Crystallization/ Recrystallization

Crystallization of solids is one of the most common methods used to purify solids. Other
techniques for purifying solids include sublimation, extraction, and chromatography.
Nevertheless, even when one of these alternative methods of purification has been used, the
solid material thus isolated may still be recrystallized to achieve a higher state of purity.
1. Solubility
The first problem in performing a crystallization is selecting a solvent in which the material to
be crystallized shows the desired solubility behavior. In an ideal case, the material should be
sparingly soluble at room temperature and yet quite soluble at the boiling point of the solvent
selected. The solubility curve should be steep, as can be seen in line A of Figure 11.1. A curve
with a low slope (line B) would not cause significant crystallization when the temperature of
the solution was lowered. A solvent in which the material is very soluble at all temperatures
(line C) also would not be a suitable crystallization solvent. The basic problem in performing
a crystallization is to select a solvent (or mixed solvent) that provides a steep solubility vs.
temperature curve for the material to be crystallized. A solvent that allows the behavior shown
in line A is an ideal crystallization solvent.
It should also be mentioned that solubility curves are not always linear, as they are depicted in
Figure 11.1. This figure represents an idealized form of solubility behavior. The solubility
curve for sulfanilamide in 95% ethyl alcohol, shown in Figure 11.2, is typical of many
organic compounds and shows what solubility behavior might look like for a real substance.

The solubility of organic compounds is a function of the polarities of both the solvent and the
solute (dissolved material). A general rule is “Like dissolves like.” If the solute is very polar,
a very polar solvent is needed to dissolve it; if the solute is nonpolar, a nonpolar solvent is
needed.
2. Priciples of crystallization
The general technique of crystallization involves dissolving the material to be crystallized in a
hot solvent (or solvent mixture) and cooling the solution slowly. The dissolved material has a
decreased solubility at lower temperatures and will separate from the solution as it is cooled.

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This phenomenon is called either crystallization, if the crystal growth is relatively slow and
selective, or precipitation, if the process is rapid and nonselective.
Crystallization is an equilibrium process and produces very pure material. A small seed
crystal is formed initially, and it then grows layer by layer in a reversible manner. In a sense,
the crystal “selects” the correct molecules from the solution. In precipitation, the crystal
lattice is formed so rapidly that impurities are trapped within the lattice. Therefore, any
attempt at purification with too rapid a process should be avoided. Because the impurities are
usually present in much smaller amounts than the compound being crystallized, most of the
impurities will remain in the solvent even when it is cooled. The purified substance can then
be separated from the solvent and from the impurities by filtration.
In some experiments, you will be instructed to cool the crystallizing mixture in an ice-water
bath before collecting the crystals by filtration. Cooling the mixture increases the yield by
decreasing the solubility of the substance; however, even at this reduced temperature, some of
the product will be soluble in the solvent. It is not possible to recover all your product in a
crystallization procedure even when the mixture is cooled in an ice-water bath. A good
example of this is illustrated by the solubility curve for sulfanilamide shown in Figure 11.2.
The solubility of sulfanilamide at 0°C is still significant, 14 mg/mL.
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Extraction
1. Priciples of extraction
Transferring a solute from one solvent into another is called extraction, or, more precisely,
liquid–liquid extraction. The solute is extracted from one solvent into the other because the
solute is more soluble in the second solvent than in the first. The two solvents must not be
miscible (mix freely), and they must form two separate phases or layers, in order for this
procedure to work. Extraction is used in many ways in organic chemistry. Many natural
products (organic chemicals that exist in nature) are present in animal and plant tissues having
high water content. Extracting these tissues with a water-immiscible solvent is useful for
isolating the natural products. Often, diethyl ether (commonly referred to as “ether”) is used
for this purpose. Sometimes, alternative water-immiscible solvents such as hexane, petroleum
ether, ligroin, and methylene chloride are used. For instance, caffeine, a natural product, can
be extracted from an aqueous tea solution by shaking the solution successively with several
portions of methylene chloride.
2. Extraction procedure
A generalized extraction process, using a specialized piece of glassware called a separatory
funnel, is illustrated in Figure 12.1. The first solvent contains a mixture of black-and-white
molecules (see Figure 12.1A). A second solvent that is not miscible with the first is added.
After the separatory funnel is capped and shaken, the layers separate. In this example, the
second solvent (shaded) is less dense than the first, so it becomes the top layer (see Figure
12.1B). Because of differences in physical properties, the white molecules are more soluble in

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the second solvent, whereas the black molecules are more soluble in the first solvent. Most of
the white molecules are in the upper layer, but there are some black molecules there, too.
Likewise, most of the black molecules are in the lower layer. However, there are still a few
white molecules in this lower phase. The lower phase may be separated from the upper phase
by opening the stopcock at the bottom of the separatory funnel and allowing the lower layer to
drain into a beaker (see Figure 12.1C). In this example, notice that it was not possible to effect
a complete separation of the two types of molecules with a single extraction. This is a
common occurrence in organic chemistry.

