Crystallization

Throughout the chemical process industries, formation of crystals is an important route to

products of high purity. Click here to find out why slow forming crystals are so pure. The
ultra pure silicon wafers for the electronics industry are made by repeated crystallization. As a
crystal forms, the ions or molecules that fit exactly into the crystal lattice are preferred while the
incorrect species are excluded. Often very pure crytals can form in quite impure solutions. Of
course, when the mother liquor (the residual solution) adheres to the crystals, purity suffers. This
is why good washing or removal of liquid from the crystals is critical.
 Rapid precipitation tends to make impure crystals.

Look at some typical crystals of the mineral aquamarine with high purity:

 Single crystal

 Translucent green crystal

 Translucent green crystal
 Crystal Formation
There are many ways to form crystals. Some ways are described here:

 Evaporation: Crystals formed by evaporation form due to the fact that there is decreasingly
less solvent available for the ions to be dissolved in, therefore causing a state of metastable or
supersaturation in which nucleation and crystal growth can occur.

 Adjust the pH: This method is commonly used to obtain homogenous nucleation and growth
because we can control pH by various reactions. In doing this, we can effectly make the change
as slow as we want and make it completely uniform throughout the solution. The crystals again
form because the extent to which the ions are soluble decreases when the pH is changed in the
right direction.

 Lower the temperature: By lowering the temperature of the solvent, you can reduce the
solubility of the ions. This is better explained here.

 Change the nature of the solvent: This method is commonly used when a faster
crystallization is desired. In order to change the nature of the solvent, one would normally add
non-solvent (something which the ions are not soluble in, or not as soluble in) to the current
solution. By doing this, you can effectively reduce the solubility of the ions in the solution and
cause rapid precipitation . There is an optimum amount of "non-solvent" to add to the system.
Usually there will be a slight degree of solubility in your "non-solvent" and there adding too
much with allow the ions to stay in solution dissolved in your "non-solvent".

Crystallization
The general idea is to avoid too high a driving force because that will force crystals to grow too
rapidly. There must be time for the correct atom, ion, or molecule to find a place in the crystal
lattice where it can fit perfectly. Intense driving force may force an impurity into the lattice. The
following graph indicates an acceptable operating region.
A concentration in solution that falls in the bluish region is below saturation, and no crystals can
form.
The red/purple region indicates where the concentration in solution is higher than saturation, and
there is a driving force for deposition of crystals. The exact transition to the yellow region cannot
be measured; this line is indistinct and depends on the conditions of the experiment.
A concentration in the yellow region is far above saturation. Too much driving force means that
we can expect crystallization to be spontaneous and fast.

In the red/purple region, especially close to the lower line, nothing may happen unless something
such as nucleation sites or seed crystals initiates crystallization.

Crystallization 2
With only a very few exceptions, solubility increases with temperature. This is shown by the blue
line in the following figure:
This solubility curve represents equilibrium, and many crystallization steps are much too fast for
attaining equilibrium. The line between the yellow and magenta regions on the same figure is not
exact and depends on several factors, one of which is cleanliness. Tiny dirt can provide sites for
nucleation. Appreciating that the change from one zone to the other is an approximation, we can
see three distinct regions on the graph. The lower region corresponds to permutations of
temperatures and concentrations where the material is soluble. If crystals were added, they would
dissolve.

The next region is labled "supersaturated"; this is also called the metastable region. Although
above the saturation line, there is no certainty that crystals will form. There are cases where
solutions have been held for many years with no crystallization. When seed crystals are added or
when nucleation is induced by dust particles or by scratching the walls of the container, crystals
can form quite rapidly. The further above the saturation line, the more likely that crystals will
form because the driving force is greater.
Same ideas worded slightly differently.

Above the approximate boundary and into the yellow region, it is very difficult to avoid
spontaneous crystallization. The metastable region is of greatest interest because that is where
conditions can be adjusted to get the desired crystal properties.

