Recrystallization of Acetanilide

Sio, Camille; Sison, Gwen; Tolentino, Ana Lou; Tolentino, Rhodelyn*; Uy, Kim;
Villanueva, A.
2F-PH Group 7

Abstract
Recrystallization is a purification process used to remove impurities from
organic compounds through the difference in solubility at different
temperatures. This process is based on the premise that the solubility of a
compound in a solvent increases with temperature and the dissolved solid
tends to separate from the solution as it is cooled. In the experiment
performed, three samples of acetanilide were dissolved in different solvents
and placed in a warm water bath set-up for solvent identification. Once the
solvent had been determined, crude acetanilide was obtained by mixing
aniline and distilled water with acetic anhydride. The crude acetanilide was
then dissolved in a water bath and cooled with an ice bath, which hastens
the formation of crystals. As the compound crystallizes from the solution,
impurities were excluded from the growing crystal layer, thus yielding pure
acetanilide.
Introduction
Impurities often contaminate
organic compounds that have been
synthesized in the laboratory or
isolated from natural sources
regardless of their physical state,
thus, requiring purification. The
methods to be employed to purify
these compounds are based on
their
physical
and
chemical
characteristics.
Liquids,
for
example are purified through
distillation. In the case of solids,
sublimation and crystallization are
more
suitable
processes
in
attaining purity. Among the two,
the latter is the most widely used
especially for organic compounds
that are solid at room temperature
and those that lack the property of
passing directly into vapour phase.

Recrystallization, in which
two crystallization processes were
performed,
is
a
purification
technique that is based on the
differences in the solubility of the
desired compound and the impurity
contaminating
the
desired
compound, as a function of varying
temperature. This is built in the
idea that as temperature increases,
the solubility of the compound
increases as well. As a heated
solution of the desired compound
cools, a small, pure seed crystal of
the compound forms in the

solution. Layer by layer, additional

molecules attach to this crystal,

forming a growing crystal lattice.
Lattice is a fixed and rigid
arrangement of atoms, molecules
or ions (Mullin, 1961).
Figure 1. Identical molecules attach to
one another, forming a crystal lattice.

The
solubility
of
the
compound, which is the degree of
the solute to be dissolved in the
solvent, is the main factor to in
crystallization.
Prior
to
the
recrystallization
process,
the
recrystallizing solvent should be
identified. In choosing the solvent,
the primary consideration is the
extent to which the compound and
impurities are soluble in the solvent
at high, and low temperatures.
Ideally, the compound to be
recrystallized
should
be
very
soluble in the chosen solvent at
elevated temperatures, but almost
insoluble in the cold solvent. The

standing in air and light because of

the darkening of its color. This is
due to the atmospheric oxidation of
the impurities present in the
benzene. Aniline is an organic base
used in the manufacture of drugs,
dyes, rubber chemicals, explosives,
etc.
Heating the aniline with an
organic acid yields amides, called
anilides, such as acetanilide (Nphenylacetamide) from aniline and
acetic acid, a process known as
acetylation.
C6H5NH2 + (CH3CO)2O
C6H5NHCOCH3 + CH3COOH
Equation 1. Acetylation

Figure 3. Structural formula of acetic

anhydride

opposite should take place with the

impurities.
Figure 2. Structure of Aniline

Aniline, C6H5NH2 is a primary

amine in which the amino group is
directly attached to the benzene
ring. This clear to slightly yellow
liquid has a boiling point of 182 C;
a density of 1.0217 g/ml; and
molecular weight of 93.13 g/mol. It
does not readily evaporate at room
temperature
and
it
exhibits
solubility in water. Impurities in this
substance
are
evident
upon

Acetic anhydride, (CH3CO)2O

is a colorless liquid that is reacted
with water to form acetic acid,
which exhibits a vinegar-like odor.
It boils at a temperature of 140 C
and melts at -73 C. Its density is
1.082 g/ml and its molecular
weight is 102.09 g/mol. It is soluble
in benzene, ether and chloroform

and in water (only when acetic

anhydride decomposes). Acetic

anhydride aids in the acetylation of

aniline to yield acetanilide.
Figure
4.
acetanilide

Structural

formula

of

Acetanilide, C6H5NH(COCH3)
is the product of acetylation of
aniline with acetic anhydride at a
decreased temperature. It is an
odourless solid chemical of leaf or
flake-like appearance. It is also
known
as Nphenylacetamide, acetanil,
or
acetanilid, and was formerly known
by the trade name Antifebrin. It is
used as a precursor in penicillin
synthesis
and
other
pharmaceuticals
including
painkillers and intermediates.

A corn-grain amount of pure

acetanilide was placed into three
different test tubes. The first test
tube contained 1 mL of water; the
second, 1 mL of ethanol; the third,

1 mL of hexane. The mixtures were

shaken and placed in a warm water
bath (37-40 C) for 1-5 minutes
and were allowed to cool after.
2. Crude acetanilide production

This experiment aims to: a)

select an appropriate recrystallizing
solvent, b) synthesize acetanilide
by acetylation of aniline, c)
produce a pure product from crude
acetanilide
by
recrystallization
process, and d) compute for
percent yield based on the actual
and theoretical yield of pure
acetanilide.
Experimentals
A. Sample Used
Pure acetanilide, aniline and
acetic acid were used as samples
to produce crude acetanilide. The
given solvents were water, hexane
and methanol.
B. Procedure
1. Identification of recrystallizing
solvent

To
produce
the
crude
acetanilide, 2 mL of aniline and 20
mL of distilled water were mixed in
an Erlenmeyer flask. 3mL of acetic
anhydride was slowly added to the
mixture. This was later on cooled in
an
ice
bath
to
hasten
crystallization. The mixture was
filtered through a fluted filter
paper.
The
residue
(crude
acetanilide) was allowed to dry and
it was weighed after.
Figure 5. Crude acetanilide

