CHM145L Organic Chemistry 1 Laboratory

1st Quarter, S.Y. 2015-2016

Recrystallization
Castro, Ethan Zachary G., Pasia, Abraham Paul L., Pulido, Froileth S.1
1

Professor Oliver Villaflores, School of Chemical Engineering, Chemistry, Biological Engineering and Materials

Science Engineering, Mapa Institute of Technology; 2Castro, Ethan Zachary G., Pasia, Abraham Paul L., Pulido,
Froileth S., CHM145L-C11, School of Chemical Engineering, Chemistry, Biological Engineering and Materials
Science Engineering, Mapa Institute of Technology

ABSTRACT
When organic compounds precipitate during a reaction or following an extraction, impurities
may undergo occlusion, or the trapping of impurities within the crystal lattice due to rapid crystal
growth of the precipitate. In the event that impurities are present in the crystals, one may wash the
compound with cold water, which removes impurities on the surface of the crystal, or redissolve the
solid in a hot solvent to allow all of the impurities to be filtered off. The resulting filtrate is then cooled
down slowly to allow recrystallization to occur. In order to achieve a successful recrystallization
process, one must consider the properties of the solvent to be used. An ideal recrystallization solvent
must dissolve the entire compound at high temperature and dissolve very little or even none of the
compound at all at low temperature. In the first part of this experiment, the appropriate solvents for
recrystallization of acetamide, acetanilide, aspirin, benzoic acid, naphthalene, and sucrose was
investigated by subjecting a small mass of each solid compound to a solubility test in both hot and
cold samples of water, ethanol, benzene, and ethyl acetate. It was found that water is suitable for the
recrystallization of acetanilide, aspirin, benzoic acid, and sucrose; ethanol is appropriate for
acetamide, benzoic acid, and sucrose; benzene is suitable for sucrose; and ethyl acetate is
appropriate for aspirin, acetamide, and naphthalene. This implies that if a recrystallization process
for each of the compounds used is to be commenced, one may have a choice of choosing the
appropriate solvent according to the correspondences shown above. Meanwhile, in the second part
of the experiment, recrystallization of pure acetanilide was performed with water as the solvent. A
3.50-gram sample of crude acetanilide was utilized. Two set-ups were assembled: the hot gravity
filtration set-up and the vacuum filtration set-up. After dissolving the sample in hot water, it was
filtered in the hot gravity filtration set-up, ending up with a colorless filtrate. After cooling the sample,
it was vacuum filtered. After drying and weighing, it was found that the percentage recovery of pure
acetanilide obtained was 75.43%. Moreover, the pure crystal was tested for its melting point using
the Thomas-Hoover apparatus, and its value was found to be 106C.
Keywords: occlusion, recrystallization
INTRODUCTION
The coffee we dissolve in water is a
molecular solid, in which the individual molecules
are being held together by relatively weak
intermolecular forces of attraction. In the case of
sugar dissolving in water, the weak bonds among

Experiment 2 | Group 4 | October 15, 2015

the molecules of sugar are broken and these

molecules are released into solution.

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able to wash away oils and grease since they are

compounds which have a polar group on one end
and a nonpolar group on the other end.

Figure 1. Dissolving sugar in the liquid representation

Figure 2. The structure of the soap compound

Always be reminded that it always takes

energy to break the bonds among the molecules
in sucrose, and to break the hydrogen bonds in
water that must be broken for the sucrose
molecules to have spaces in the solution. In the
given scenario, again, the sugar dissolves in
water due to the energy given off when the
partially polar sucrose molecules coming from
intermolecular bonds with the polar water
molecules. The weak bonds that arise between
the solute and the solvent compensate the
energy required to break or disrupt the structure
of both the pure solute and the solvent.

The polar group represents the loving

water region of the compound (hydrophilic
region), while the nonpolar group represents the
water fearing region of the compound
(hydrophobic region). Eliminating the oil
molecules is achieved by surrounding it by the
hydrophobic tails of the soap molecules, forming
a micelle.

Solubility is also based on the principle,

like dissolves like. This only means, polar
compounds are only soluble in polar solvents,
while nonpolar compounds are soluble in
nonpolar solvents. This principle is possible since
polar compounds exercises dipole-dipole
interactions with the molecules of a polar solvent,
making the process achievable. In nonpolar
compounds, the case is the same as well. A
nonpolar compound exercises London dispersion
forces with the molecules of a nonpolar solvent,
proving the principle possible.
A good example of this case is when a
part of clothing is stained with a polar compound.
If that case happens, the stain can be easily
washed away with water. Otherwise, water will
not be able to dissolve or wash away this stain.
Oils can stain clothing, sticks on plate, etc. and
soap is normally used to eliminate it. Soaps are
Experiment 2 | Group 4 | October 15, 2015

Figure 3. A figure on how soap compound eliminates oil

molecules.

