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Patrick Apipanyakul
Ben Furlan
September 7, 2011

Recrystallization of Impure Naphthalene

Introduction

Recrystallization is the preferred method for purification of organic solids with less impurity
because because some of the impurity would co-crystallize.
1
The most important aspect of the
recrystallization technique is the selection of the solvent. A solvent, which works for one
recrystallization, may be totally unsuitable for purification of a different compound because of
the variation of solubility of different organic compounds in these solvents.
2
Some characteristics
desirable for a recrystallization solvent are that the substance to be purified must have a high
solubility in the solvent at its boiling point, and a significantly diminished solubility at lower
temperatures.
3
The solvent should be able to dissolve the impurities at all temperatures.
2,3
And
one of the most important is that the solvent must not react with the compound to be purified.
3


The seven steps of recrystallization

The process of recrystallization can be broken into seven discrete steps: (1) choosing the solvent
and solvent pairs; (2) dissolving the solute; (3) decolorizing the solution with pelletized Norit;
(4) filtering suspended solids; (5) recrystallizing the solute; (6) collecting and washing the
crystals; and (7) drying the crystals.
2
These steps can be categorized into three distinguishable
partsheating, cooling, and drying. First of all, it is known that the solubility of most
compounds in a given solvent will increase at elevated temperatures. Therefore heating is used to
dissolve the sample. It is also known that the solubility near the boiling point greatly increases;
thus it is imperative to bring the solution to a boil.
4
Furthermore, it is important to keep the
volume of the solvent to the minimum since recrystallizations from dilute solutions usually lead
to poor yields of recovery of the material.
5
In addition, this step usually uses a boiling chip or
boiling stick in heated reactions since a solution can become superheated or heated above its
boiling point without actually boiling with almost explosive violence, a process called bumping.
2

To prevent this from happening, a wood applicator stick can be added to the solution. Air trapped
in the wood comes out of the stick and forms the nuclei on which even boiling can occur.
5


During the cooling step, the molecules of a given compound will be assembling into aggregates
with the molecules that have a similar nature. These aggregates will grow in size and eventually
will be deposited from solution to form a solid with a particular crystal lattice.
1
Other types of
molecules that are not capable of engaging in the same types of interactions with the above
aggregates (and/or possess a different size, shape) will be excluded from the solid and, ideally,
will remain in the solution. To maximize the amount of product that crystallizes out of solution,
the solution is cooled from boiling to 0
o
C. If only cooling this solution to room temperature, for
example, instead of 0
o
C, the result is lower percent recovery yield.
2
At room temperature, not as
many crystals would form as they would at 0
o
C. The colder the solution, the more crystals will
come out of solution.
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For the last part, drying of the crystals will rid of the solvent molecules to produce the desired
compound in a purer form than the initial solid. The drying step is usually done either on air over
a prolonged period of time or under a vacuum. For air- and moisture-sensitive materials, the
drying should be done under vacuum, and the solid should be stored in a desiccator.
6


Solvent selection

Obviously, the most crucial step is the choice of an appropriate solvent. There are few empirical
rules that can be used as a guide to select a proper solvent, but for the most parts, the selection of
the optimal recrystallization solvent is a trial and error method.
4
The age-old rule is the key
Like dissolves like. Also, the solid should be insoluble or only sparingly soluble in a cold
solvent, and completely soluble in a hot solvent.
5
The impurities should have a different
solubility profile in the particular solvent than the compound of interest.
3
The melting point of
the compound should be higher than the boiling point of the solvent.
4
Finally, given the choice of
solvents, the one with a lower boiling point will be a better option.
5

Decolorizing agents

On a number of occasions, the presence of highly colored impurities will significantly contribute
to the color of the compound. Colored impurities can be removed by the addition of decolorizing
carbon (charcoal) to the hot, yet not boiling, solution.
5
The charcoal has a very fine surface,
which is filled with air. Once it is placed in a solution, the air is displaced by the solvent
molecules; at boiling temperatures, the displacement process is extremely rapid, which usually
results in frothing of the solution and usually leads to the loss of the compound and potential
injury.
4
After the charcoal is added, the solution is heated at or near the boiling point for several
minutes, while continuously being swirl to avoid bumping. Subsequently the charcoal is removed
by gravity filtration, and the filtrate is allowed to cool to yield the crystalline material. Note that
the traces of decolorizing charcoal can cause the gray color in the pure sample after
recrystallization.
2

