RECRYSTALLIZATION

AND
DETERMINATION OF BENZOIC ACID

MELTING

POINT

J.V. DE GUZMAN
DEPARTMENT OF CHEMICAL ENGINEERING, COLLEGE OF ENGINEERING
UNIVERSITY OF THE PHILIPPINES, DILIMAN QUEZON CITY, PHILIPPINES
DATE PERFORMED: JANUARY 28, 2015
INSTRUCTORS NAME: ALLAN KENNETH REGUNTON

ANSWERS TO QUESTIONS
1. How does a fluted filter paper hasten filtration? Why is it
advisable to place a small piece of wire between the funnel and the
mouth of the flask during hot filtration?
Compared to a conventional filter paper, fluted filter paper hastens the
filtration by maximizing the contact area between the filter paper and the
solution and minimizing the contact area between the funnel and the filter
paper. The rate of liquid flow through the filter paper increases because the
flutings of the filter paper permits air to enter the flask along its sides
allowing for pressure to rapidly equalize. Placing a small piece of wire
between the funnel and the mouth of flask, on the other hand, relieves any
pressure increase brought by the hot filtrate. The wire prevents formation of
a solvent seal between the flask and the funnel since such seal will block the
vent of air displaced by the filtrate thus relieving the pressure.
2. Enumerate 2 techniques that can help prevent premature
recrystallization. Explain each item. What can be the consequence if
premature recrystallization was not avoided to occur?
a.) Keeping the filtration set-up warm- the hot solution cools as it runs
through the filter allowing crystallization to occur. Warming the funnel and
the filter paper thus prevents the hot solution from crystallizing during
filtration. Heating the receiving flask helps prevent premature
recrystallization as the filtrate accumulates since this produces vapors that
keeps the funnel and filter paper warm thus preventing crystallization.
b.) Pouring the hot solution in small amounts- It prevents
recrystallization since it lessens the solution's time in the filter preventing it
to cool and crystallize. If crystallization already occurs, pouring small amount
of the hot solvent dissolves the solids.
If premature recrystallization was not avoided, it gives a lower percent
yield and a negative error since the sample that prematurely recrystallized
cannot be accounted in the total yield (unknown mass) and thus considered
to be lost sample.

3. A mixture containing 2.0 g of A and 8.0 g of B is to be separated

and the components purified by one crystallization from 100 mL of
solvent. Their solubilities are given in the table below:

Solvent

cold

hot

cold

hot

Ethanol

0.5

10.0

5.0

20.0

Acetone

5.0

20.0

0.1

8.0

water

0.6

15.0

0.5

10.0

a. What solvent would you choose? Support your answer by

means of a schematic diagram.
The appropriate solvent to be used is acetone since it satisfies
the requirement for an ideal solvent: dissolve the solute of interest at
high temperature and sparingly only at lower temperature. The desired
solute should also recrystallize specifically from the solvent when
cooled. Acetone would effectively dissolve both solutes but it will
selectively recrystallize solute A upon cooling.
100 ml of hot acetone solution can dissolve 20 g A and 8 g B
20 g A
100 ml acetone x
=20 g A
100 ml acetone
8.0 g B
=8.0 g B
100 ml acetone
100 ml of cold acetone solution can dissolve 5 g A and 0.1g of B
5g A
100 ml acetone x
=5 g A
100 ml acetone
0.1 g B
100 ml acetone x
=0 .1 g B
100 ml acetone
100 ml acetone x

Mixture of 2 g A and
8 g B dissolves in
hot acetone solution
Cool solution.

2 g of A and 0.1 g
of B remains in
the mother liquor

7.9 g of B
crystallizes out

b. Theoretically, what is the purity of A and B after one crystallization?