One of the earliest methods developed

for separating mixtures and one of the most
commonly used physical properties is the
differential solubility. Differential solubility
depends on the different substances having
different solubility in different solvents. It is
defined as the amount of solid that can be
dissolved in a suitable solvent as variations in
temperature affect it.
It is important to have an idea and learn
the solubility rules and differential solubility since
one important laboratory technique is being
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governed by the aforementioned topics. Impure

organic substances or compounds can be made
pure through recrystallization, and this process is
mainly follows solubility rules and conditions.
As crystals form during a reaction or
following an extraction, impurities will be caught
within the crystal lattice or settle upon the surface
of the solid. Impurities from the surface of the
crystal lattice can be removed through washing
the crystal with cold solvent however, it fails to
remove the impurities caught within the lattice.
Since, washing with cold solvent alone does not
eliminate the impurities trapped in the lattice, it
will sometimes require the performer to redissolve the solid again in a hot solvent to allow
the undissolved impurities to be filtered off. By
the same process, the resulting filtrate is then
cooled to allow the pure solid to crystallize again.
Furtherly, recrystallization, also known as
fractional crystallization, is a common procedure
performed in the laboratory to purify an impure
organic compound in a solvent. The method is
based on the principle that the solubility of most
solids increases with temperature is increased.
Which means, that when the temperature is
increased, the number of solute that can be
dissolved in a solvent increases as well.

amount of hot solvent insufficient to dissolve it

when cold, it is expected that crystals will form
when the hot solution is allowed to cool. The
scale of precipitation of the solid rely on the
difference in its solubility in the specific solvent at
specific temperatures between the used
extremes. These extremes have two extents,
which are the upper and lower extremes. The
upper extreme is determined by the poling point
of the solvent while the lower limit is usually
dictated by experimental convenience.
At the first part of the experiment, the
procedure requires the researchers to properly
select or choose the solvent. It is important to
conduct this part since this will determine the
suitable recrystallization solvent for an unknown
compound. A compound typically exhibits three
general solubility behaviors:
1. A compound which has a high solubility
in both hot and cold solvent
2. A compound which has a low solubility in
both hot and cold solvent
3. A compound which has a high solubility
on hot solvent, and a low solubility in
cold solvent.

Figure 4. Graphical representation of the general solubility

behaviors

Also, as temperature is concerned,

almost all solids are more soluble in a hot solvent
than in cold and this fact is being taken
advantage by recrystallization. Henceforth, if a
solid compound is initially broken down in an

Solvents that exhibits the first two

behaviors are not useful for the recrystallization
of the compound. A solvent showing the third
behavior is the most suitable for use as a
recrystallization solvent.

Experiment 2 | Group 4 | October 15, 2015

SOLUBILITY

As mentioned earlier, it is important to

consider first the solubility behavior in order to
understand the recrystallization process. It is
usually stated in solubility that like dissolves like,
but technically and more correctly, it should be
stated as the compounds having the same
structural features will be soluble in one another,
these structural features that may affect solubility
include polarity and the ability to hydrogen bond.

1. BAD
2. BAD
3. GOOD

TEMPERATURE

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To sum up, an ideal recrystallization

solvent should:
1. Dissolve all of the compound at high
temperature
2. Dissolve very little or none of the
compound at low temperature
3. Have different solubilities for the
compound and the impurities
4. Have a boiling point below the melting
point of the compound
5. Have a relatively low boiling point (60100 Celcius)
6. Be inert with respect to the compound
7. Be relatively inexpensive
With the second part of the experiment, it
is useful to note that if the impurities present in
the original mixture have dissolved and remain
dissolved after the solution is cooled, the
isolation of the crystals that have formed should
ideally provide pure material. An alternative
procedure may be done since the impurities
might not be dissolved at all in the hot solution
and may be removed by filtration before the
solution is cooled. Now, the crystals that
subsequently made should be purer than the
original mixture.

