University of Santo Tomas

Faculty of Pharmacy
Organic Chemistry Laboratory

RECRYSTALLIZATION OF ACETANILIDE

Jane Catherine SP. Villanueva, Edenn Claudine C. Villaraza, Lorenz Oliver C. Villegas and
Cristel Bernice T. Wee

Group 10 2G-Medical Technology Organic Chemistry Laboratory

ABSTRACT
Recrystallization is one of the simplest and most widely used technique for purifying organic solids through the
differences in solubility at different temperatures. It is also the process in which the solid to be crystallized is dissolved
to either a hot solvent or a hot solvent mixture and is cooled in a solution.
In this experiment, acetanilide, the crude product of acetylation of aniline and acetic anhydride, was used as
the pure organic compound. Crude acetanilide underwent crystallization process using the preferred recrystallizing
solvent, water. The crystallization process was when crude acetanilide was placed in hot water bath and was cooled
after in an ice bath which would then yield to the formation of crystals of pure acetanilide. The percentage yield form
the crude acetanilide was 73.72% while the percentage yield from pure acetanilide was 61.93%. The percentage
recovery in the experiment was 84.00 %

INTRODUCTION

Organic compounds that came from the
nature, whether solid or liquid, contain impurities
in them. Different purification methods can be
used to remove the impurities present in a
compound. For liquids, distillation is the most
common used purification method. It separates
volatile liquids on the basis of their boiling points.
As for solids, either sublimation or
Recrystallization can be used. Sublimation is only
use for solids which can directly pass into vapor
phase without passing through the liquid phase.
On the other hand, Recrystallization involves
solid which doesn’t have the same property of
liquids used in sublimation. It is a method which
purifies organic solids base on its solubility. It is
also a process which dissolves solid to be
crystallized in a hot solvent mixture and cools it
afterward. The dissolve solid decreases in
solubility at a low temperature and separates as
it cools resulting to small seed crystals.
solvents than they were in cold solvents. The
crystals formed have a lattice structure that is a
fixed and rigid arrangement of atoms, molecules
or ions.
Solubility refers to the degree of
substance in which the solute is to be dissolved in
solvent. It was the main factor that affects
crystallization. Identifying the recrystallizing
solvent was very important in crystallization
process. The substance to be crystallized must
exhibit ideal solubility behavior in the chosen
solvent. Purification of substances could take
place when both the desired substance and the
impurities have similar solubility at its boiling
point temperature; and the impurities correspond
to only a small portion of the total solid. The
desired compound will crystallize in cooling
temperature while impurities will not.