Filtration

After the crystallization is finished, the crystals should be separated from the liquid. In principle,
the supernatant solution can be decanted from the solid.
4
However, a loss of the solid as well as
an incomplete removal of the liquid, which might contain the impurities, take place. A better
technique to separate the solid from the liquid is by filtration. Fundamentally, filtration is a
process that involves passing the suspension of the solid in the liquid through a membrane that is
permeable only to a liquid.
7
The filtrate, often called mother solution or mother liquor, is
collected in a separate receiving flask, whereas the solid remains on the membrane.
4
there are
two types of filtration used for recrystallization: gravity and vacuum filtration.
2
Gravity filtration
is the best way to remove insoluble material is to filter the hot mixture, while the desired material
is dissolved. Insoluble debris will be trapped on the filter paper. This technique is mostly used to
remove impurities, drying or decolorizing agents.
1
Vacuum filtration, on the other hand, is
usually used to collect solids from the solvents after either precipitation of recrystallization.
2

However, this technique should not be used for filtering hot solutions. During filtration some of
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the solvent is evaporated, which cools down the solution. Since application of vacuum will
enhance the rate of solvent evaporation, the solution will cool off much faster than at ambient
pressure. This can lead to premature crystallization of the solid on the filter paper. The clogging
of the filter paper will occur, which will significantly slow down the filtration process.
4
Thus,
one should keep in mind that vacuum filtration is faster, sometimes much faster, but carries an
increased risk of losing some of the solids if the person doing the filtering is not careful. It
should be used only to collect insoluble solids, because applying a vacuum will sharply increase
loss of the solvent from evaporation.
1,4


As one can tell, gravity filtration rather than suction filtration is used to remove suspended
impurities and charcoal from a hot solution. During suction filtration of a hot solution,
evaporation of the solvent takes place with attendant evaporative cooling. The combination of
these two effects causes crystals to form and clog the Bchner or Hirsch funnel. However,
vacuum filtration is a much more efficient method for removing solvent from the crystals than is
gravity filtration.

Purposes:
From the concepts and theories, one should learn that recrystallization is a purification technique
used for solid compounds. In addition, the keys to recrystallization are: 1) Finding a solvent that
will dissolve your sample while hot; 2) That same solvent should not dissolve your sample while
cold; and 3) The cold solvent must keep impurities dissolved in it forever.

Other techniques used in this lab

Thin-layer chromatography or TLC will also be used in this experiment. TLC is a solid-liquid
form of chromatography where the stationary phase is normally a polar absorbent (solid) and the
mobile phase (liquid) can be a single solvent or combination of solvents. TLC is a technique that
can be used to determine the number of components in a mixture and verify a substances
identity.

After the TLC experiment is completed, the retention factor (

) value is calculated. The


retention factor of a compound is a measure of how far it has moved up a plate under certain
conditions and it is can be use a quick way of identification. The

value is calculated using this


formula:

=
Distance spot travels
Distance solvent travels


Once recrystallization is performed the melting point will also be determined to verify the purity
of the compound and used for identifying the unknown solids. The melting point or melting
range of a solid is defined as the temperature at which the solid and liquid phases of a substance
are in equilibrium.




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Experimental Procedures and Observations

Part 1: Determine solvent/solvent system.

0.010 g of pure naphthalene was weighed out and placed in a reaction tube. 0.5 mL of each
solvent (water, dichloromethane (DCM), methanol, and hexanes) was added and the tube was
shaken. The solubility of naphthalene was recorded. If all of naphthalene sample dissolved at
room temperature then it was not a good choice of solvent for recrystallization. If the sample was
not dissolved, the tube was heated in a sand bath. A sand pit burner was used instead of the
traditional boiling water like in the MIT video. If the sample completely dissolved while hot, the
solvent would be chosen for recrystallization. If not completely dissolved, that particular solvent
shouldn't have been used. Then, the test tube was cooled down until room temperature and then
cooled in an ice bath. If no crystals formed, the inside of the tube would be scrapped with a
spatula or glass stirring rod. If the precipitation was seen, the solvent for recrystallization was
found. The best solvent found for this experiment was methanol.

Part 2: Recrystallization

10 mL of methanol was heated it in Erlenmeyer flask on a hotplate. 0.454 g of impure (red)
naphthalene was added in another Erlenmeyer flask. Small amounts of heated methanol was
pipetted and added to the flask with sample until the crystals were dissolved. The solution turned
red. Thus, a small amount of activated charcoal was added because of the sample was colored.
Activated charcoal traps high molecular weight molecules such as colored impurities. While the
solution was hot, gravity filtration was utilized with a stemless funnel. During the gravity
filtering process, a very high frequency of recrystallization could prevent the solution to pass
through the filter paper. Then the solution was allowed to cool to room temperature and placed in
an ice-bath. The recrystallization process was left undisturbed for five more minutes, and
vacuum filtration was used. The obtained crystals were dried by squeezing technique with a
larger filter paper. The obtained crystals looked grayish. The weight was recrystallized
naphthalene was recorded as 0.39 g.

