
mortar and pestle to produce a fine powder. In a
capillary tube, put at least a centimeter of
triturated pure Acetanilide. Put it in a oil bath and
determine the melting point of the pure
Acetanilide.
Results and Discussion
Recrystallization starts with finding the
right recrystallizing solvent for the given
compound. The solubility of Acetanilide was
tested for the three (3) given solvents, Water,
Hexane, and Methanol respectively. A compound
usually exhibits one of the three general solubility
behaviors: (1), the compound has a high
solubility in both hot and cold solvent, (2), the
compound has a low solubility in both hot and
cold solvent, and (3), the compound has a high
solubility in hot solvent and low solubility in cold
solvent. A solvent showing the 3 rd characteristic
or behavior is the one suitable as a
Recrystallizing Solvent.
Fig.4 A graph showing the three general
behaviors of solubility. The “Good” line is the
Recrystallizing Solvent.
When Acetanilide was added to the three
solvents in room temperature, Acetanilide was
insoluble in Water and Hexane while soluble with
Methanol. Immediately after that, the test tubes
were heated through water bath. The behavior of
Acetanilide in Water solvent changed when
submerged in water, it became soluble.
Compared to Water, the Acetanilide in Methanol
and Hexane remains soluble and insoluble
respectively. After heating the test tube, they
were cooled using ice bath. Upon cooling, the
Acetanilide in the water were again insoluble
same as Hexane which is also insoluble. For the
outcome of Acetanilide in Methanol, some
problem occurred, due to Acetanilide became
soluble when cooled but it should be insoluble.
The problem was that, Methanol dried up during
heating in the water bath. The temperature in the
water was greater than the boiling point of
Methanol causing it to evaporate easily.
At Room During Upon
Sovent
Temp Heating Cooling
Water Insoluble Soluble Insoluble
Methanol Soluble Soluble Insoluble
Hexane Insoluble Insoluble Insoluble
Table 1. Solubility of Acetanilide with the three
given solvents: Water, Methanol, and Hexane.
Water And Methanol both exhibits the
third behavior, the compounds has a high
solubility in hot solvent and low solubility in cold
solvent. But Water is still the best Recrystalizing
Solvetn compared to Methanol because it is
insoluble in room temperature.
The first Crystallization starts with the
Acetylation of Aniline with Acetic Anhydride. The
solution then undergoes heating and cooling that
will produce the crude Acetanilide. As the solution
cools, the solubility of the compound, and of the
soluble impurities, decreases, and the solution
becomes saturated with the desired compound,
and the compound starts to crystallize. Crude
Acetanilide still contains impurities than affects
the weight of the Acetanilide. This part is the first
Crystallization process. When the crude
Acetanilide dried up, repeat the process using the
determined Recrystallizing solvent, which should
be Water. But some, just like our Group, used
Methanol as their Recrystallizing Solvent.
Choosing the right Recrystallizing solvent is vital
because it affects the Percent Yield of Acetanilide
from the solution. Methanol, a volatile substance,
can cause disintegration of Acetanilide causing to
yield less Acetanilide than Water can. If the
solution changed in color during heating, put
some activated charcoal in the solution to remove
the color. Activated Charcoal absorbs colored
materials in a solution. After heating, filter
immediately the solution to as beaker. Filtering
while still hot is essential because it affects the
percent yield of Acetanilide. Place the beaker in a
ice bath to hasten the crystallization of the
solution. Filter the crystals and wash with distilled
Water to remove the remaining impurities
present in the product. The product of the second
crystallization is the Pure Acetanilide or the
Recrystallized Acetanilide. The impurities present
in the product is less or almost completely gone
compared to the crude Acetanilide.
Weight of Crude Acetanilide :
2.4902 g
Weight of Pure Acetanilide :
0.8807 g
To determine the purity of the product or
the Acetanilide, determine the melting point of
the product using Capillary Method. Triturate the
Pure Acetanilide using the Mortar and Pestle to
Pure Acetanilide granules inside, together with a
thermometer in a beaker of cooking oil. Using
cooking oil is essential because it has a higher
boiling point compared to water. The boiling point
of water is 100˚C while cooking oil is around
200˚C. Another reason is that a Pure Acetanilide
has a higher melting point than the boiling point
of water. If water was used to determine the
boiling point, water will evaporate immediately
even before reaching the melting point of
Acetanilide.
Melting Point of Pure Acetanilide :
acquire fine granules that can fit the opening of a
capillary tube. Submerge the capillary tube, with
114-116˚C
Melting Point of Recrystallized Acetanilide :
108-109˚C
Calculating the Percent Yield of the Recrystallized
Acetanilide, the limiting reagent must be
determined first. Limiting Reagent is the reactant
in a chemical reaction that limits the amount of
product that can be formed. Percent Yield is the
percent of the pure form of a compound formed
during the reaction. This refers to the percent of
Pure Acetanilide formed after Recrystallization.

Calculations for Percent Yield:

Grams Aniline Grams Acetic Anhydride

Limiting Reagent

Percent Yield

Aniline is the Limiting Reagent because it needs 2.96 g to completely react with 3mL of Acetic
Anhydride. The Percent yield of the reaction is 43.10%. It means that only 43.10% pure Acetanilide was
formed after the reaction. It did not reach the value of 90-100% mainly because the Recrystalizing solvent
used was not that effective with Acetanilide. Methanol might have cause disintegration with the Acetanilide
causing it to lose some of its molecules giving a poor weight.
References

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Newtown, Massachusetts, USA.: Allyn and Bacon Inc. Pp. 44-61.

Lehman, J.W. (2009). Operational Organic Chemistry A Problem-Solving Approach to the Laboratory
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Recrystallization (n.d.) http://www.chem.umass.edu/~samal/269/cryst1.pdf

Wigal C. (n.d.) Purifying Acetanilide by Recrystallization. Lebanon Velley College.

http://www.cerlabs.com/experimen ts/1087540703X.pdf