Dagondon, Vanessa Olga

Date Performed: February 16, 2015

Sanchez, Diandra Dawn

Date Submitted: February 23, 2015

Recrystallization and Melting Point Determination

Experiment 3
I.

Objectives
This experiment aims to elucidate the meaning of purity chemically by
applying the method of recrystallization in purifying a solid sample. Melting point
determination will also be used to compare the melting point of a pure vs. impure
sample of a substance.

II.

Results and Discussion

Recrystallization is one of the many techniques used to purify organic
compounds presumably solids. This technique involves the dissolution of a solid in a
pre-selected solvent at an elevated temperature thereby re-forming crystals upon
cooling, leaving the impurities to remain in solution to be filtered. This type of
recrystallization is called solution recrystallization. Other methods in purifying
compounds are sublimation, extraction and chromatography. Nevertheless, the overall
purpose of these methods is to separate impurities from the desired substance in order
to achieve the highest possible state of purity.
Recrystallization is not a perfect method and thus, needs further verification.
The compound/substance under consideration might still contain impurities, however
minimal. To check whether the recrystallized compound already achieved its highest
state of purity, melting point determination is often performed. Melting point
determination is one of the easiest ways to verify the purity of a recrystallized
substance. The melting point of a solid is defined as the temperature at which the
solid and liquid phases are in equilibrium. It is usually the melting point range (from
the first sign of melting to the complete melting of the solid) of the substance that is
obtained rather the exact time consumed to acquire the said equilibrium. This is
because in evaluation, a narrow melting point range would indicate high purity
compare to that of a broader range. Also, relative to a compounds crude state to its
pure state: a crude compound would yield a lower melting point compare to its
recrystallized form.

The principle behind recrystallization is the utilization of the solubilities of the

involved compounds (the crude sample and solvent) while being subjected to
different temperatures. Compounds tend to be more soluble in liquids (solvents) at an
elevated temperature than in liquids at low temperatures. Considering this, if a solid
was found out to be soluble in a solvent when exposed to a high temperature (and was
insoluble at room temperature) then it (the solution) will most likely to form or grow
crystals when cooled. This is because the solid (the solute) will no longer be soluble
in the solvent and thus will re-form back to its solid state (now, crystals). These
crystals will form without the soluble impurities (they will remain in the solution)
making the separation possible through gravity filtration.
In this experiment, caffeine and naphthalene were supposed to undergo
recrystallization followed by melting point determination to verify the compounds
extent of purity. However, only a small amount of caffeine was isolated (from the
previous experiment) and therefore, would be insufficient in the execution of the
experiment. Due to this scarcity, only one group was tasked to perform the
recrystallization of caffeine collecting all the classs isolated sample. The
naphthalene, however, were done by group.
The following are the parts were done in the experiment:
Selection of an appropriate solvent
This is first and the most crucial step in recrystallization. A larger yield of a pure
solid crystal is obtained successfully not only by carrying the whole technique
properly but also by selecting the appropriate solvent. A large yield is defined to
be 80 to 90 % of the original weight of the crude sample. As explained earlier,
manipulating the solubilities and temperature is the main idea incorporated in
recrystallization and therefore the likelihood of this method highly depends on the
properties of solvent used to dissolve the target compound to be purified.
In the experiment, three solvents were tested on both caffeine and naphthalene:
Water, 95% ethanol, CCl4. The solvent that must be chosen is one that could
dissolve caffeine and naphthalene when heated. Conversely, the solvent must be
incapable of dissolution if its temperature is low or only at room temperature.
Other qualifications are further enumerated (as seen on part III #3).
In this case, it was found out that the appropriate solvent that must be used in
recrystallizing naphthalene is the 95% ethanol; and for caffeine, the solvent
suitable is water. Both solvents were unable to dissolve their respective solutes in
room temperature and were able to do so in an elevated temperature.