METHODOLOGY
The experiment is divided into two parts,
choosing the solvent and the recrystallization of
impure Acetanilide.
In the first part of the experiment, initially,
the performer must weigh approximately 0.10 g
of acetamide and place it in a micro test tube.
This then will be dissolved in 2 milliliter of cold
water and the researcher must observe the
solubility behavior of the compound (this must be
recorded). If the compound fails to dissolve, boil
the mixture, observe the solubility behavior and
record it again. Repeat the first two procedures
Experiment 2 | Group 4 | October 15, 2015

with the other solvents (cold ethanol, benzene

and ethyl acetate). If the mixture fails to dissolve,
heat the mixture in a water bath. Repeat again
the procedures with each of the following
compounds (acetanilide, aspirin, benzoic acid,
naphthalene and sucrose) as solute.
In the second part of the experiment, the
researchers must initially prepare fluted filter
paper, hot gravity filtration set-up and vacuum
filtration set-up. To start the second part of the
experiment, heat approximately 100 milliliters of
water. Taking note of the exact weight,
approximately weigh 3.50 g crude acetanilide.
Dissolve the compound (impure acetanilide) in 30
mL of water using the 150 milliliter-beaker. Then,
slightly boil the mixture using the hot plate. As
the solution starts to boil, add 2 milliliter-portions
of the previously heated water and stirring it at
the same time until the white solid completely
dissolves. Carefully observe and maintain the
temperature at 90C while adding hot water.
Take note of the total volume of the water used, it
should not exceed 70 milliliters since the
solubility of acetanilide is 4.30 g/100 milliliters of
water. Then, if the solution is colored, add a
small amount of activated carbon.
This time, the hot gravity filtration set-up
will now be used, pour the solution into the fluted
filter paper situated in the steam glass funnel. It
is expected at this point that the performers must
observe a colorless filtrate. If not, activated
carbon should be added again and then
reheating the mixture; filtration process should be
repeated. After this procedure, remove the flask
from the hot plate and the residue must be
properly discarded.
The filtrate must now be cooled down to
room temperature, then place it in an ice bath
and stir continuously the mixture until
crystallization is complete. This process will
approximately take 10 to 15 minutes. If it fails to
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occur, scratch the side of the flask or add some

crystals of acetanilide.
Once the crystallization is complete,
vacuum filter the solution and wash the crystals
obtained with 2 milliliters of cold water. Then dry
the crystals and weigh them, through this,
compute the percentage recovery. Once
complete, determine the melting point of the
purified crystals.

Figure 5. Determination of the appropriate solvent for

recrystallization

RESULTS and DISCUSSION

For the first part of the experiment, the
researchers were able to determine the
appropriate solvent for recrystallization of the test
compounds acetamide, acetanilide, aspirin,
benzoic acid, naphthalene and sucrose. These
test compounds were tested in hot and cold
water, ethanol, benzene and ethyl acetate to
know which of the given solvents is the most
appropriate one. Table 1 summarizes the
solubility of the test compounds in each solvent
in hot and cold temperatures.
TABLE 1
Water

Compound
Acetamide
Acetanilide
Aspirin
Benzoic
Acid
Naphthalene
Sucrose

Ethanol

Benzene

Ethyl
Acetate
Cold Hot
I
S
I
I
I
S

Cold
S
I
I

Hot
S
S
S

Cold
S
S
S

Hot
S
S
S

Cold
I
S
S

Hot
S
S
S

I
I

S
S

I
I

I
S

S
I

S
I

I
S

S
S

Experiment 2 | Group 4 | October 15, 2015

Figure 6. Testing the solubility of the solvent

It is important to appropriately select the

solvent for recrystallization. In fact, it is the most
critical part in the process of recrystallization
since choosing the correct solvent helps in
forming a product of high purity with high percent
recovery. Accordingly, a solvent should satisfy
certain criteria and these are the basis in
selecting the most appropriate solvent/s for each
test compound. For a solvent to be highly
suitable for recrystallization of a certain
compound, it should dissolve all of the compound
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at high temperature and dissolve very little or

none of the compound at low temperature. Also,
it must have different solubilities for the
compound itself and its impurities. The impurities
should be either insoluble in the solvent at all
temperature or at least be slightly soluble at low
temperatures otherwise, if both the compound
and the impurities are soluble, it would crystallize
simultaneously from the solvent which will fail the
goal of purifying the compound. The solvent must
also have a boiling point lower than the melting
point of the compound and a relatively low boiling
point, around 60-100C. Lastly, the solvent
should be inert, relatively inexpensive and it
should not react with the compound. From this
criteria and the observations that we were able to
record in Table 1. We were able to select the
appropriate solvent for each test compounds. For
Acetamide, it is best to use benzene and ethyl
acetate. Water should be used for Acetanilide.
Ethanol and water are best used for Sucrose and
Benzoic acid while water and ethyl acetate are
best used for Aspirin and Naphthalene. These
conclusions were supported by the evident
recrystallization of the compound after cooling
down.