Precipitation in Environmental Engineering

Chemical engineers almost always use crystallization to get highly pure products. Environmental
engineers strive for purified water as their product; their precipitates are thrown away. If an
environmental precipitation makes impure solids, it does not matter. In fact, operating the crystallization
so that the crystals pick up impurities and remove them from the water can be highly advantageous.
Because of their very low solubility products, aluminum hydroxide and ferric hydroxide are
almost impossible to precipitate slowly. Adding a solution of the chemical for coagulation to the
water produces relatively high local concentrations as solutions of these chemicals contact the
water. Even with violent mixing, these local concentrations persist long enough to initiate an
uneven precipitation. This effect, and the very rapid precipitation, result in an opalescent
precipitate that is gelatinous in character. Fortunately, it tends to settle quite well. The
sedimentation of ferric or aluminum hydroxide captures other particles and aids greatly in their
collection. This gives rise to the name sweep floc for a gelatinous precipitate that carries just
about all colloidal material with it.

Not only does a sweep floc entrap other particles, it incorporates foreign ions into the precipitate
itself. When ionic salts precipitate very slowly, each ion finds its proper place in the crystal
lattice. A well-formed crystal tends to be extremely pure- this is why the electronics industry
makes silicon wafers by slicing crystals that have been melted and recrystallized several times.
When a crystalline material must form very rapidly, as in the case of aluminum or ferric
hydroxide driven by great insolubility, there is insufficient time for putting each ion in the correct
place. In fact, a foreign ion may be substituted for the correct ion. This gives the desirable effect
of removing some metal ions by jamming them into the precipitate.

Rapid formation of precipitates

When crystals form slowly, each ion or molecule finds its correct place in the crystal lattice. Very careful
crystallization is the best method of preparing materials that are extremely pure. In environmental
engineering, there is no need for pure crystals or precipitates. The rate of precipitation depends, in part,
on the degree of supersaturation. You can select the time for the crystal to form in the following Java
applet. If the material that precipitates is fairly insoluble and forms crystals at a moderate rate, a long
time to form the crystal can deliver high purity. Note that a few red circles stand for a low level of
impurities.

When the precipitate is highly insoluble and precipitates very rapidly (e.g., ferric hydroxide),
there is not enough time for ions to find their place in the lattice, and foreign ions can take their
places. The crystal can be quite impure.

Crystalization and Purity

Purity of slow forming crystals is usually due to the limited space and tight bonding nature of the
atoms in the lattice structure. You can see below how each molecule is bonded with each of its
neighbors.
These lattices as shown above are very ordered and have very precise dimensions. Contaminants
do not fit within the lattice structure itself.

Things that effect purity:

 Size: The size of the crystal can greatly determine the purity of the crystal. This is due to the
complete order of the lattice structure. One can see the inside points of the lattice structure are
very precise dimensions and can only have the correct atoms at those points. You may also see
that the edge points have usually only 3 to 5 bonds (Corners, Edges, and Sides). Because of this,
there is a greater chance of an impurity being able to fit in one of these spaces. Therefore the
purity a function of the internal volume (all of which is very pure) and the surface area (Corners,
Edges, and Sides) which have lower purity. To maximize purity, one would therefor want the
greatest internal volume with the least amount of surface area.

 Process by which crystals are formed: The rate at which the crystals grow determines
whether or not the crystals will have a large or smaller number of internal impurities. This is
better explained here.

 Wash method or recrystallization: Typically a crstyal is washed after it is formed to remove

many of the surface impurities. When selecting a solvent to use for the washing step in you
crystallization process, one must consider solubility of the crystal as well as solubility of the
impurities. A good choice of solvents is ice water. This is due to the temperature dependance of
solubility for water. See this example for temperature effects. So crystals, such as silicon are
melted and recrystallized slowly to increase the selectivity of the surface atoms towards the
desired products.