Naphthalene is a non-polar aromatic hydrocarbon. Recalling like dissolves like:

polar solutes will be soluble in polar solvents and nonpolar solutes will be soluble
in non-polar solvents. Water, as one the three options, would be a bad choice. As a
non-polar compound, Naphthalene would be insoluble in the very polar water.
CCl4, on the other hand, is non-polar (although its four bonds are polar, the
polarity of the whole molecule will be cancelled because of its symmetric
tetrahedral molecular geometry). However, Ethanol, also non-polar is a better
choice than CCl4. Ethanol has a relatively low boiling point (78.37 C) compared to
that of naphthalene (218 C). This property of the solvent makes it compatible in
the recrystallization of the compound. Caffeine (boiling point of 178 C) is a polar
compound and therefore water (boiling point of 100 C), being the only polar
solvent present as choices, would be a good solvent.
Recrystallization
The next part of the experiment is the recrystallization. 1.0117 grams of
Naphthalene was dissolved on a 25-ml test tube with 15- ml ethanol. This
dissolution was done in the presence of heat (up to the solvents boiling point)
with constant stirring to avoid bumping of the solution. The solution was not
colored and therefore will not need any addition of decolorizing agent (activated
carbon). Afterwards, the saturated hot solution underwent gravity filtration. This is
done to remove insoluble impurities. Next, the solution was cooled slowly using an
ice water bath. The solvent was also cooled alongside the saturated solution. This
cooled solvent will be used later on to wash the crystals formed during the suction
filtration. The cooing process should be done slowly without any agitation because
this may cause smaller crystals and thereby would result to larger surface area that
may cater adsorption of impurities. Exposing the solution to a cooler environment
will form the crystals. The soluble impurities will remain in solution. After
cooling, the crystalline product and the soluble impurities are then separated by
vacuum filtration using a Buchner funnel, a clean, dry filter flask and a preweighed filter paper (0.5385g). The crystals are washed by a small amount of cold
solvent. It took about 30 minutes to finish the vacuum filtration. The next step
would be drying the crystals. After the filtration, the filter paper with the
crystalline product was transferred into a watch glass. This is then set aside to be
dried. This step is to get rid of the unwanted solvent in the crystals (this is also the
reason why a solvent with low boiling point is desired so it is easily evaporated).
Afterwards, the filter paper with the crystals was weighed (0.7484g).

The table below shows the data gathered and the yield for Naphthalene.
Table 1: Naphthalene Data
Crude Naphthalene
Pre-weighed filter paper
Filter paper + naphthalene crystals
Recovered purified naphthalene
Percentage yield

Mass in grams (g)

1.0117
0.5385
0.7488
0.7488 0.5385 = 0.2103

As seen on the table, the percentage yield was only 20.79%. Errors must have
occurred during the experiment. These errors with this magnitude, however, were
already anticipated. Recrystallization needs a lot of careful handling and practice
since the procedure itself can induce errors. Loss of sample cannot be avoided in
filtering: some materials might be left behind. This error, however, can be
minimized by practice. Some loss may be caused by the prolonged contact of the
solid and its recrystallization solvent. This is because the solid is somehow still
soluble in the solvent even at low temperature. Another cause might root in rinsing
the crystals during vacuum filtration. It may be that too much solvent is used.
Melting Point Determination
Verification of the purity of the recrystallized solids must be done. Using a
melting point apparatus, the meting points of the crude and recrystallized solids
were taken. Small amount of the solids were put into capillary tubes to be placed
in the apparatus. Four temperatures were taken in the following time frames: Stage
1 the appearance of bubbles and darkening of the solution; Stage 2 the
breaking down of the solid; Stage 3 formation of meniscus; Stage 4 complete
liquefaction of the solids.
Table 2: Naphthalene Meting Point Data
Stage 1
Stage 2
Crude
80 C
81.1 C
Naphthalene
Recrystallized
80.2 C
81.3 C
Naphthalene

Stage 3
81.5 C

Stage 4
82.0 C

81.7 C

82.0 C

The table above shows the melting point of the crude and recrystallized
naphthalene. As expected, the melting point of the crude naphthalene is lower than

the recrystallized one. The range of the crude sample is wider than the
recrystallized naphthalene.
Table 3: Caffeine Meting Point Data
Stage 1
Stage 2
Crude Caffeine 231
Recrystallized
232
Caffeine

Stage 3
234
233

Stage 4
235
235

The table above shows the melting point of the crude and recrystallized caffeine.
The stage 1 melting point wasnt observed since it was hard to tell if there were
already bubbles. Errors can also appear in this part of the experiment because it
depends on visual judgments.
III.