TLC

The developing chamber was prepared with a beaker with a watch glass on the top. The solvent
(1:1 Ethyl acetate/hexanes) was decanted into the beaker to a depth of just less than 0.5 cm and
the beaker was covered with a watch glass. A TLC plate was cut with a size that only fit the
beaker. The size of the TLC plate was 3 cm x 5 cm. A line was drawn across the TLC plate with
a pencil, 1 cm from the bottom of the plate and two hatch marks were drawn evenly spaced along
the line. The impure and purified naphthalene were spotted with a separated clean TLC spotters
on the hatch marks on the TLC plate. The plate was placed in the developing chamber. As the
mobile solvent traveled up the plate and got close to the top (3.5 cm), the plate was removed
from the beaker, and a line was drawn across the solvent front (0.5 cm from the top) before the
solvent evaporated. The spots were visualized under the UV lamp and the spots were circled with
a pencil. The retention factor,

, value of each spot was calculated. Before recrystallization,


there were two visible spots. The lowest spot traveled 0.4 cm and the highest spot traveled 2.7
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cm. The Rf of the lowest spot or impure substance was 0.114 and of the top spot or naphthalene
was 0.771. However, TLC was performed twice because the plate became contaminated from
touch.

Melting Point Determination

The open end of a melting point capillary tube was thrust into the purified naphthalene several
times. The closed end of the capillary was dropped down several times to fill and pack the
sample. This step was repeated until the height of accumulated sample is about 1-2 mm in the
bottom of the tube. The start temperature was set at 70C, the ramp rate at 1C and the stop
temperature at 260C. Once the apparatus was ready, the capillary was inserted into the chassis
hole and the start button was pushed. The melting point range was recorded when the first drops
of liquid were observed and completely melted. While doing the Melting point determination,
the fast ramp was performed as well as a slow ramp even though identity of the compound was
known. However, to be certain that the process of recrystallization was successful, free from
impurity, the fast ramp was performed. The melting point range was recorded as 80.581.4C.
Cleaning Up
Any organic waste was disposed in the organic waste container. The melting point capillary
tubes were disposed in the broken glass container. For faster drying, acetone was used for
cleaning the glassware in the lab kit.

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Experimental Data

Table 1: Solubility Test
ROOM TEMPERATURE HEATED
WATER INSOLUBLE INSOLUBLE
DCM SOLUBLE SOLUBLE
MeOH INSOLUBLE SOLUBLE
HEXANES INSOLUBLE Partially-SOLUBLE

Chart 1: TLC (before and after Recrystallization)











Table 2: Recrystallization Results
Impure naphthalene 0.454 g
Amount recovered 0.390 g
% recovery 85.9%

value 0.777
MP fast ramp 79.982.0
MP slow ramp 80.581.4


Before After

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Results and Discussion
In Part 1 of the experiment, the solubility of naphthalene in different solvents was determined to
identify the best solvent used for recrystallization. The solubility was recorded as soluble,
partially soluble, or insoluble in water, dichloromethane (DCM), methanol (MeOH), and
hexanes. In water, naphthalene was insoluble at room temperature and insoluble while heated. In
DCM, naphthalene was soluble at room temperature and soluble while heated. In hexanes,
naphthalene was insoluble at room temperature and partially-soluble while heated. In MeOH,
naphthalene was insoluble at room temperature and soluble while heated. Therefore, MeOH was
the best solvent and could be used for part 2 of the experiment. This result confirmed one
concept of recrystallizationthe suitable solvent used for recrystallization that the solute should
be insoluble at room temperature, but should be soluble at the boiling point of the solvent. Note
that this part of the procedure was crucial because without the right solvent, recrystallization
would not be accurate.
In Part 2 of the experiment, 0.5 g of impure naphthalene was recrystallized and verified the
purity by performing TLC and melting point analysis. The amount of the solid recovered was
calculated. 0.454 g of impure naphthalene was used to perform the recrystallization. 0.39 g of
purified naphthalene was recovered. Thus, the recovery yield was 85.9%. Next, the TLC
experiment was performed with 1:1 Ethyl acetate/hexanes. The visual results of the TLC can be
found in Chart 1. The impurity spot traveled 0.4 cm and the purified spot traveled 2.7 cm. The
solvent front traveled 3.5 cm. Thus, the R
f values of the lowest spot or impure substance was
0.114 and of the top spot or naphthalene was 0.771. Next the Melting point determination was
performed which gave a melting range of 80.581.4C. Consequently, TLC and melting point
analysis results confirmed that the recrystallized naphthalene was pure. And the technique of
recrystallization was effective. Moreover, 85.9% of the initial amount of the solid was recovered
meaning that approximately 14.1% was impurities.
As one can tell, recrystallization technique allows for the purification of a crude material. The
small loss in percent recovery was made up by the high gain in purity as shown in the TLC plate.
Furthermore, the purity of the material obtained was correlated to the sharpness and veracity of
the melting point data and this was observed. And the result was proven by determining the
melting point range of the recrystallized material, which was very narrow and was close to the
literature value

