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Recrystallization of Acetanilide

Authors: ABESAMIS, M.F., ACOSTA, M.C., AGUSTIN, F., AQUITANIA, M.C.,


BAGSICAN, M.J.

Abstract
Recrystallization is a common method of purifying organic substances
through the difference in solubility at different temperature. In this
experiment, acetanilide was produced by acetylation of aniline with acetic
anhydride. The crude acetanilide was dissolved in a solvent in a heating
water bath. The solution was cooled slowly in an ice bath as crystals form
out. As the compound crystallizes from the solution, molecules of other
compounds dissolved in solution are excluded from growing crystal lattice,
yielding pure acetanilide.

I. Introduction
Organic compounds that are solid at room temperature are usually
purified by crystallization. Crystallization is the deposition of crystals from a
solution. During the process of crystal formation, a molecule have the
tendency to be attached to a growing crystal composed with the same type
of molecules because of a better fit in a crystal lattice of a molecule of the
same structure than for other molecule. (Pastro, John, & Miller) Lattice is a
fixed and rigid arrangement of atoms, molecules or ions. (Mullin, 1961)
Recrystallization is a method in which two crystallization processes was
performed. It is referred to the second crystallization. (Pavia, Lampman, Kriz,
& Engel, 1999) It depends on the difference of solubility of a substance in a
hot and in a cold solvent.

Solubility is the degree of substance which is the solute to be dissolved


in solvent. It is the main factor that affects crystallization. Before performing
crystallization, identifying a recrystallizing solvent is significant. The
substance to be crystallized should show the ideal solubility behavior in
solvent. A substance can be purified when both the desired substance and
the impurity have similar solubility at its boiling point temperature, and when
the impurity represents only a small fraction of total solid. The desired
substance will crystallize on cooling, but the impurities will not. (Pavia,
Lampman, Kriz, & Engel, 1999)

Figure 1 Structural formula of Aniline

Aniline is a primary amine in which the amino group is


directly attached to the benzene ring and the final product of the reduction of
most nitrogen derivatives of benzene. Aniline is a colorless, oily, poisonous
liquid that boils at 182°C when pure. The density of aniline is 1.0217 g/ml
and its molecular weight is 93.13 g/mol. On standing in air and light, it
gradually darkens in color due to oxidation due to atmospheric oxidation of
an impurity commonly present in the benzene from which the aniline was
prepared. Acetylation is a reaction in which acetyl functional group is
introduced into an organic compound. Aniline is acetylated by warming
mixture of aniline with acetic anhydride, acetyl chloride or even glacial acetic
acid forming N-phenylacetamide, which is commonly known as acetanilide.
(Wood, 1964)

Equation 1 Acetilation, a chemical reaction of Aniline with Acetic anhydride to


produce Acetanilide and Acetic acid

Figure 2 Structural formula of Acetic anhydride

Acetic anhydride is a colorless liquid with a pungent


vinegar-like odor when it reacts with water to form acetic acid. The boiling
point of acetic anhydride is 140°C and the melting point is -73°C. It is
soluble in ether, chloroform and benzene. It is soluble in water when acetic
anhydride decomposes. The density of acetic anhydride is 1.082 g/ml in
liquid state and its molecular weight is 102.09 g/mol. Acetic anhydride is
most widely used for the conversion of cellulose to cellulose acetate, which is
a component of photographic film and other coated materials. It plays an
important role in the acetylation of aniline to form acetanilide. (ACETIC
ANHYDRIDE (ACETYL ETHER))

Figure 3 Structural formula of Acetanillide

Acetanilide [C6H5NH(COCH3)] is the product of acetylation of aniline


with acetic anhydride at low temperature. It is a white, odorless flake solid or
crystals that boils at 304°C and melts in the range of 114-116°C. The density
of acetanilide is 1.219 g/ml. Acetanilide is soluble in hot water, alcohol, ether,
chloroform, acetone, glycerol and benzene. It is stable under normal
condition and can undergo self-ignite at 545°C. (ACETANILIDE (N-
PHENYLACETAMIDE)) Acetanilide is used as a precursor in penicillin synthesis
and other pharmaceuticals including painkillers and intermediates. In
medicine, it is a prodrug with analgesic and antipyretic, or fever-reducing
properties which is in the same class of drugs as acetaminophen, in generic,
paracetamol. However, direct application of acetanilide may cause
methmoglobinemia and damage liver and kidneys. (ACETANILIDE (N-
PHENYLACETAMIDE))

The objectives of the experiment are as follow: (1) to synthesize


acetanilide by the acetylation of aniline; (2) to purify crude acetanilide
product by recrystallization; and (3) to calculate the percentage yield of pure
acetanilide.

