Recrystallization

and Melting Point Determination of Benzoic Acid

Comia, Joshua Paul L.
National Institute of Molecular Biology & Biotechnology, University of the Philippines, Diliman, Quezon City
Date Performed: 03 September 2014
Date Submitted: 05 September 2014


Answers to Questions

1. How does the use of 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?

A fluted filter paper allows faster filtration due to having a larger surface area that allows for better airflow
between the filter paper and the funnel wall (Ledgard, 2003). In addition, fluted filtration is an effective way in
removing impurities when the volume of the liquid has exceed 10 mL and charcoal is used, as in the case of the
experiment. Placing a small piece of wire between the funnel and the mouth of the flask allows better
directional flow for the liquid and a relief of pressure that could be produced by the hot filtrate (Pavia et al,
2012).

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?

The receiving container should be kept warm to prevent premature recrystallization during filtration (Myers &
Pedersen, 2011). This can be done by placing the receiving container in a warm bath or placing some of the hot
solvent into the receiving vessel. In addition, minimal addition of the hot solvent to the solution being filtered
might be needed to prevent recrystallization within the solution itself (Gilbert & Martin, 2002). Post-filtration,
the added solvent is commonly removed through evaporation. In some cases where some crystals form, pouring
a small amount of boiling solvent would result to its dissolution but in the case of premature recrystallization, a
lower yield would be present in the calculation of the percent (%) recovery since some of the desired crystals
would be lost.

3. A mixture containing 2.0 g of A and 8.0 g of B is to be separated and purified by one recrystallization from 100
mL of solvent. Their solubilities are given in the table below:

A
B
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 choice by means of a schematic diagram.
Addition of 100 mL h ot
(a) ethanol/ (b) acetone/
(c) water would allow
the solutes to remain in
the solution

After filtration, the

addition of 100 mL cold
(a) ethanol/ (b) acetone/
(c) water

(a) 1.5 g of A and 3.0 g of B forms as

crystals; (b) 0 g of A and 7.9 g of B forms
as crystals; (c) 1.4 g of A and 7.5 g of B
forms as crystals. The rest of the original
amount of solutes remain in solution.

Theoretically speaking, the solvent that would be most efficient is A since it separates the two compounds
efficiently by allowing compound A to stay in the solution while recrystallizing 7.9 g of compound B.

b) Theoretically, what is the purity of A and B after one recrystallization?

Theoretically, from the best solvent that would produce the most crystals, the purity of A and B after one
recrystallization should be 0% and 100%, respectively.

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

a) If a mixture containing 4.0g each of A, B, and C was recrystallized from 100 mL ethanol, which compound
would be obtained pure?

Compound A would be obtained pure due to the fact that in the process of cooling the hot filtrate for each
of the three compounds, 2.95 g of A was the only recrystallized compound while B and C remained within
the solution. Initially, 1.7 g of B and 0.5 g of C remained as crystals after the addition of the hot solvent but
after the addition of the cold solvent, the remaining crystals dissolved completely in the solution.

b) If the filtrate from (a) is evaporated to 50 mL, which of the compound(s) will separate upon cooling? What
is its purity?

Tracing the quantities from the remaining solution in (a), within the 100 mL ethanol solvent is 1.05 g of
compound A, 4.0 g of compound B, and 4.0 g of compound C. Using rational values to determine the
solubility of each compound, as shown in Appendix A, the solubilities of A, B, and C per 50 mL of ethanol are
0.525, 2.800, and 2.100 respectively. Upon cooling, all three compounds will separate due to the
recrystallization of 0.525 g of A, 1.2 g of B, and 1.9 g of C. The purity of the three compounds post-cooling is
14.48% for A, 33.10% for B, and 52.42% for C.

5. You need to perform a recrystallization using a mixed solvent system. Which of the following solvents could
not be used as solvent pairs for the experiment? Explain your selection.

a) Hexane and water
b) Chloroform and diethyl ether
c) Acetone and methanol

It is a key factor to remember as a general rule that like dissolves like substances with similar properties and
intermolecular forces would have strong solute-solvent interactions that can result to the formation of solutions
(Goode et al, 1997). Due to the polarity of the compounds, Hexane being considerably non-polar and water
being a polar compound, the solvent pair could not be used since the combination of both substances would
result to the formation of immiscible layers. This immiscibility fails to meet the initial requirement that both
compounds must be miscible in order for the solvent pair to be considered in the experiment for mixed solvent
systems.

6. What are the advantages/disadvantages of mixed solvent recrystallization over single solvent
recrystallization?

If a single solvent cannot be found for recrystallization, mixed solvent systems prove to be very useful. This
usually involves the dissolution of a given solute in a small amount of soluble solvent heated to its boiling point.
The addition of the second solvent should be done slowly while keeping the solution constantly hot until
turbidity or cloudiness can be observed. It is important to remember that this observation is caused by the
reaction of your insoluble solvent with your desired compound in the solution. While it can be quite specific in
recrystallizing compounds, a disadvantage for the use of this approach is the possible use of excess amounts of
initial solvent which can result to the need of unduly large volumes of the second one (Gilbert & Martin, 2011).
In addition, mixed solvent recrystallization allows the filtration and purification of a desired compound through
the use of two different solvents with varying solubilities. Unlike single-solvent recrystallization, there is a better
chance at receiving a higher percent (%) purity since impurities are more likely to be filtered and separated.

References

[1] Gilbert, J. C., & Martin, S. F. (2002). Recrystallization and Melting Points. Experimental organic chemistry: a miniscale
and microscale approach. (3rd ed., pp. 97-98). Fort Worth: Harcourt College Publishers.

[2] Ledgard, J. B. (2003). Filtration. The preparatory manual of chemical warfare agents: a book (Third ed., pp. 20-21).
South Bend, IN: Paranoid Publications Group.

[3] Pavia, D., Lampman, G., Kriz, G., & Engel, R. (2012). Semimicroscale Recrystallization. A microscale approach to
organic laboratory techniques (Fifth ed., p. 684). USA: Cengage Learning.

[4] Pedersen, S. F., & Myers, A. M. (2011). Isolation and Purification of Compounds. Understanding the principles of
organic chemistry: a laboratory course (pp. 98-99). Belmont, CA: Brooks/Cole Cengage Learning.

[5] Reger, D. L., Goode, S. R., & Mercer, E. E. (1997). Principles of Solubility. Chemistry, principles & practice (2nd ed., p.
477). Fort Worth: Saunders College Pub.

Appendix A
Calculations


For the instance of evaporating the filtrate to 50 mL, the determination of the solubility per compound is as follows:

( )
( )
=

100
50

Compound A

1.05

=

100
50
1.05 50
=

100
= 0.525
therefore, the solubility of compound B after evaporation to 50mL and upon cooling is 0.525 g/100mL solvent

Compound B

5.60

=

100
50
5.60 50
=

100
= 2.8
therefore, the solubility of compound B after evaporation to 50mL and upon cooling is 2.8 g/100mL solvent

Compound C

4.20

=

100
50
4.20 50
=

100
= 2.1
therefore, the solubility of compound B after evaporation to 50mL and upon cooling is 2.1 g/100mL solvent

For percent purity of each compound,

=
100

Compound A
0.525
=
100
0.525 + 1.2 + 1.9
= 14.42%
Compound B
1.2
=
100
0.525 + 1.2 + 1.9
= 33.10%
Compound C
1.9
=
100
0.525 + 1.2 + 1.9
= 52.42%