Crystallization was done twice. During the

first crystallization a crude product would be
formed which would still have some impurities
that needs to be remove. This was the reason for
doing crystallization for a second time yield to a
Fig.1 Structure of Aniline
pure product which contained fewer or no
impurities at all. The level of purity of the product
Aniline (C6H5NH2) also known as
can be checked through its melting point range.
aminobenzene or benzenamine is a primary
Formation of crystals was due to the difference in
amine in which the amino group is directly
solubility of the solid with the solvent. Solutes or
attached to the benzene ring and the final
compounds tend to be more soluble in hot
product of the reduction of most nitrogen
derivatives of benzene. Its IUPAC name is
phenlyamine, has a density of 1.0217 g/ml and a
molecular weight of 93.13 g/mol. Aniline is a
clear to slightly yellow liquid with a characteristic
odor. It does not readily evaporate at room
temperature. Aniline is slightly soluble in water,
3.6g/100mL at 20°C, and mixes readily with
most organic solvents. It is used to make a wide
variety of products such as polyurethane foam,
agricultural chemicals, synthetic dyes,
antioxidants, stabilizers for the rubber industry,
herbicides, varnishes and explosives.
When exposed to light and air, it slowly
changes it color and 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.
Figure2. Structure of Acetic Anhydride
Acetic Anhydride (C4H6O3) or Acetyl Ether
or Acetyl Oxide 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 fibers. 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. Structure of Acetanilide
Acetanilide (C6H5NH(COCH3)) which has a
IUPAC name of 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. 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 also 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 objectives of the experiment were to
synthesize acetanilide by the acetylation of
aniline, to purify crude acetanilide product by
recrystallization, and to calculate the percentage
yield of the pure acetanilide.
EXPERIMENTAL
A. Sample Used
 Acetic Anhydride
 Aniline
 Acetanilide
 Activated charcoal
 Methanol
 Hexane
 Water
B. Procedure
1. Determination of best and
appropriate recrystallizing solvent
A corn-grain size amount of crude
acetanilide was put into three different test tubes.
Distilled water was placed in one of test tube,
hexane to another, and methanol to the last.
They were then shaken well and were noted base
on each of its solubility of acetanilide. Afterwards,
they underwent water bath for about 1-5 minutes,
again, the solubility of acetanilide in its
respective solvents under heat were noted.
Immediately they were place onto an ice bath.
For the last time, solubility of acetanilide in each
test tube was noted. This process would
determine the appropriate and the best solvent
that would yield pure Acetanilide which came
from the acetylation of Aniline and Acetic
Anhydride.
2. First crystallization
In an Erlenmeyer flask, 2ml of aniline,
20ml of distilled water and 3ml of Acetic
Anhydride were added. Changes were noted.
Afterwards the flask was placed in an ice bath to
cool which would hasten the crystallization. When
the crystals were fully formed, the solution was
filtered to be able to obtain the formed crystals,
the crude Acetanilide. Then the residue was dried
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 was completely dry,
it was weighed using the analytical balance.
Figure 4. Ice Bath Set-up
3. Second crystallization
When the crude Acetanilide was
completely dry, 20-mL of recyrstallizing solvent,
water, was added. It was then placed in a hot
plate until the solid was dissolved. Afterwards the
solution was removed from the water bath, to be
able to put a small amount of activated charcoal
because the solution was colored. A small
amount of activated charcoal was placed to
absorb the colored impurities. Afterwards the
solution was quickly subjected to filtration while
hot. Allow it to cool then collect crystals. It was
then washed by distilled water. Dry the residue
just like the procedure in first crystallization by
pressing the crystals with filter paper that would
sip the remaining liquid, or leaving the crystals
over-night for the liquid to evaporate on its own.
When the pure acetanilide was completely dry, it
was then weighed using the analytical balance.
Figure 5. Filtration Set-up
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
The first step involved in recrystallization
was selecting the recrystallizing solvent for the
solute. Recrystallizing solvent is a solvent that
shows the desired solubility behavior for the
substance to be crystallized. Trial-and-error
method was commonly done when the compound
to be purified is unknown.
Identifying the ideal recrystallizing solvent
of a compound was essential to purify the organic
compound. A compound usually exhibits one of
three general solubility behaviors. It is either the
compound has a high solubility in both hot and
cold solvent or it has a low solubility in both hot
and cold solvent or it has a high solubility in hot
solvent and a low solubility in cold solvent.
The important properties for in a good
solvent for recrystallization were exhibit by the
third behavior. The compound should be insoluble
at room temperature at the same time it should
be very soluble during heating or at high
temperatures and it should be insoluble upon
cooling or at low temperatures. The unwanted
impurities should also be considered. It must be
either very soluble in the solvent at room
temperature or insoluble in the hot solvent. This
way, after the impure solid had dissolved in the
hot solvent, any undissolved impurities could be
removed by filtration. After the solution had
cooled and the desired compound had crystallized
