recrystallizing solvent is necessary.

The
substance to be crystallized must exhibit
ideal solubility behavior in the chosen

Recrystallization of Acetanilide
Introduction
Reyes, K.B., Rivera, G.I., Samonte, A.A., Soliven,
solvent. R.Y.*, Sotto,
Purification of K.C.
substances can
Organic compounds 2CMT, that Faculty
are of Pharmacy, UST
take place when both the substance to be
synthesized in laboratories or isolated purified and the impurities have similar
from natural recourses are often taintedAbstract solubility at its boiling point temperature;
Recrystallization
by impurities. is the primary method
Recrystallization is a for purifyingthe solid organic compounds through the
differences in solubility at different temperatures. Theand dissolved impurities correspond
solid has a decreased to only
solubility at a
process that removes these impurities small portion of the total solid. In this
lower temperature and separates from the solution as it is cooled. A small seed crystal is formed
from solidand
initially, organic
it thencompounds
grows layerthat are atIn this experiment,
by layer. manner, the substance
acetanilide to be by
was formed purified
the
room temperature.
acetylation of anilineThis
and process is built on
acetic anhydride. The crudewould be thewas
acetanilide only one crystallized.
dissolved in a solvent in a
the principle
hot water bath.that the solubility
The solution was then of a in an ice bath as crystals start to form. As the
cooled
compound
compound increases with temperature
formed crystals, and compounds dissolved in the solution are excluded
molecules of other
decreases as it cools
from the growing layerdown, into its
of crystals; crystal
hence, pure acetanilide is formed.
form.
Very pure compounds can be made
by recrystallization. A small pure seed
crystal of the compound forms in the
solution as it cools down after being
heated. Additional molecules are attached
to the crystal in uniform layers, forming a Figure 1 Structure of Aniline
growing crystal lattice. Crystal molecules Aniline [ C 6 H 5 N H 2 ] is a primary
have a higher affinity for the same kind of
amine in which the amino group is directly
molecules than impurities. This process of
attached to the benzene ring and the final
crystallizing removes one kind of molecule
product of the reduction of most nitrogen
from the solution. Recrystallization is a
derivatives of benzene. It has a density of
method in which two crystallization
1.0217 g/ml and a molecular weight of
processes were performed. It is usually
93.13 g/mol. Aniline is a clear to slightly
known as the second crystallization. It
yellow liquid with a characteristic odor. It
depends on the difference of solubility of a
does not readily evaporate at room
substance in a hot and in a cold solvent.
temperature. Aniline is slightly soluble in
Solubility refers to the degree of
water and mixes readily with most organic
substance which is the solute to be
solvents. It is used to make a wide variety
dissolved in solvent. It is the main factor
of products such as polyurethane foam,
that affects crystallization. Prior to the
agricultural chemicals, synthetic dyes,
recrystallization process, identifying the
antioxidants, stabilizers for the rubber
industry, herbicides, varnishes and
explosives.
When exposed to light and air, it
slowly changes color. It darkens because
of atmospheric oxidation of an impurity
usually present in the benzene from which
the aniline was prepared. Aniline is
acetylated by warming a mixture of aniline
and acetic anhydride, forming N-
phenylacetamide, which is more
commonly known as acetanilide.
Figure 2 Structural formula of Acetic
anhydride
Acetic Anhydride or Acetyl Ether is
a clear, colorless liquid with a very
pungent, penetrating, vinegar-like odor
that combines with water to form acetic
acid. It is soluble in ether, chloroform and
benzene. It has a density of 1.082 g/ml
and a molecular weight of 102.09 g/mol.
Its boiling point is at 140°C while its
melting point is at -73°C.
Acetic anhydride is used in the
manufacture of cellulose acetate having
the application as a base for magnetic
tape and in the manufacture of textile
fibres. Also, it is heated with salicylic acid
to produce acetylsalicylic acid (aspirin). It
is also used in the manufacture of
pigments, dyes, cellulose and pesticides
etc. Most importantly, it plays an
important role in the acetylation of aniline
to form acetanilide.
Figure 3 Structural formula of Acetanillide
Acetanilide [C6H5NH(COCH3)] or N-
Phenylacetamide is the product of
acetylation of aniline with acetic anhydride
at low temperature. It is an odorless,
white flake solid or crystalline powder
(pure form). Acetanilide is soluble in hot
water, alcohol, ether, chloroform, acetone,
glycerol, and benzene. It melts at a range
of 114-116°C and boils at 304°C. It can
undergo self-ignite at 545 C, but is