Many substances are soluble in both water and organic solvents. Water can be used to extract,
or “wash,” water-soluble impurities from an organic reaction mixture. To carry out a
“washing” operation, you add water and an immiscible organic solvent to the reaction mixture
contained in a separatory funnel. After stoppering the funnel and shaking it, you allow the
organic layer and the aqueous (water) layer to separate. A water wash removes highly polar
and water-soluble materials, such as sulfuric acid, hydrochloric acid, and sodium hydroxide,
from the organic layer. The washing operation helps to purify the desired organic compound
present in the original reaction mixture.
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 Sublimation
1. Introduction to sublimation
Like the vapor pressure of a liquid, the vapor pressure of a solid increases with temperature. If
the vapor pressure of a solid is greater than the ambient pressure at its melting point, then the
solid undergoes a direct phase transition to the gas phase without first passing through the
liquid state. This process is called sublimation. Because the vapor can be resolidified, the
overall vaporization–solidification cycle can be used as a purification method.
2. Vapor pressure behavior of solids and liquids
In Figure 17.1, vapor pressure curves for solid and liquid phases for two different substances
are shown. Along lines AB and DF, the sublimation curves, the solid and vapor are at
equilibrium. To the left of these lines, the solid phase exists, and to the right of these lines, the
vapor phase is present. Along lines BC and FG, the liquid and vapor are at equilibrium. To the
left of these lines, the liquid phase exists, and to the right, the vapor is present. The two
substances vary greatly in their physical properties, as shown in Figure 17.1.
In the first case (Figure 17.1A), the substance shows normal change-of-state behavior upon
being heated, going from solid to liquid to gas. The dashed line, which represents an
atmospheric pressure of 760 mmHg, is located above the melting point B in Figure 17.1A.
Thus, the applied pressure (760 mmHg) is greater than the vapor pressure of the solid–liquid
phase at the melting point. Starting at A, as the temperature of the solid is raised, the vapor
pressure increases along AB until the solid is observed to melt at B. At B, the vapor pressures
of both the solid and liquid are identical. As the temperature continues to rise, the vapor
pressure will increase along BC until the liquid is observed to boil at C. The description given
is for the “normal” behavior expected for a solid substance. All three states (solid, liquid, and
gas) are observed sequentially during the change in temperature.

In the second case (Figure 17.1B), the substance develops enough vapor pressure to vaporize
completely at a temperature below its melting point. The substance shows a solid-to-gas

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transition only. The dashed line is now located below the melting point F of this substance.
Thus, the applied pressure (760 mmHg) is less than the vapor pressure of the solid–liquid
phase at the melting point. Starting at D, the vapor pressure of the solid rises as the
temperature increases along line DF. However, the vapor pressure of the solid reaches
atmospheric pressure (point E) before the melting point at F is attained. Therefore,
sublimation occurs at E. No melting behavior will be observed at atmospheric pressure for
this substance. For a melting point to be reached and the behavior along line FG to be
observed, an applied pressure greater than the vapor pressure of the substance at point F
would be required. This could be achieved by using a sealed pressure apparatus.
3. Sublimation behavior of solids
Sublimation is usually a property of relatively nonpolar substances that also have highly
symmetrical structures. Symmetrical compounds have relatively high melting points and high
vapor pressures. The ease with which a substance can escape from the solid state is
determined by the strength of intermolecular forces. Symmetrical molecular structures have a
relatively uniform distribution of electron density and a small dipole moment. A smaller
dipole moment means a higher vapor pressure because of lower electrostatic attractive forces
in the crystal.
Solids sublime if their vapor pressures are greater than atmospheric pressure at their melting
points. Some compounds with the vapor pressures at their melting points are listed in Table
17.1. For the first three entries in the table, at atmospheric pressure, they would sublime rather
than melt, as shown in Figure 17.1B.