out, any remaining soluble impurities would
remain dissolved in the solvent. Another thing
needed to be considered was that the solvent
should not react with the compound being
purified. The desired compound could be lost
during recrystallization if the solvent reacts with
the compound. Lastly, the solvent must be
volatile enough to be easily removed from the
solvent after the compound has been crystallized.
This would allow easy and rapid drying of the
solid compound after it has been isolated from
the solution.
Solvent Room During Upon
temp. heating cooling
Water Insoluble Soluble Insoluble
Methanol Soluble Soluble Soluble
Hexane Insoluble Insoluble Insoluble
Table1. Solubility of Pure Acetanilide in
Different Solvent
Three solvents namely distilled water,
methanol, and hexane were used and tested to
identify which solution would suit best for the
experiment. As shown in Table 1, methanol was
soluble in all temperature and hexane was
insoluble in all temperature. Therefore these two
solvents could not be used for acetanilide that
would undergo recrystallization. Both methanol
and hexane were also flammable and volatile.
However, distilled water showed a different result
and matched the behavior of an ideal
recrystallizing solvent for acetanilide. At room
temperature it was insoluble; during heating it
was soluble; and upon cooling, it was insoluble.
In conclusion, water was the desired solvent to
be used in this experiment.
The reaction of aniline with acetic
anhydride had produced acetanilide which was
crystals with some impurities. This exhibited
exothermic reaction which means the release of
heat from the system. To hasten crystallization,
ice water bath was done which could easily
decrease the solubility of acetanilide. During the
process of cooling, the temperature had lowered
which was a result of release of heat or an
exothermic reaction. Therefore, crystals were
formed again which means crystallization
happened. These crystals were the crude
acetanilide that was collected after the solution
was filtered in a wet filter paper and the residue
was dried overnight. The residue contained the
crude acetanilide which weighed 2.1897g.
Weight of the crude 2.1897 g
acetanilide
Weight of pure acetanilide 1.8394 g
Table 2. The weight of crude and pure
acetanilide
The collected crude sample still had some
small amount of impurities which could affect the
weight of pure acetanilide so recrystallization
should be done. The solution which contained the
crude acetanilide and water was placed again in a
hot water bath. It would be noted that the
recrystallizing solvent was enough to dissolve the
substance which may result to reduction of the
crystallized acetanilide. While water bathing took
place, the solution would look as if it was colored.
This was an effect of impurities. These impurities
may be decolorized by the putting small activated
charcoal which is a highly absorbent carbon. It
was used as an effective adsorbent and
purification or removal of impurities medium.
This was because of its property of having large
surface area and highly porous form. However,
just specified small amount of activated charcoal
should only be added because too much of it
would absorb the desired substance too.
Filtration was the most effective way to
remove unwanted impurities most especially
when decolorization was utilized; hence, the
solution should be immediately filtered in an ice
water bath while it still hot. One should be
cautious because premature recrystallization may
occur when the solution in the flask was not kept
in its boiling point temperature. Mother liquor
refers to the solution that remains in the crystals.
To reduce the amount of mother liquor, washing
of crystals with cold distilled water must be done.
However, during filtration, some part of the
solution was lost that resulted to reduction of the
pure acetanilide.
After filtration, the crystals were dried by
pressing-in between filter paper and were kept in
the locker overnight. The dried crystals where
then weighed in the analytical balance. The
weight of the pure acetanilide collected was
reduced to 1.8394 g. One reason that affected
the reduction of pure acetanilide was the
attachment of some acetanilide in which where
not weighed.
 To calculate the percentage yield, the Based on the experiment the percentage
theoretical yield which the limiting reagent was yield in crude acetanilide was 73.72% and in
the basis must be first identified. The theoretical pure acetanilide was 61.93%. There was a
yield is the maximum yield of pure crystals that reduction in weight on the pure acetanilide due to
could be obtained by cooling or evaporating a removal of weight of impurities. It was also
given solution. This refers to the quantity of pure because of some crystals which were dissolved
crystals deposited from the solution. On the other and some which could not be separated in the
hand, limiting reagent is the reactant that is used filtration paper.
up first in a reaction. The solution below would
indicate the limiting reagent and the theoretical
yield of both the crude acetanilide and the pure
acetanilide. The percentage recovery of pure
acetanilide from the crude acetanilide was also
computed which is shown below.
𝐶𝐻3 𝐶𝑂2 𝐻
𝐶6 𝐻5 𝑁𝐻2 + (𝐶𝐻3 𝐶𝑂2 )𝑂 → 𝐶𝐻3 • 𝐶𝑂 • 𝑁𝐻 • 𝐶6 𝐻5 + 𝐶𝐻3 𝐶𝑂𝑂𝐻 mass of pure acetanalide
% Recovery = × 100
mass of crude acetanalide
1.8394 g
𝐴𝑛𝑖𝑙𝑖𝑛𝑒 𝑖𝑛 𝑔𝑟𝑎𝑚𝑠: % Recovery = × 100
1.0217𝑔 2.1897 g
2𝑚𝑙 𝐶6 𝐻5 𝑁𝐻2 × = 𝟐. 𝟎𝟒𝟑𝟒𝒈
1𝑚𝑙
% Recovery = 84.00%
𝐴𝑐𝑒𝑡𝑖𝑐 𝑎𝑛ℎ𝑦𝑟𝑑𝑟𝑖𝑑𝑒 𝑖𝑛 𝑔𝑟𝑎𝑚𝑠:
1.082𝑔 The percentage recovery of pure
3𝑚𝑙(𝐶𝐻3 𝐶𝑂2 )𝑂 × = 𝟑. 𝟐𝟒𝟔𝟎𝒈 acetanilide was 84.00% which means there was
1𝑚𝑙
only a minimum amount of acetanilide lost and
the experiment was a success. The pure
Identify the limiting reagent: acetanilide that was collected was colored white.

