RECRYSTALLIZATION

Group 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 acetani l i de was 94.59%. The
percentage recovery of the experi ment was 46.43%.

INTRODUCTION

Organic compounds that are synthesized in
laboratories or isolated from natural recourses
are often tainted by impurities. Different
purification methods can be used to remove the
impurities present in a compound. One example
of these is recrystallization. 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
insolubility at a low temperature and separates
as it cools resulting to small seed crystals.
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 pure
product which contained fewer or no impurities at
all. The level of purity of the product can be
checked through its melting point range.
Formation of crystals was due to the difference
insolubility of the solid with the solvent. Solutes
or compounds tend to be more soluble in hot
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.



Figure 1. Structure of Aniline

Aniline (C
6
H
5
NH
2
) also known as aminobenzene
or benzenamine 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. 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 20C, 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.


Figure 2. Structure 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 140C while its melting point is at -


73C. 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 (C
6
H
5
NH(COCH
3
)) 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-
116C and boils at 304C. It can undergo self-
ignite at 545C, 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 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.

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
Temperature
During
Heating
Upon
Cooling
Water insoluble soluble insoluble
Methanol soluble soluble Soluble
Hexane insoluble insoluble insoluble

Table 1. Solubility of Pure Acetanilide in Different
Solvents

Three solvents (distilled water, methanol, and
hexane) were tested. As shown in Table 1,
methanol is soluble and hexane is insoluble at
room temperature, during heating, and upon
cooling. Hence, acetanilide, when placed on these
two solvents, cannot undergo recrystallization.
Both methanol and hexane are flammable and
volatile. Thus, extra caution must be utilized.
However, distilled water exhibited a different
result. At room temperature it was insoluble;
during heating it was soluble; and upon cooling,
it was insoluble. Water shows the desired
solubility behavior of an ideal recrystallizing
solvent. 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 2.80 g.



Weight of crude
acetanilide
2.80 g
Weight of pure
acetanilide
1.30 g

Table 2. The Weight of Crude and Pure
Acetanilide

The weight of the crude acetanilide is 2.80
g. The acetylation of aniline and acetic anhydride
would yield to acetanilide but it may contain
small amount of impurities which may affect the
weight of pure acetanilide. During
recrystallization, the solution was placed in a hot
water bath. It would be noted that the
recrystallizing solvent is not enough to dissolve
the substance which may result to reduction of
the crystallized acetanilide.
During the water bath in recrystallization, the
solution would look as if it was colored because of
impurities. These impurities may be decolorized
by the use of activated charcoal which adsorbs
impurities because it has a large surface area and
it can remove impurities more effectively.
However, just a small amount of activated
charcoal should be added. Too much activated
charcoal will also adsorb the desired substance.
Filtration is 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 still hot. Take note that premature
recrystallization may occur when the solution in
the flask was not kept in its boiling point
temperature. Evaporation of solvent may initiate
premature crystallization.
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
theoretical yield which the limiting reagent was
the basis must be first identified. The 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. On the other
hand, limiting reagent is the reactant that is used
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.

Identification of the limiting reagent:
Aniline

Acetic Anhydride
(

)
Hence, the limiting reagent is Aniline (

),
now for the computation of the theoretical yield.

Theoretical yield = mass of LR
Actual Yield = crude acetanilide

Based on the experiment the percentage yield
in crude acetanilide was 94.59%. The weight of
the pure acetanilide was not used as the actual
yield for the computation of the percentage yield
because the weight of the crude acetanilide is
closer to the actual weight.
The percentage recovery of pure acetanilide
from the crude acetanilide was also computed
which is shown below.









% Recovery = 46.43%

The percentage recovery of pure acetanilide
was 46.43% which means half of the amount of
acetanilide was lost and the experiment was quite
efficient. The pure acetanilide that was collected
was color white.


In conclusion, the more the solute had
undergone recrystallization, the purer it get but
the amount decreases

REFERENCES
From books:
[1]. Ault (1983). Techniques & Experiments fo
Organic Chemistry (4th Ed.). Massachusets:
Ally & Bacon Incorporated.
[2]. Martin & Gilbert (2011). Organic Laboratory
Experiment (5th Ed.). Boston: Cengage
Learning.
[3]. University of Santo Tomas. Faculty of
Pharmacy. Organic Chemistry Group. (2014).
Laboratory Manual in Organic Chemistry
(Revised Edition). Quezon City: C&E Publishing
Inc.
From websites:
[4]. ACETANILIDE (N-PHENYLACETAMIDE).
(n.d.). Retrieved September 28, 2014 from
http://chemicalland21.com/lifescience/phar/ACET
ANILIDE.htm
[5]. ACETIC ANHYDRIDE (ACETYL ETHER). (n.d.).
Retrieved September 28, 2014, from
http://chemicalland21.com/petrochemical/ACETI
C%20ANHYDRIDE.htm
[6]. PURIFYING ACETANILIDE BY
RECRYSTALLIZATION. Retrieved September 24,
2014,from
http://www.cerlabs.com/experiments/108754070
3X.pdf
[7]. RECRYSTALLIZATION.Retrieved September
27,2014 from
http://chemistry.barnard.edu/orgolab/lab2 and
http://web.centre.edu/muzyka/organic/lab/24_re
crystallization.htm