otherwise stable under most conditions.
Acetanilide is used as an inhibitor
of peroxides and stabilizer for cellulose
ester varnishes. It is used as an
intermediate for the synthesis of rubber
accelerators, dyes and dye intermediate
and camphor. It is used as a precursor in
penicillin synthesis and other
pharmaceuticals including painkillers and
intermediates. Phenylacetamide structure
shows analgesic and antipyretic effects;
however, acetanilide is not used directly
for it may cause methemoglobinemia (the
presence of excessive methemoglobin
which does not function reversibly as an
oxygen carrier in the blood).
The experiment aims to synthesize
acetanilide by the acetylation of aniline,
purify crude acetanilide product by
recrystallization, and calculate the
percentage yield of the pure acetanilide.
Methodology
A corn-grain amount of acetanilide
was placed into each of the three test
tubes. 1-ml of water was added to the
first test tube. 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 water bath.
Observations were recorded. For the
second and third test tubes, methanol and
hexane were used respectively using the
same procedure.
To produce crude acetanilide, 2-ml
of aniline and 20-ml distilled water were
mixed in an Erlenmeyer flask. A 3-ml
acetic anhydride was then added slowly
into the solution. All changes that took
place were noted. To hasten
crystallization, the solution was placed in
an ice bath then filtered through a wet
filter paper. The crude acetanilide was
dried and weighed by the use of an
analytical balance.
 A 20-ml recyrstallizing solvent was impure solid is dissolved in the hot
poured into the crude acetanilide. It was solvent, any undissolved impurities can be
then placed in a hot water bath until the removed by filtration. After the solution
solid dissolved. cools and the desired compound
If the solution is colored, it must crystallizes out, any remaining soluble
be removed from the water bath and a impurities will remain dissolved in the
small amount of activated charcoal must solvent.
be added to adsorb the colored impurities. Third, the solvent should not react
However, if the solution is colorless, it with the compound being purified. The
must be quickly filtered while still hot desired compound may be lost during
using a fluted filter paper. The filtrate was recrystallization if the solvent reacts with
allowed to cool by placing the receiver in a the compound.
beaker containing tap water. The crystals Lastly, The solvent should be
were collected, washed with distilled water volatile enough to be easily removed from
and dried by pressing-in between filter the solvent after the compound has
paper. It was then placed inside the locker crystallized. This allows for easy and rapid
until next meeting. drying of the solid compound after it has
The pure acetanilide collected was been isolated from the solution.
weighed using an analytical balance. The
melting point was likewise, determined. Solvent Room During Upon
temp. heating cooling
Results and Discussion
Water Insoluble Soluble Insoluble
The primary step involved in
recrystallization is selecting a suitable Methano Soluble Soluble Soluble
solvent. Recrystallizing solvent is a solvent l
that shows the desired solubility behavior
for the substance to be crystallized. Hexane Insoluble Insoluble Insoluble
Identifying the ideal recrystallizing
solvent of a compound is necessary to Table 1 Solubility of Pure Acetanilide
purify the organic compound. There are in Different Solvent
four important properties that you should
look for in a good solvent for Three solvents (distilled water,
recrystallization. methanol, and hexane) were tested. As
A compound usually exhibits one of shown in Table 1, methanol is soluble and
three general solubility behaviors: (1), the hexane is insoluble at room temperature,
compound has a high solubility in both hot during heating, and upon cooling. Hence,
and cold solvent, (2), the compound has a acetanilide, when placed on these two
low solubility in both hot and cold solvent, solvents, cannot undergo recrystallization.
and (3), the compound has a high Both methanol and hexane are flammable
solubility in hot solvent and a low and volatile. Thus, extra caution must be
solubility in cold solvent. Solvents which utilized. However, distilled water exhibited
exhibit the first two behaviors are not a different result. At room temperature it
useful for recrystallizing a compound. The was insoluble; during heating it was
first characteristic of a good recrystallizing soluble; and upon cooling, it was
solvent is exhibited by a solvent showing insoluble. Water shows the desired
the third behavior, that is, high solubility solubility behavior of an ideal
at high temperatures and low solubility at recrystallizing solvent.
low temperatures. Absorption of heat is exhibited