II. Experimental
A corn grain amount of pure acetanilide was placed into each of the
three test tubes. The first test tube contained 1-ml distilled water. The test
tube was shaken and placed in a warm water bath (37 – 40°C) for 1 – 5
minutes. Then, it was cooled through an ice bath. Solubility of pure
acetanilide was recorded. For methanol and hexane, the same procedure was
done.

To produce crude acetanilide, a 20-ml distilled water and 2-ml aniline


was place in an Erlenmeyer flask respectively. A 3-ml acetic anhydride was
added slowly in the solution. All changes that occurred were noted. To hasten
crystallization, it was placed in an ice bath then filtered to a wet filter paper.
The crude acetanilide was dried and weighed using an analytical balance.

A 20-ml recyrstallizing solvent was poured into the crude acetanilide.


It was placed in a hot plate until the solid was dissolved. The solution was
removed from the water bath when the solution was colored. A small amount
of activated charcoal was added to adsorb the colored impurities. The
solution was quickly subjected to filtration while hot. The filtrate was placed
in a receiver in a water bath to hasten recrystallization. The crystals were
washed using distilled water. Then, crystals collected were dried through
pressing-in between filter paper. The pure acetanilide was weighed using an
analytical balance.

III. Results and Discussion


Recrystallizing solvent is a solvent that shows the desired solubility
behavior for the substance to be crystallized. Identifying the ideal
recrystallizing solvent of a compound is necessary to purify the organic
compound. Trial-and-error method is commonly done when the compound to
be purified is unknown. In choosing the recrystallinzing solvent, the
compound should be insoluble at room temperature. While heating, the
compound should be very soluble and upon cooling, it is insoluble. The
unwanted impurities should be soluble at room temperature or insoluble
during heating. The applied amount of heat energy associated with a given
temperature in a given system is the heat capacity. (Mullin, 1961) It should
not go beyond the melting point of the substance to be crystallized. If the
boiling point of the solvent is high, the solid may melt in the solvent rather
than dissolve. In such case, the solid may oil out. Oiling occurs when the
solid substance melts and forms a liquid that is insoluble in the solvent.
When cooling, the liquid refuses to crystallize; rather, it becomes a
supercooled liquid, or oil. Oils may solidify if the temperature is lowered, yet
will not crystallize. (Pavia, Lampman, Kriz, & Engel, 1999) In addition,
volatility of the solvent is a factor in selecting the correct recrystallizing
solvent. The solvent should be volatile enough to be easily removed from the
solution after crystallization. Volatile solvents having low boiling point is
preferable. (Pavia, Lampman, Kriz, & Engel, 1999) The chemical reactivity of
recrystallizing solvent should be low. It should neither decompose nor oxidize
the desired substance. The solvent should not react with the compound to be
purified. Thus, the desired substance may be contaminated with impurities.
(Mullin, 1961)

Table 1 Solubility of Pure Acetanilide in Different Solvent

Solvent At room During Upon


temp. heating cooling
Water Insoluble Soluble Insoluble
Methanol Soluble Soluble Soluble
Hexane Insoluble Insoluble Insoluble

On Table 1, there were three (3) solvent that was tested, distilled
water, methanol and hexane. Methanol is soluble while hexane is insoluble in
all system. This shows that acetanilide that will be place in this solvent
cannot undergo recrystallization. Nevertheless, recystallization will not occur.
In addition, extra precaution must be taken because methanol and hexane
are flammable and highly volatile. However, distilled water exhibits different
result; rather, it shows the desired solubility behavior of an ideal
recrystallizing solvent for acetanilide. At room temperature it was insoluble;
during heating it was soluble; and when placed upon cooling it was insoluble.
Water is quite suitable for melting points of pure organic compounds from
about room temperature to about 70°C in heating water bath.