The recrystallized B is 100% pure though its yield is only 98.75%
(based from 8 g on the sample initially). On the other hand, compound A is
only 95.24 % pure.
4. A mixture of three compounds, A, B and C, is to be separated and
purified by crystallization. Their solubilities in g/100 mL ethanol are
given below.
Solvent
A
B
C
Cold

1.05

5.6

4.2

Hot

20.5

2.3

3.5

MIXTURE: 4.0
g A + 4.0 g B +
4.0 g C

Heat
solution

MOTHER
LIQUOR: 4.0
g A + 2.3 g B +
3.5 g C

UNDISSOLVED
CRYSTALS: 1.7
g B and 0.5 g C

Cool
solution

MOTHER LIQUOR:
1.05 g A + 2.3 g B
+3.5 C
RECRYSTALLIZED:
2.95 g A

a. If a mixture containing 4.0 g each of A, B and C is recrystallized from 100

mL

[1]University of Sydney Faculty of Science. Skills. [Online] 2014.

https://scilearn.sydney.edu.au/fychemistry/LabManual/Skills.pdf
(accessed February 9, 2015).
[2]University of Calgary Department of Chemistry.Organic Laboratory
Techniques.
[Online].
2014.
http://www.chem.ucalgary.ca/courses/351/laboratory/filtration.pdf
(accessed February 9, 2015).
[3]Pavia, D., Kriz, G., Lampman, G., Engel, R. A Microscale Approach to
Organic Laboratory Techniques. Chapter 11: Crystallization: Purification
of Solids. Brooks/Cole: California, 2013. pg 684.
[4]Gilbert, J. and Martin, S. Experimental Organic Chemistry 5th ed. Chapter
2: Techniques and Apparatus. Brooks/Cole: California, 2013. pg 66.
[5]University
of
Wisconsin-Madison
Department
of
Chemistry.
Recrsytallization.
[Online].
2014.
http://chem.wisc.edu/deptfiles/genchem/Chm346/pdf/recrystallization.p
df (accessed February 9, 2015)
[6] University of Toronto Department of Chemistry.Recrystallization.
[Online].2014
http://www.chem.utoronto.ca/coursenotes/CHM249/Recrystallization.pd
f (accessed February 9, 2015).

Portland Community College. Extraction of Caffeine from Tea Leaves.

[Online].
2014.
http://spot.pcc.edu/~chandy/241/CaffeineExtractionCH2CCl2.pdf
(accessed February 9, 2015)
http://www.xula.edu/chemistry/documents/orgleclab/Caffeineprocedure.pdf
http://infohost.nmt.edu/~jaltig/Caffeine.pdf

