RECRYSTALLIZATION

THEORY
It is a method to purify solids. The trick is to find a solvent which dissolves your
solid crystals and the impurity when hot and lets your desired pure crystals precipitate out
upon cooling the solution, leaving the impurities still dissolved in the cooled solution.
In any case, you will have to remember a few things.
1. Find a solvent that will dissolve the solid while hot.
2. The same solvent should not dissolve it while cold.
3. The cold solvent must keep impurities dissolved in it forever or longer.
4. The solvent should be unreactive towards the sample. Otherwise it gives reaction
with sample and changes its chemical structure.
5. The solvent may be a pure substance, such as diethyl ether or ethyl alcohol, or it may
be a mixture of two or more substances that give the desired solubility characteristics.
For crystallization to occur the concentration of a dissolved compound must exceed
the equilibrium solubility; that is, the solution must be supersaturated at the given
temperature. With few exceptions, the solubility of solid increases with an increase in
temperature, often many fold over a 30 C to 40 C temperature increase. Thus, a solid
sample is dissolved in a minimum of hot solvent, and crystallization occurs on cooling. For
a proper solvent system, the sample’s solubility should increase rapidly as the melting
point of the solid sample is approached during heating.

The solubility of crystalline organic compounds in a solvent depends on two major factors:
1. The relative polarity of the solvent and solute.
2. The energy of the crystal lattice of the solute.
The effect of polarity can be summed up by the statement “like dissolves like’’. Thus,
compounds that contain one or more polar groups, such as, -OH, -NH2, -COOH, or -
CONH2, are usually more soluble in hydroxylic solvents (e.g., water or alcohols) than in
hydrocarbons, such as toluene or hexane. Conversely, the latter more easily dissolve
compounds of low polarity. Within a series of compounds of the same polarity, the
relationship is that the higher the melting point (high crystal lattice energy), the lower the
solubility is in a given solvent.

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 In selecting a solvent for recrystallization process, the main requirement is a suitable
solvating power, that is, one that provides high solute solubility in hot solvent and a
significantly lower solubility at room temperature or below. Frequently, this requirement is
met by using mixture of two solvents in which the solute has quite different solubilities.
Water is a convenient solvent for recrystallizing some moderately polar compounds
with melting points above 100 0C. Mixtures of water and alcohols are widely used. The low
boiling points of diethyl ether and methylene chloride (dichloromethane) make them
attractive for recrystallizing low melting solids.
The general procedure for recrystallization involves the following steps:
1. Selection of a suitable solvent through experiment or from data on solubility.
2. Dissolution of the material in the hot solvent (near the boiling point).
3. Filtration of the hot solution to remove insoluble impurities or impurities absorbed a
decolorizing agent.
4. Crystallization of the solute from the cool solution.
5. Collection of the purified crystals.
6. Washing and drying the product.

The most commonly used recrystallization solvents are presented in the following table.

FINDING A GOOD SOLVENT

Place some amount of your solid in a test tube and some amount of solvent, and
shake it. If all of the solids are dissolved at room temperature, then your solid is soluble.
Do not use this solvent as a recrystallization solvent.
If the solid does is not dissolved at room temperature, heat the test tube in water bath
(near the boiling point) and shake it (do not forget boiling stones). If the sample still does

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not dissolve, the solvent is not suitable. If the sample dissolves when hot, and does not
dissolve at room temperature, you are on trail of a good recrystallization solvent. One last
test: Place the test tube (no longer hot) in an ice bath and cool it. If precipitation ensues, it
will be your recrystallization solvent.
If you cannot find a suitable solvent at all, try mixtures of solvents. You can perform
a mixed-solvent recrystallization. Try adding another solvent to the cooled solution to start
precipitation.

DECOLORIZING
A color in a supposedly white product is an impurity, a color in a colored product is
not an impurity. The wrong color in a product is an impurity. Thus, highly colored
contaminants may be removed from solution by adding activated carbon (activated
charcoal) to the completely dissolved hot solution followed by a hot filtration to remove
the charcoal. Activated carbon sucks up big, huge, polar, colored impurity molecules and
they are removed with the charcoal. Polar substances with chromophores that are usually
responsible for imparting a color to the solution are strongly adsorbed on the surface of the
carbon.
Unfortunately, if you use too much, it will suck up your product. If the compound to
be purified is known to be colorless but the solution is dark, it will often be worthwhile to
try the effect of carbon on a small portion. Activated carbon is usually most effective in
polar solvents, such as, water or alcohol. The amount of charcoal used should be about 1–
5% of the weight of the sample being recrystallized.

FILTRATION
Insoluble matter is removed from the hot solution by gravitational filtration. Hot
filtration must be carried out with precaution to avoid premature crystallization in the
funnel or on the filter paper because of the cooling of the solution. Thus, a conical funnel
with a short stem should be used. The solution to be filtered should be maintained close to
the boiling point, and a small amount of additional solvents should be added as necessary.
Rapid filtration can be achieved by using filter paper.

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 Figure 1. The gravity filtration setup and the preparation of a fluted filter paper

CRYSTALLIZATION
In the optimum case, crystallization occurs spontaneously when the solution is cooled
to room or ice-bath temperature; however, in some cases, crystallization has to be induced.
Sometimes the volume of the solvent is too large and the solution must be concentrated.
Moreover, crystallization can be induced by scratching the inside walls of the flask.
The size of crystals depends on the rate of formation and the number of particles
present. Rapid cooling and shaking or stirring the solution leads to the rapid formation of
small crystals. In delicate selective crystallization, it may be crucial to allow crystals to
form slowly and without agitation.

COLLECTION AND WASHING OF CRYSTALS

When crystallization is complete, the solid is scraped loose from the wall of the flask
and collected in a porcelain Büchner or Hirsch funnel using vacuum. These porcelain
funnels are fitted with a circle of filter paper that should lie flat and cover the porcelain
base, which permits liquid to drain rapidly into the evacuated flask. The paper is wet with a
few milliliters of solvent and the flask is connected to suction. This will seat the filter paper
firmly on the funnel. Normally, crystals are washed free of the mother liquor using small
portion of chilled solvent. This ensures the removal of impurities that might be carried
along in the mother liquor.
The crystal mass may be compacted with a cork or spatula to hasten the removal of
solvent, and is often possible to remove traces of solvent by drawing air through the funnel
using suction. The crystals are transferred to a watch glass, filter paper for further drying in
air or in an oven with the temperature well below the melting point of the sample.

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 Figure 2. How to use a Büchner funnel

QUESTIONS
1. A compound is quite soluble in toluene, but only slightly soluble in petroleum
ether. How could these solvents be used in combination in order to recrystallize this
compound?
2. How can you separate the mixture of meta-nitrobenzoic acid and para-nitrobenzoic
acid? Give a brief explanation.

3. During recrystallization, a yellow solution of a compound in hot recrystallization

solvent was treated with activated carbon and then filtered through fluted paper. On
cooling, the filtrate yielded gray crystals, although the compound is colorless. Explain
why the crystals were grey, and how can you prevent this?

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