Heat is generally absorbed when acetanilide is introduced to heating water


bath. The solute dissolves in the solvent. (Mullin, 1961) In acetylation of
aniline with acetic anhydride, yielding acetanilide exhibits an exothermic
reaction. Exothermic reaction is the release of heat from the system. In case
of cooling, the heat has to be removed from the system, the temperature is
lowered. Thus, crystals form. Hastening crystallization is done through ice
bath. This method decreases the solubility of acetanilide.
Table 2 The actual yield of crude and pure acetanilide, and the percent yield of pure
acetanilide

Weight of the 2.7370g


crude acetanilide
Weight of pure 1.8997g
acetanilide
Percentage Yield 64%

The weight of the crude acetanilide is 2.7370g. Acetylation of aniline


and acetic anhydride contains small amount of impurities that may affect the
weight of the substance from crystallization. During recrystallization process,
the solution was subjected to heating water bath. The recrystallizing solvent
should not be enough to dissolve the substance. This is a common error that
may reduce the solid yield returned into crystals. (Pavia, Lampman, Kriz, &
Engel, 1999)
During heating water bath in recrystallization, highly colored impurities
may make the solution appeared colored. These colored impurities can often
be removed by decolorization by using activated charcoal, often called Norit.
A decolorizing step is performed only if the color is due to impurities, not to
color the desired product, and if color is significant. Small amount of colored
impurities will remain in solution during crystallization, making decolorizing
step unnecessary. Activated charcoal adsorbs the impurities because it has a
large surface area and it can remove impurities more effectively. Only small
amount of activated charcoal should be added. Too much activated charcoal
used will not only adsorb the impurities but also the desired product. When
adding activated charcoal, be cautious so that the solution will not erupt.
Using activated charcoal in a minimum amount may reduce the risk of lung
irritation. (Pastro, John, & Miller, 1998)

When the acetanilide was dissolved, the solution should be


immediately filtered while hot in an ice bath. Filtering is most effective way to
remove solid impurities, especially when decolorization is applied. The
solution in the flask should be kept in its boiling point temperatures to
prevent premature crystallization. Premature crystallization may contain
some of the impurities from the solvent. Evaporation of solvent may initiate
premature crystallization. Washing of crystals with cold recystallizing solvent
was done to help reduce the amount of mother liquor retained by the mass of
crystals. (Mullin, 1961) The mother liquor is the solution that remains in the
crystals. (Pavia, Lampman, Kriz, & Engel, 1999) Distilled water was used for
washing because it is the recrystallizing solvent for acetanilide. However,
during filtration, some part of the solution was lost and was not subjected to
fitration that resulted to reduction of the yielded pure acetanilide.

Drying the crystals was done after filtration. The most common
method involves placing the crystals on a watch glass, a clay plate or a piece
of paper and allowing it to dry in air. Acetanilide crystals were dried by
pressing-in of crystals with filter paper. During the process, some of the
residue was not weighed because the particles were attached to some part of
the filter paper. Rushing the drying process resulted to reduction of the
yielded pure acetanilide. The weight of the pure acetanilide was reduced to
1.8997g.

To calculate the percentage yield, the limiting reagent and theoretical


yield should be identified. Limiting reagent is the reactant that is used up
first in a reaction. (Chang, 2008) Theoretical yield is the maximum yield of
pure crystals that could be obtained by cooling or evaporating a given
solution. This refers to the quantity of pure crystals deposited from the
solution. (Mullin, 1961)

Calculate for the limiting reagent:

Thus, the limiting reagent is aniline because it needs 2.96g to react


with 3ml

The percentage yield calculated is 93%. This is the pure acetanilide


obtained from the 2ml aniline and 3ml acetic anhydride.

IV. References
Books:
Chang, R. (2008). General Chemistry: The Essential Concepts (5th Ed.). New
York: McGraw-Hill. Pg. 81-85

Mullin, J. W. (1961). Crystallization. London, England: Butterworth & Co. Pg.


1, 21, 29-35, 39-55, 57-58, 62, 120-121, 140-141

Pastro, D. J., John, C. R., & Miller, M. S. (1998). Experiment and Techniques
in Organic Chemistry. New Jersey: Prentice Hall. Pg. 43-46

Pavia, D. L., Lampman, G. M., Kriz, G. S., & Engel, R. G. (1999). Organic
Laboratory Techniques: A Microscale Approarch (3rd Ed.). Harcourt College
Publiser. Pg. 558-576

Wood, C. (1964). Organic Chemistry (2nd Ed.). London: Butterowowrths &


Co. Pg. 139-140, 264-273

Web sites:
ACETANILIDE (N-PHENYLACETAMIDE). (n.d.). Retrieved August 16, 2009 ,
from http://chemicalland21.com/lifescience/phar/ACETANILIDE.htm

ACETIC ANHYDRIDE (ACETYL ETHER). (n.d.). Retrieved August 16, 2009,


from http://chemicalland21.com/petrochemical/ACETIC%20ANHYDRIDE.htm