Chapter 4

CRYSTALLIZATION

24/3/2014

Crystallization of organic solids

Crystallization: a first
order phase change
in
which
solid
product is isolated
from a solution,
melt, vapor or even
from solid phase
Supersaturation:
prerequisite
for
achieving
crystallization from
solution

Types of Crystallization

Crystallization Process: Nucleation

Initiation of a phase change in a small region, such as the
formation of a solid crystal from a liquid solution
Consequence of rapid local fluctuations on a molecular
scale in a homogeneous phase that is in a state of
metastable equilibrium
This transformation requires traversing a free energy
barrier
Primary nucleation (homogeneous)-spontaneous
Secondary nucleation (heterogenous)-induced by the
presence of foreign particles

Free energy diagram for nucleation explaining

the existence of critical nucleus

Crystallization process: Crystal Growth

Crystal growth is a 2nd stage of a crystallization process after
nucleation, and consists in the addition of new atoms, ions, or
polymer strings into the characteristic arrangement of a crystalline
Bravais lattice.
Once a crystal is stabilized from the critical nucleus, the growth
units can diffuse from the surrounding supersaturated solution to
the surface of the critical nucleus an incorporate themselves onto
the crystal
Bravais lattice: is an infinite array of discrete points generated by a
set of discrete translation operations described by:
where ni are any integers and ai are known as the primitive vectors
which lie in different directions and span the lattice.

Type of Crystal Growth

1. Continuous (rough) Growth

Referring as continuous growth or rough growth, in which several crystalline

materials with high roughness contain enough kink and step sites on the
surface to integrate basically all close to growth units with small complication.

A
B
C

Molecules A as the surface only (one attachment)

B as the surface and a growing step (two attachments)
C as a kink site (three attachments) wheres in energetically C is the most
favourable for successful bonding to the surface followed by B and lastly is A.

2. Growth by Two-Dimensional (2-D)

Most of the materials which are crystallized do not have enough
roughness to exhibit continuous growth.
To accept the incoming growth units, some steps must be created.
The creation of steps is done by the two-dimensional nucleation at
the surface which involves nucleated circles forming on the flat
crystalline surface.
Molecules are being adsorbed onto, desorbed from, and diffusing on
the crystal surface.

Formation of Two Dimensional Critical Nucleuses on a Crystal Surface (Tung et al. 2009)

3. Screw Dislocation (Spiral Growth)

In the existence of screw dislocations, crystal
faces grow through the spiral growth
mechanism at supersaturation lower than the
value where 2D nucleation and growth is the
dominant mechanism (Lovette et al. 2008).
In spiral growth, self-generating step process
are take placed as a result of screw
dislocations that terminate on a crystal face
act as continuous sources of edges.

 Figure below shows the configuration of screw

dislocation that possibly occurs within crystals
as result of stresses in crystal growth on seeds
and around surface nuclei and inclusions.

Development of a Growth Spiral Starting from a Screw Dislocation: (a) Start, (b) Later, (c) Final Spiral

Crystal Gallery

Polymorphism
Polymorph: Crystals in which chemical compound
takes different arrangements of molecules-solid
state phenomenon
Different morphologis, solubilities, color, melting,
sublimation temperatures, densities, thermal/
elctrical conductivities
Pharmaceutical
industry-affect
processing
properties such as filtering, drying, flow,
tabletting, rate of dissolution, shelf life and
bioavailability

Thermodynamics of Polymorphism

Industrial Crystallization

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