Conclusion
Recrystallization is an important method for purifying solid organic compounds. It is also a very
powerful, convenient, and efficient method of purification, and it is an important industrial
technique that is still relevant in the chemical world today.


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References

1. Caron, S. Practical synthetic organic chemistry; 1st ed.; Wiley: Hoboken, N.J ., 2008.

2. Williamson, K.; Masters, K. Macroscale and microscale organic experiments; 6th ed.;
Brooks/Cole: Belmont, CA, 2011.

3. Bunnelle, W.; Meyer, L.; R. E. Glaser, R. Recrystallization Notes by Tiyupaniss
http://www.studymode.com/course-notes/Recrystallization- Notes-1832858.html
(accessed Sep 7, 2011).

4. Tabacco, S.; Siddiqui, A. Recrystallization | MIT Digital Lab Techniques Manual
https://www.youtube.com/watch?v=7LBGQHjgHEw (accessed Sep 7, 2011).

5. Allen, S. Organic Chemistry Lab: Recrystallization
https://www.youtube.com/watch?v=XK0MZk3Q4jk (accessed Sep 7, 2011).

6. Harwood, L.; Moody, C.; Percy, J . Experimental organic chemistry; 1st ed.; Blackwell
Science: Malden, MA, 1999.

7. Lehman, J . Operational organic chemistry; 1st ed.; Pearson Prentice Hall: Upper Saddle
River, N.J ., 2009.


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Post Lab Questions
1. A sample of naphthalene, which should be pure white, was found to have a grayish color after
the usual purification procedure. The melting point was correct, and the melting point range was
small. Explain the gray color.
The gray color of the naphthalene is due to traces of decolorizing charcoal. It can be removed by
filtration through fine filter paper.
2. How many milliliters of boiling water are required to dissolve 25 g of phthalic acid? If the
solution were cooled to 14C, how many grams of phthalic acid would recrystallize out?
The amount of water required to dissolve 25 g of phthalic acid (using the solubility information
in Experiment 2) is 139 mL. On cooling to 14C, this solution should deposit 24.25 g of phthalic
acid.
3. Why should activated carbon be used during a recrystallization?
Activated carbon is added to adsorb high-molecular-weight impurities, which are often colored
and relatively less soluble.
4. If a little activated charcoal does a good job removing impurities in a recrystallization, why
not use a larger quantity?
Activated carbon will adsorb some of the product, decreasing the yield.
5. Under which circumstances is it wise to use a mixture of solvents to carry out a
recrystallization?
A mixture of solvents is used when no single solvent has the desired property of rendering the
substance soluble when hot and insoluble when cold.
6. Why is gravity filtration rather than suction filtration used to remove suspended impurities and
charcoal from a hot solution?
During suction filtration of a hot solution, evaporation of the solvent takes place with attendant
evaporative cooling. The combination of these two effects causes crystals to form and clog the
Bchner or Hirsch funnel.
7. Why is a fluted filter paper used in gravity filtration?
A fluted filter paper has a larger surface area through which the solvent can flow than an
unfluted filter paper, which presses against the glass side of the funnel.
8. Why are stemless funnels used instead of long-stem funnels to filter hot solutions through
fluted filter paper?
If a long-stem funnel is used for filtration, the filtrate will cool and deposit crystals as it passes
down the stem, clogging the stem.
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9. Why is the final product from the recrystallization process isolated by vacuum filtration rather
than gravity filtration?
Vacuum filtration is a much more efficient method for removing solvent from the crystals than is
gravity filtration.
10. Why should wood applicator sticks not be used when carrying out a chemical reaction?
Wood applicator stick will often interact with the reagents being used in the reaction,
contaminating the product.
11. Why should you never use a beaker for recrystallization?
The large opening in a beaker allows solvent to evaporate too easily when trying to dissolve a
solute. A crust of impure material appears around the edge on cooling. The Erlenmeyer flask
solves these problems.

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