The next four entries in Table 17.1 (camphor, iodine, naphthalene, and benzoic acid) exhibit
typical change-of-state behavior (solid, liquid, and gas) at atmospheric pressure, as shown in
Figure 17.1A. These compounds sublime readily under reduced pressure, however.
Compared with many other organic compounds, camphor, iodine, and naphthalene have
relatively high vapor pressures at relatively low temperatures. For example, they have a vapor
pressure of 1 mmHg at 42°C, 39°C, and 53°C, respectively. Although this vapor pressure
does not seem very large, it is high enough to lead, after a time, to evaporation of the solid

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from an open container. Mothballs (naphthalene and 1,4-dichlorobenzene) show this behavior.
When iodine stands in a closed container over a period of time, you can observe movement of
crystals from one part of the container to another.
Although chemists often refer to any solid–vapor transition as sublimation, the process
described for camphor, iodine, and naphthalene is really an evaporation of a solid. Strictly
speaking, a sublimation point is like a melting point or a boiling point. It is defined as the
point at which the vapor pressure of the solid equals the applied pressure. Many liquids
readily evaporate at temperatures far below their boiling points. It is, however, much less
common for solids to evaporate. Solids that readily sublime (evaporate) must be stored in
sealed containers. When the melting point of such a solid is being determined, some of the
solid may sublime and collect toward the open end of the melting-point tube while the rest of
the sample melts. To solve the sublimation problem, seal the capillary tube or rapidly
determine the melting point. It is possible to use the sublimation behavior to purify a
substance. For example, at atmospheric pressure, camphor can be readily sublimed just below
its melting point at 175°C. At 175°C, the vapor pressure of camphor is 320 mmHg. The vapor
solidifies on a cool surface.
3. Sublimation procedure
To be purified by sublimation, a compound must have a relatively high vapor pressure, and
the impurities must have vapor pressures significantly lower than that of the compound being
purified. A simple sublimation apparatus is shown in figure 17.2.

Figure 17.2: A sublimation apparatus

The impure substance is taken in an evaporating dish covered with a perforated sheet. An
inverted glass funnel is plugged with cotton wool and placed on the sheet. The sample is then
heated under reduced pressure to a temperature below the melting point of the solid. The solid
will be vaporized and transferred via the vapor phase to the cooler wall of the funnel, where it
condenses to form a pure solid (sublimate). After the sublimation is complete, pure crystals
are scraped from the funnel with a spatula.

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Homework questions
1) List 3 techniques that can be used to purify solids.
2) What is the (re)crystallization technique used for?
3) The solubility of solids often increases or decreases with increased temperature.
4) In crystallization, why shouldn’t we cool the solution too quickly?
5) Can we recover all of the product by recrystallization? Why?
6) What are the criteria/ standards to select a solvent for crystallization of a solid?
7) The graph below shows the relationship between solubility and temperature of compound
X in solvent A, B, and C.
- A solvent that allows the behavior shown in line A is an ideal crystallization solvent.
Why?
- The solvents as shown in lines B and C are not suitable crystallization solvents.
Explain the reasons.

8) What is extraction?
9) List 3 solvents that are commonly used in extraction
10) Why does a solute move from one solvent to another in an extraction?
11) Is it possible to completely separate two types of solute with a single extraction? Why?
12) How can extraction be used to isolate natural product?
13) How can washing with water help to purify organic compounds?
14) Below are vapor pressure curves of compound A (left) and B (right). Which compound
will sublime at 760 mmHg? Why? How can you measure the melting point of that
compound?

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15) Describe briefly the process of (re)crystallization.
16) What are the differences between crystallization and precipitation?
17) What is sublimation?
18) What is sublimation used for?
19) When does a solid sublime?
20) How do vapor pressures of solids and liquids change with increased temperature?
21) What are the apparatus/ equipment needed for sublimation?
22) Why should we store mothballs (naphthalene and 1,4-dichlorobenzene) in a closed
container?
23) Sublimation is usually a property of relatively nonpolar substances that also have highly
symmetrical structures.
24) When can the technique of sublimation be used to purify an impure solid?

(From Pavia, D. L. 2011. A small-scale Approach to organic laboratory techniques. Belmont,

CA: Brooks/Cole Cengage Learning)