Figure 9. Cooling the solution

Figure 10a. Vacuum Filtration Set-up

Figure 8. Hot Gravity Filtration Set-up

Experiment 2 | Group 4 | October 15, 2015

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because the filtrate can cool as it passes to the

stem and such cooling will enable crystals to
form. The solution was not placed immediately in
the ice bath for cooling because doing so will
prevent the formation of large well-defined
crystals which is easier to handle and wash. After
cooling, the solution was vacuum filtered to
separate the crystals from the mother liquor and
washed using cold water. At the end, the
researchers were able to recover 75.43 percent
of acetanilide which has a melting point of 106C.

Figure 10b. Vacuum Filtration Set-up

For the second part of the experiment,

the performers recrystallize impure acetanilide to
remove its impurity. In purifying the crude
acetanilide, the performers were initially asked to
use water, which was proven in the first part of
the experiment as one of the appropriate
solvents in recrystallization of acetanilide, as a
solvent. High solubility of acetanilide in water at
high temperature permits dissolution to happen in
lesser amount of water which will allow recovery
of pure acetanilide in high yield. After boiling the
crude acetanilide solution and dissolving the
white precipitate using a previously boiled water,
activated carbon were added to remove colored
impurities. The added amount of activated
carbon used was minimal since an excess could
result to absorption of acetanilide or simply a
decrease in the desired amount of the product.
Other impurities were remove by filtration using a
fluted filter paper which allows the filtrate
containing the acetanilide to pass through very
quickly and a stemless funnel. Stemless funnels
are preferred over a funnel with stem because it
is not prone to premature recrystallization
Experiment 2 | Group 4 | October 15, 2015

Figure 11. Crystals formed after the second part of the

experiment

CONCLUSION and RECOMMENDATIONS

The experiment done focused on topics
of solubility and recrystallization using solvents
best suited for the organic compounds. Solvent
efficiency, when it came about recrystallization, is
making sure that the solid and the impurities
have different solubilities in the solvent chosen.
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Choosing the correct solvent is crucial in

assuring that in the recrystallization process, they
are able to obtain a product that is of high purity
and of high yield.

ice bath in order to induce further formation of

large and well-defined crystals. The product
yielded 75.43% in percentage recovery of the
crude Acetanilide taken.

The first part of the experiment aimed to

identify the proper choice of solvent for each of
the organic compounds. It was tested whether or
not they are soluble or insoluble in the given
conditions of their preset solvent. The test
compounds were Acetamide, Acetanilide,
Aspirin, Benzoic Acid, Naphthalane, and Sucrose
and the solvents were Water, Ethanol, Benzene,
and Ethyl Acetate. One of the criteria for
choosing the appropriate solvent for
recrystallization is that it has to be insoluble (or
have very little solubility) in low temperatures and
completely soluble in high temperatures. This
criterion was accomplished with Benzene and
Ethyl Acetate for Acetamide, Water for
Acetanilide, Water and Ethyl Acetate for Aspirin,
Water and Ethanol for Benzoic Acid, Water and
Ethyl Acetate for Naphthalene, and finally Water
and Ethanol for Sucrose.

It is recommended for other researchers

to always make sure of the volume of solvent
added as this can really affect the yield of your
product. It is also recommended to take all
cautions in making sure that you are able to
recover as much of the product as you can,
spillages, sticking to apparatus, etc.

The second part of the experiment dealt

with purification of impure Acetanilide by
methods of recrystallization. The impure
Acetanilide was treated with an appropriate
solvent (water) to be able to dissolve the mixture
and separate the Acetanilide from its impurities.
Minimal amounts of the solvent were added one
at a time due to it being able to lessen the
chance of precipitation of crystals during the
cooling of the solution if more than the allowed
volume of solvent were added. The fluted filter
paper allowed the solution containing the
dissolved Acetanilide to pass through it very
quickly and leave behind the impurities in the
mixture. Any coloration of the filtrate, that
contained the purified Acetanilide, was dealt with
small amounts of activated carbon by absorbing
the colored impurities. The hot solution was then
made to cool down first before being placed in an
Experiment 2 | Group 4 | October 15, 2015

References
Baluyut, J. G., & De Castro, K. A. (2001). Organic
Chemistry Laboratory Manual for Chemistry
Students Part 1. Intramuros, Manila: Mapua
Institute of Technology.
Klein, D. (2012). Organic Chemistry. In D. Klein,
Organic Chemistry (p. 41). New Jersey: John
Wiley and Sons, Inc.
Samal. (2015). Department of Chemistry. Retrieved
from Univeristy of Massachusetts:
http://www.chem.umass.edu/~samal/269/cry
st1.pdf

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