1.0217𝑔 1𝑚𝑜𝑙𝑒 102.09𝑔

2𝑚𝑙 𝐶6 𝐻5 𝑁𝐻2 × × ×
1𝑚𝑙 93.13𝑔 1𝑚𝑜𝑙𝑒
In conclusion, the more the solute had
= 𝟐. 𝟐𝟒𝒈 (𝑪𝑯𝟑 𝑪𝑶𝟐 )𝑶
undergone recrystallization, the purer it get but
the amount decreases.

1.082𝑔 1𝑚𝑜𝑙𝑒 1𝑚𝑜𝑙𝑒 REFERENCES:

3𝑚𝑙(𝐶𝐻3 𝐶𝑂2 )𝑂 × × ×
1𝑚𝑙 102.09𝑔 93.13𝑔
= 𝟐. 𝟗𝟔𝒈 𝑪𝟔 𝑯𝟓 𝑵𝑯𝟐 From books

Hence, the limiting reagent is Aniline (C6 H5 NH2 ). Martin & Gilbert (2011). Organic Laboratory
Experiment (5th Ed.). Boston: Cengage
Theoretical yield = mass of LR Learning.

Actual Yield = crude acetanilide

University of Santo Tomas. Faculty of
𝐴𝑐𝑡𝑢𝑎𝑙 𝑌𝑖𝑒𝑙𝑑 Pharmacy. Organic Chemistry Group. (2009).
% 𝑌𝑖𝑒𝑙𝑑 = × 100
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑌𝑖𝑒𝑙𝑑 Laboratory Manual in Organic Chemistry.
𝐴𝑐𝑡𝑢𝑎𝑙 𝑌𝑖𝑒𝑙𝑑
Quezon City: C&E Publishing Inc.
% 𝑌𝑖𝑒𝑙𝑑 𝑜𝑓 𝑐𝑟𝑢𝑑𝑒 𝑎𝑐𝑒𝑡𝑎𝑛𝑖𝑙𝑖𝑑𝑒 = × 100
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑌𝑖𝑒𝑙𝑑

2.1897 𝑔 Ault (1983). Techniques & Experiments fo

= × 100 = 𝟕𝟑. 𝟕𝟐% Organic Chemistry (4th Ed.). Massachusets:
2.0434 𝑔
Ally & Bacon Incorporated.

𝐴𝑐𝑡𝑢𝑎𝑙 𝑌𝑖𝑒𝑙𝑑 From websites

% 𝑌𝑖𝑒𝑙𝑑 𝑜𝑓 𝑝𝑢𝑟𝑒 𝑎𝑐𝑒𝑡𝑎𝑛𝑖𝑙𝑖𝑑𝑒 = × 100
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑌𝑖𝑒𝑙𝑑
ACETANILIDE (N-PHENYLACETAMIDE). (n.d.).
1.8394 𝑔
= × 100 = 𝟔𝟏. 𝟗𝟑% Retrieved August 12, 2011 from
2.0434 𝑔 http://chemicalland21.com/lifescience/phar/ACET
ANILIDE.htm
ACETIC ANHYDRIDE (ACETYL ETHER). (n.d.).
Retrieved August 12, 2011, from
http://chemicalland21.com/petrochemical/ACETI
C%20ANHYDRIDE.htm

PURIFYING ACETANILIDE BY
RECRYSTALLIZATION. Retrieved August 12,
2011,from
http://www.cerlabs.com/experiments/108754070
3X.pdf

RECRYSTALLIZATION.Retrieved August 12, 2010,

from http://chemistry.barnard.edu/orgolab/lab2
and
http://web.centre.edu/muzyka/organic/lab/24_re
crystallization.htm