CRYSTALLIZATION

BY:
TAHSEEN ISMAIL

Crystallization
Definition:
Crystallization is the (natural or
artificial) process of formation of solid crystals
precipitating from a solution, melt or more rarely
deposited directly from a gas.
Crystallization is also a chemical solid-liquid
separation technique, in which mass transfer of
a solute from the liquid solution to a pure solid
crystalline phase occurs.

Crystal:
A crystal or crystalline solid is a solid
material, whose constituent atoms, molecules, or
ions are arranged in an orderly repeating pattern
extending in all three spatial dimensions.
The scientific study of crystals and crystal
formation is crystallography.
The process of crystal formation via
mechanisms of crystal growth is called
crystallization or solidification.

TYPES OF CRYSTALS:
a) Based on physical & chemical
properties.
1) Covalent crystals
2) Metallic crystals
3) Ionic crystals
4) Molecular crystals

Covalent Crystals:
This is a crystal which
has real chemical covalent between all of
the atoms in the crystal. A single crystal
of a covalent crystals is really just one big
molecule.
Covalent crystals can have extremely
high melting points.
Example: Diamond or Zinc sulphide.

Metallic Crystals:
Individual metal atoms occur
on lattice sites while the outer electrons
from these atoms are able to flow freely
around the lattice.
Metallic crystals normally have high
melting points and densities.

Ionic Crystals:
A crystal in which the
individual atoms don't have covalent
bonds between them, but are held
together by electrostatic forces.
Ionic crystals are hard and have
relatively high melting points.
Example: Sodium chloride (NaCl).

Molecular Crystals:
A crystal in which there are
recognizable molecules in the structure
and the crystal is held together by noncovalent interactions like van der Waals
forces or hydrogen bonding.
They are soft and have lower melting
points
Example: Sugar

b) Based on crystal system.

1) Triclinic
2) Monoclinic
3) Orthorhombic
4) Tetragonal
5) Trigonal
6) Hexagonal
7) Cubic

Crystalline phases:
1) Polymorphism is the ability of a solid to exist
in more than one crystal form. For example,
water ice is ordinarily found in the hexagonal
form Ice, but can also exist as the cubic Ice, the
rhombohedral ice.
2) Amorphous phases are also possible with the
same molecule, such as amorphous ice. In this
case, the phenomenon is known as
polyamorphism.

Mechanism:
It involves 2 steps.
1) Nucleation (creation of crystalline
nuclei)
2) Crystal growth (nuclei grow in to
crystals)

NUCLEATION:
It is the step where the solute
molecule dispersed in solvent, start to
gather into clusters, elevating solute conc.
in small region.
It may arise spontaneously or by
introduction of minute crystal of dissolved
substance in the solution.

Seeding:
Addition of same solute in that
solution creates crystal nuclei this process
is known as seeding.
Theory of Miers:
It postulates that a definite
relationship exists between the conc. &
temp. at which crystals will spontaneously
form in an initially un seeded soln.

This form of relationship is a super solubility

curve roughly parallel to and above the normal
solubility curve.
Such a curve may be imagined as solubility for
exceedingly fine particles hence have solubility
greater than large crystals.
Solubility curve (diagram).
Metastable zone:
There will no appreciable
spontaneous nucleation. But above solubility
curve there is copious spontaneous nucleation.

E spontaneous crystalline solution its

concentration falls to that given by normal
solubility curve at prevailing temp. i.e, G.
Solution represented at point F in meta
stable zone will be unchanged unless
seeds are added and when nucleation
occurs the conc. will again drop to G.

CRYSTAL GROWTH:
Crystal growth is the
subsequent growth of nuclei that succeed
in achieving the critical cluster size.
nucleation and growth occurs
simultaneous while super saturation exist.

Super saturation:
It is the driving force of crystallization
hence rate of nucleation and growth is
driven by the existing super saturation in
the solution.

Size of crystals:
Depends on conditions of crystallization
1) very small size:
By rapid cooling with frequent stirring of soln.,
almost saturation at their bp usually avoided.
2) Median size:
Soln. saturated about 60 -80 c.
3) Large size:
BY evaporation the solvent may be facilitated by
seeding.

Mother liquor:
Liquid remaining after crop of crystals.
Again used till whole crop of crystal is
obtained.

Applications of crystallization:
1) Crystal production:
Macroscopic crystal, tiny size crystal.
2) Purification:
Use to obtain very pure
substances and to verify their purity.

thatz all