3.
Recrystallization
(Purification)

Process

20 mL of the previously
determined recrystallizing solvent
was added to the crude acetanilide
and the mixture was heated in a
water bath until all the solid
dissolved. Activated charcoal was
added to the colored solution (the
Erlenmeyer flask was removed
from the water bath in the addition
of activated charcoal). The solution
was quickly filtered while still hot
using a fluted filter paper. The
filtrate was allowed to cool by
placing the receiver on a beaker
containing tap water. The crystals
were collected and washed with
distilled water. To facilitate drying,
the obtained crystals were pressed
in-between filter papers. These
crystals were the pure acetanilide.
The dried crystals were then
weighed for the computation of
percent yield.
Figure 6. Pure acetanilide

Results and Discussion

It is necessary to identify the
recrystallizing solvent in order to
purify the organic compound. The
compound should be insoluble at
room temperature when mixed
with the solvent; soluble while
heating; and separates from the
solution as it is cooled. The
unwanted impurities, on the other
hand, should be soluble at room
temperature or insoluble with the
presence of heat. The heat applied
should not go beyond the melting
point of the substance to be
crystallized. Otherwise, inaccurate

results will be obtained. If the

boiling point of the solvent is at a
higher temperature, there is a
possibility that the substance will
melt, instead of dissolving. This
may result to oiling of the solid.
This occurs when the substance
forms an insoluble liquid after it
was melted. The formed liquid
refuses to crystallize upon cooling
and becomes oil. Volatility should
also be considered in choosing the
appropriate
solvent.
Volatile
solvents are easily separated from
the solution after crystallization.
Ideally, volatile solvents with low
boiling points are used. In addition,
the solvent should have a minimal
chemical reactivity. It should not
react with the solvent to be
purified.
Table 1. Solubility of Pure Acetanilide in
different solvents
Solvent

Water
Methan
ol
Hexane

At
room
temp.
Insolubl
e
Soluble

During
heatin
g
Soluble

Upon
cooling

Soluble

Insolubl
e
Soluble

Insolubl
e

Insolubl
e

Insolubl
e

Table 1 shows the solubility

of pure acetanilide in three
different solvents namely water,
methanol and hexane. In water, the
solid was soluble only at a higher
temperature
and
exhibited
insolubility as temperature was
lowered. The acetanilide was
soluble in methanol and insoluble
in hexane in all systems. Recall in
the previous discussion that the
compound should be insoluble at
room temperature when mixed

with the solvent; soluble while

heating; and separates from the
solution as it is cooled. These
criteria were all evident in water.
Therefore, water is the suitable
recrystallizing solvent. It is quite
appropriate for melting points of
pure organic compounds from
about a room temperature to about
70 C in heating water bath.
In acetylation of aniline with
acetic
anhydride,
yielding
acetanilide, an exothermic reaction
was exhibited because heat was
released. In the case of cooling, the
heat has to be removed from the
system so the temperature was
decreased. Hence, the crystals
were formed. The ice bath hastens
the formation of crystals.
Table 2. Actual and theoretical yield of
pure acetanilide and Percentage yield

Actual yield
Theoretical
yield
Percentage
yield

2.20 g
2.97 g
74.07%

The weight of acetanilide

obtained from the experiment was
2.20 g and the theoretical yield
was 2.97 g, which was computed
from the density and molecular
weights of aniline (limiting reagent)
and
acetanilide.
The
limiting
reagent is the reactant that is used
up first in a reaction (Chang, 2008).
It was determined as follows:
C6H5NH2 + (CH3CO)2O
C6H5NHCOCH3 + CH3COOH

Given:
MW of Aniline = 93.13 9
Density of Aniline = 1.0217 g/mL
Aniline: 2 mL x 1.0217 g x 1 mol
1 mL
93.13 g
= 0.02194 mol
0.2194 mol x 1 mol x 135.17 g
1 mol 1 mol
= 2.97 g acetanilide

MW of Acetic Anhydride = 102.09

g/mol
Density of Acetic Anhydride =
1.082 g/ml
Acetic: 3 mL x 1.082 g x 1 mol =
0.03180
Anhydride
1 mL
102.09 g
mol
0.3180 mol x 1 mol x 135.17 g
1 mol 1 mol
= 4.30 g acetanilide

The limiting reagent is the reactant

with
the
lower
amount
of
theoretical yield therefore, aniline
is the limiting reagent.
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).
Percentage yield is the pure
acetanilide obtained from the 2 mL
aniline and 3 mL acetic anhydride.
It is computed as follows:
% yield = actual yield of pure
acetanilide
theoretical yield of pure
acetanilide
x 100

% yield = 2.20 g
74.07%
2.97 g

x 100 =

*The theoretical yield used in the

formula is the theoretical yield of
aniline, the limiting reagent.
The percentage yield was only
74.07% probably because some of
the substance were dissolved while
heating. This is a common error
that may reduce the solid yield
returned into crystals.
References
Mullin, J.W. (1961). Crystallization.
London, England: Butterworth &
Co.
Pastro, D. J., John, C.R., & Miller,
M.S. (1998). Experiment and
techniques in organic chemistry.
New Jersey: Prentice Hall.
Chang, R. (2010). Chemistry (10th
ed.). New York, NY: McGraw-Hill
Companies, Inc.

Aniline
(Chemical
Compound).
Retrieved September 17, 2014,
from
http://www.
Britannica.com/EBchecked/topic/25
473/aniline
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5. http://lulelaboratory.blogspot.
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