Experiment: Recrystallization – Part I: Solvent Selection

Recrystallization is a classic technique that is widely used by organic chemists to purify solids.
The key to this process is the recrystallization solvent, the substance that enables us to separate
the solid we are trying to purify from the impurities which contaminate it. In a real lab situation,
when you are trying to purify an unknown solid, you will not be told which solvent to use.
Rather, you will have to find one on your own. The purpose of this experiment is to show you
how this is done.
Types of Impurities to be Removed during a Recrystallization:
Impurities ideally fall into one of two categories: soluble impurities and insoluble impurities.
Soluble impurities are impurities which are very soluble in the recrystallization solvent at room
temperature. Insoluble impurities are impurities that are insoluble in the recrystallization solvent
even at the solvent’s boiling point.
Characteristics of a Good Recrystallization Solvent:
1. The recrystallization solvent should NOT dissolve the substance to be purified at
room temperature, but it should dissolve it well at the solvent’s boiling point
2. The solvent should dissolve soluble impurities well at room temperature.
3. The solvent should not dissolve insoluble impurities even at the solvent’s boiling
point. These insoluble impurities can then be removed by gravity filtration.
4. The solvent must not react with the substance to be purified.
5. The solvent should be volatile.
6. The solvent should be inexpensive.

Characteristics 1, 2, 3, and 4 are essential for a good recrystallization solvent. Characteristics 5

and 6 are desirable, but not essential.

 Pre-lab Preparation

1. Carefully read the material in the background section of this experiment as well as an
outside reference on recystallization, such as the material from discussion or on the
internet.

2. Write the structural formulas for each of the four solutes and five solvents in your
notebook. On each structure, identify the polar and non-polar parts. In a column next
to the structures, list what type or types of intermolecular forces would be exerted by
these molecules or parts of molecules.

3. Prepare a table containing the boiling point of any solvent used in this experiment and
the melting point of all solutes. This information will be valuable for you in lab in
determining the appropriate temperature to heat your solutions during the lab.
 Experimental Procedure

! Safety Considerations

! When heating your solid-solvent mixtures take care to select the correct temperature bath to
avoid heating too rapidly. If any of the solids, solvents, or solutions spill on your hands, wash
them thoroughly with soap and water.

In today’s experiment, you will be working with a partner. There are four “substances to be
purified” and five potential recrystallization solvents. Each of you will select two known organic
solids from the list on the next page and test its solubility in five different solvents. Even though
each of you will be working with only two of the four “substances to be purified,” you are
required to show your partner your set of test tubes and review the results of your solubility tests.
By the end of the experiment, you should both be confident of the results you will be reporting
for all four compounds.

Potential
Solids to be Structure of
Structure of Solid Recrystallization
Recrystallized Solvent
Solvents

biphenyl water (W) H2O

benzoic acid OH methanol (M) CH3OH

O
HO Mixture of low
adipic acid OH petroleum ether (P)
boiling alkanes
O
NH2
CH3

4-nitroaniline toluene (T)

NO2
O
acetone (A)
H3C CH3
1. Into five test tubes labeled with the names of the potential recrystallization solvents, place
0.10 gram of one of the solids you have chosen. (To save time, measure out one 0.10-g
sample and estimate visually the other four.) To each test tube, add 1 mL of the potential
recrystallization solvent. You should now have five test tubes, each with the same solid
but a different solvent.

2. Using a stirring rod or some other means of mixing, mix the solid-liquid mixture
vigorously to see if the solid dissolves. If it does dissolve, no further testing with this
solvent is necessary.

3. If it does not dissolve, heat the tubes, with vigorous mixing, in a hot water bath. This
should either be the 60 ºC water bath available for you or a boiling water bath that you
need to prepare. Based on your pre-lab data, decide which bath should be used for each
sample. Note that you do not want to boil off your solvent, so you should not heat longer
than 2 minutes or remove immediately if the solvent begins to boil. If the level of these
solvents drops significantly during the 2 minutes of heating, add more solvent to restore
the volume to its original value.

Note: One of these solids has a melting point below 100ºC (see your pre-lab data). It will
melt in a boiling water bath. Do not confuse melting with dissolving. If it melts, it will
not dissolve but appear as a second phase at the top or bottom of the test tube.
4. If the solid does not dissolve in 1 mL of hot solvent, cool the tube, add another 1 mL of
solvent and again bring the system to a boil with mixing. If the solid dissolves, cool and
check for crystallization again.

5. If the solid still does not completely dissolve in 2 mL of hot solvent, cool the mixture and
add another 1 mL of solvent and heat with mixing. If it dissolves in 3 mL of hot solvent,
cool the mixture to see if crystallization occurs.

6. Repeat the above steps for your second solute.

7. When you have completed the solubility testing, discard all solutions and undissolved
solid in the waste container provided. Remove all labels from the test tubes, wash them
thoroughly and place them in the correct bin for washed tubes.

7. Collect solubility data for the solids that your partner tested.

By the end of the experiment, you should know one of the following things about each solid:

1. The solid is soluble in 1 mL of room temperature solvent.

2. The solid is soluble in 1 mL of hot solvent.
3. The solid is soluble in 2 mL of hot solvent.
4. The solid is soluble in 3 mL of hot solvent.
5. The solid is insoluble in 3 mL of hot solvent.

The chart shown below should appear in your lab notebook for each of the solutes whose
solubility you tested. Use the symbols S (soluble), SS (somewhat soluble), and I (insoluble).
 W M P T A

Solubility at room
temperature (1 mL)

Solubility at boiling
point (how many mL?)

 Post-Lab and Report Requirements

For this short experiment, you should prepare a neat, well organized table of solubility data
similar to the one in your notebook for all four of the solids that you and your partner collected.

Questions

1. For each of the four solids tested, tell which solvent or solvents could be used to
recrystallize it. Explain your selections.

2. A student has tested a solvent for suitability for recrystallizing compound X. Some of the
sample dissolved but not all. What conclusions would you draw about the suitability of
this solvent for recrystallizing X? Would you discard this solvent as an option or do
further testing?

3. Solid X does not dissolve in methanol at room temperature, but does dissolve well at
methanol’s boiling point. Solid Y, a common impurity produced during the synthesis of
X has similar solubility properties in methanol to those of X. How effective would
recrystallization using methanol be for isolating pure solid X from a mixture containing 5
grams of X and 3 grams of Y? Explain your answer in detail.