1. Solvents for extraction experiments should have desirable properties. Here is a list.
For both liquid-liquid and liquid-solid extractions, the solvent should have a relatively low
boiling point for easy removal by evaporation; and it should not react with any of the
substances present (unless you are performing an acid-base extraction).
In liquid-liquid extraction, the compound being extracted should have a favorable
distribution coefficient in the extracting solvent; in liquid-solid extraction, the solvent
must
dissolve
the
compound
being
extracted.
2. The caffeine extraction procedure has several features that may seem pointless at
first.
Here
are
some
explanations.
Caffeine is an alkaloid, an organic base. Sodium carbonate also a base, and it is added in
the first extraction to make sure that the caffeine remains in the free base form (that
is, to prevent it from reacting with any acids that may be present).
An emulsion is a suspension of one liquid as droplets in another (the two liquids must be
insoluble in one another). Emulsions are almost always undesirable. To avoid them, you
can shake mixtures of insoluble liquids gently and add salt to aqueous
layers. You will use a centrifuge in this experiment break up emulsions once they form.
The visualization technique used in the TLC portion of this experiment involves the use of
ultraviolet (UV) light. The caffeine absorbs the UV light and gives off visible light.
This
phenomenon
is
called
fluorescence.
3. The equation for calculating the percentage of caffeine in tea is as follows:
amount
of
caffeine
recovered
percentage
of
caffeine
=
-------x
100%
weight
of
tea
There are some systematic errors in this experiment as we perform it. For example, you
do
not weigh the tea, you weigh the tea bag, which has not only tea but also string and
paper
in
its weight. When you squeeze the tea (liquid) out of the tea bag, some of the liquid
(containing caffeine) remains behind in the wet bag. The distribution coefficient of
caffeine between water and dichloromethane is not perfect; some caffeine will remain
behind in the water. Dichloromethane evaporates rapidly, cooling the watch glass as it
does; water can condense on the cool watch glass, influencing the weight of your final
product.
http://www.xula.edu/chemistry/organic/No...
Caffeine can be extracted easily from tea bags. The procedure one would use to make a
cup
of
tea, simply "steeping" the tea with very hot water for about 7 min, extracts most of the
caffeine.
There is no advantage to boiling the tea leaves with water for 20 min. Since caffeine is a
white, slightly bitter, odorless, crystalline solid, it is obvious that water extracts more than
just
caffeine.
When the brown aqueous solution is subsequently extracted with dichloromethane,
primarily caffeine dissolves in the organic solvent, leaving the other substrates in the
aqueous layer. Evaporation of the solvent leaves crude caffeine, which on sublimation
yields a relatively pure product. When the concentrated tea solution is extracted with
dichloromethane, emulsions can form very easily. There are substances in tea that cause
small droplets of the organic layer to remain suspended in the aqueous layer. This
emulsion
formation
results
from
vigorous
shaking.
To avoid this problem, it might seem that one could boil the tea leaves with
dichloromethane first and then extract the caffeine from the dichloromethane solution
with water. In fact, this does not work. Boiling 25 g of tea leaves with 50 mL of
dichloromethane gives only 0.05 g of residue after evaporation of the solvent. Subsequent
extractions give less material. Hot water causes thetea leaves to swell and is obviously a
much more efficient extraction solvent. An attempt to sublime caffeine directly from tea
leaves
also
was
unsuccessful.
Procedure
In a 50-mL beaker place 20 mL of water, 2 g of sodium carbonate, and a wooden boiling

stick.
Bring the water to a boil on the hotplate, remove the boiling stick, and brew a very
concentrated
tea solution by immersing a tea bag (2.4 g tea) in the very hot water for 5 min. While
wearing latex gloves, squeeze as much tea from the bag as possible after it cools enough
to handle. Be careful not to break the bag. Again bring the liquid to a boil, and add a new
tea bag to the hot solution. After 5 min, remove the tea bag and squeeze out as much
water as possible. This can be done easily on the Hirsch funnel. Rinse the bag with a few
milliliters of very hot water, but be sure the total volume of aqueous extract does not
exceed
12mL.
Pour
the
extract
into
a
15-mL
centrifuge tube, and cool the solution in ice to below 40C (the boiling point of
dichloromethane).
Using three 2-mL portions of dichloromethane, extract the caffeine from the tea. Cap the
tube
and use a gentle rocking motion to carry out the extraction. Vigorous shaking will produce
an intractable emulsion, while extremely gentle mixing will fail to extract the caffeine. If
you have ready access to a centrifuge, the shaking can be very vigorous because any
emulsions formed can be broken fairly well by centrifugation for about 90 sec. After each
extraction, remove the lower organic layer into a reaction tube, leaving any emulsion
layer behind. Dry the combined extracts over anhydrous sodium sulfate for 5 or 10 min in
an Erlenmeyer flask. Add the drying agent in portions with shaking until it no longer
clumps together. Transfer the dry solution to a weighed 25-mL filter flask containing a
boiling chip, wash the drying agent twice with 2-mL portions of dichloromethane, and add
the washes to the test tube or filter flask. Evaporate the dichloromethane to dryness by
carefully
placing
the
tube/flask
into
a
hot
water
bath
(NOT
ON
A
HOTPLATE) and allowing the ether to boil away. You can facilitate the removal of the
vapors by holding a Pasteur pipette connected to a water aspirator just above the surface
of the boiling liquid. Be careful not to touch the liquid or your product will be drawn into
the pipet and lost down the drain. Continue the evaporation until no trace of the smell of
dichloromethane can be detected. The residue remaining in the filter flask will be crude
caffeine (determine its weight) that is to be purified by sublimation.