Second, the unwanted impurities when acetanilide is placed in a hot water
should be either very soluble in the bath. Thus, the solute dissolves in the
solvent at room temperature or insoluble solvent. In contrast, the reaction of aniline
in the hot solvent. This way, after the with acetic anhydride, producing
acetanilide exhibits release of heat or amount of mother liquor, washing of
exothermic reaction. During cooling, the crystals with cold distilled water must be
temperature is lowered so that heat shall done. However, during filtration, some
be removed. Therefore, crystals form. part of the solution was lost that resulted
Hastening of crystallization is done to reduction of the pure acetanilide.
through ice water bath which decreases After filtration, the crystals were
the solubility of acetanilide. dried by pressing-in between filter paper.
However, some were not weighed because
Weight of the crude 2.24 g the crystals were attached to some part of
acetanilide the filter paper. The weight of the pure
Weight of pure 1.00 g acetanilide collected was reduced to 1.00
g.
acetanilide
To calculate the percentage yield,
Percentage Yield 64% the theoretical yield and the limiting
Table 2 The actual yield of crude and reagent must be first identified. The
pure acetanilide, and the percentage theoretical yield is the maximum yield of
yield of pure acetanilide pure crystals that could be obtained by
cooling or evaporating a given solution.
The weight of the crude acetanilide This refers to the quantity of pure crystals
is 2.24 g. The acetylation of aniline and deposited from the solution. On the other
acetic anhydride would yield to acetanilide hand, limiting reagent is the reactant that
but it may contain small amount of is used up first in a reaction.
impurities which may affect the weight of
pure acetanilide. During recrystallization,
the solution was placed in a hot water C 6 H 5 NH 2 + ( CH 3 CO 2 ) OCH 3 CO 2 H CH 3 • CO • NH •C 6 H 5+
bath. It would be noted that the →
recrystallizing solvent is not enough to
dissolve the substance which may result Aniline∈grams:
to reduction of the crystallized acetanilide. 1.0217 g
During the water bath in 2 ml C 6 H 5 NH 2 × =2.0434 g
1 ml
recrystallization, the solution would look
Acetic anhyrdride ∈grams :
as if it was colored because of impurities.
These impurities may be decolorized by
1.082 g
3 ml ( CH 3 CO 2 ) O× =3.2460 g
the use of activated charcoal which 1 ml
adsorbs impurities because it has a large
surface area and it can remove impurities
more effectively. However, just a small Identify the limiting reagent:
amount of activated charcoal should be
added. Too much activated charcoal will 1.0217 g 1mole
2 ml C 6 H 5 NH 2 × × =0.0219 moles C 6 H 5 NH
also adsorb the desired substance. 1 ml 93.13 g
Filtration is the most effective way
to remove unwanted impurities most 1.082 g 1mole
especially when decolorization was 3 ml ( CH 3 CO 2 ) O× × =0.0318 moles ( CH 3 C
1 ml 102.09 g
utilized; hence, the solution should be
immediately filtered in an ice water bath Hence, the limiting reagent is
while still hot. Take note that premature
recrystallization may occur when the Aniline (C 6 H 5 NH 2 ).
solution in the flask was not kept in its
boiling point temperature. Evaporation of Theoretical yield = mass of LR
solvent may initiate premature
crystallization. Actual Yield
% Yield= ×100
Mother liquor refers to the solution Theoretical Yield
that remains in the crystals. To reduce the
 1.00 g CA/CCA6/MAIN/1ChemLabMenu/Separatin
¿ ×100=49 % g/F_1SOLVE_MENU/F_1SOLVE/F_1SOLVE
2.0434 g
_01/F_1SOLVE_10/MOVIE.HTM
The percentage yield based on the
experiment is 49%. This is the pure RECRYSTALLIZATION
acetanilide obtained from the 2-ml aniline Retrieved August 21, 2010, from
and 3-ml acetic anhydride. http://www.chem.umass.edu/~samal/269
/cryst1.pdf
The melting point of pure
acetanilide was also determined by
immersing a capillary tube with pure
acetanilide attached to a thermometer
into an oil bath.
The melting point of the crude
acetanilide ranges from 115-118°C while
the pure acetanilide melts at 110-116°C.
Hence, the recrystallized acetanilide
obtained is pure.

References

Books:
Bayquen, A., Cruz, C. et.al. (2009).
Laboratory Manual in Organic Chemistry.
Philippines: C & E Publishing, Inc. Pg. 47-
48

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

Web sites:
ACETANILIDE (N-PHENYLACETAMIDE).
(n.d.). Retrieved August 21, 2010, from
http://chemicalland21.com/lifescience/pha
r/ACETANILIDE.htm

ACETIC ANHYDRIDE (ACETYL ETHER).

(n.d.). Retrieved August 21, 2010, from
http://chemicalland21.com/petrochemical
/ACETIC%20ANHYDRIDE.htm

PURIFYING ACETANILIDE BY
RECRYSTALLIZATION. Retrieved August
22, 2010, from
http://www.cerlabs.com/experiments/108
7540703X.pdf

RECRYSTALLIZATION SOLVENT. Retrieved

August 21, 2010, from
http://jchemed.chem.wisc.edu/JCESoft/C