Questions
1. What is a crystal and what is meant by recrystallization?
A crystal is "a three-dimensional atomic, ionic, or molecular structure consisting
of periodically repeated, identically constituted, congruent unit cells" and to
crystallize is "to cause to form crystals or assume a crystalline form". (American
Heritage Dictionary of the English Language, 1973) Recrystallization, then, is a
process in which impure crystals undergo series of procedures from dissolution in
a selected solvent to subjection in a low temperature to attain their purest state.
2. How does recrystallization free a substance from impurities? Explain how each
step in recrystallization contributes to the removal of the impurities.
Recrystallization takes advantage of the solubility properties of the impure
organic crystal/solid in a hot solvent to remove its impurities. The first thing that
must be done is selecting a suitable solvent where the impure solid is dissolved.
In choosing the appropriate solvent, one must take note of the temperature in
which the solid is dissolved. Ideally, the solubility of the solid should be at its
maximum in the solvent with an elevated temperature and at its minimum in the
solvent with low temperatures. This step is crucial because the properties of the
chosen solvent make the whole process possible. After choosing, the solid must
be dissolved in it (selected solvent) while subjected to heat. By doing so, the
impurities on the solid will be vulnerable to separation. The next step would be
the addition of decolorizing charcoal (activated carbon). This is only done,
however, if the solution is colored. What the activated carbon does is making the

colored molecules be adsorbed on its surface thus decolorizing the solution. This
step is then followed by cooling the solution to reform crystals, now, without the
soluble impurities that remained in solution. Suction filtration is done next to
separate the solid compound to its soluble impurities. The recovered solids are
then dried to remove the remainder of the recrystallized solvent (also an
impurity).
3. What must be considered in choosing a solvent for recrystallization?
A solvent considered for recrystallization must satisfy the following: (a) the
solvent must dissolve the organic solid in an elevated temperature (ideally about 5
g/100 mL) and must not able to do so in low temperature/ room temperature; (b)
the impurities must be insoluble or partially soluble in the cold solvent; (c) the
solvents boiling point should be low enough so that it is easily removed from the
recrystallized solid by merely letting it dry; (d) the boiling point of the solvent
must be lower than that of the purified solids melting point; (e) lastly, the solvent
should not react with the organic solid chemically to avoid complications.
4. What is melting point? Why can it be used as an index of purity?
The melting point of a solid is defined as the temperature at which the solid and
liquid phases are in equilibrium. In recrystallization, the meting point taken (as
basis of purity) is temperature range at which a compound melts from the
observation of the initial melting of the first to the last crystal.
Taking account that crystals with high melting points have strong intermolecular
forces acting on its molecules, one can deduce that crystals or solids with
impurities will have a lower melting point. This is why melting point can be used
as an index of purity. The more pure the substance, the higher and sharper the
melting point.
IV.

Conclusion
Purity, in the chemical sense, is very important in organic chemistry
especially in carrying out chemical reactions. If the reactant used is in its purest state
then it is very likely for the reaction to succeed and thus, getting the desired product.
There are a lot of purifying techniques and one of these is recrystallization.
Recrystallization is a technique that aims to separate the solid from its impurities by
using the principle of solubility. This method was applied to the crude Naphthalene
and caffeine. Although the percentage yield wasnt that favourable in terms of
magnitude, the recrystallization was a success. This is proved by melting point

determination. The crude samples were found out to have lower melting point and a
broader range while the recrystallized samples have high and sharp melting points.
V.

References

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City, Philippines: C&E Publishing, Inc.
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http://www.xula.edu/chemistry/documents/orgleclab/07Recrnotes_v3
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http://www.chem.utoronto.ca/coursenotes/CHM249/Recrystallization.pdf
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http://www.chem.umass.edu/~samal/269/cryst1.pdf
I hereby certify that the undersigned made his/her best effort in the creation of this
laboratory report.

______________________
Dagondon, Vanessa Olga J.

______________________
Sanchez, Diandra Dawn J.