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Lecture 8

Crystallization
Definition
Crystallization is the process for crystals production from a
solution. Crystallization is applied for:
Purification
Crystallography
The crystallization only takes place under supersaturated
solution. Supersaturated refers to a state in which the
solvent contains more solute than can ordinarily be
accommodated at that temperature.
The crystallization process consists of two major events:
nucleation and crystal growth.
Crystallization vs. Precipitation

Description Crystallization Precipitation


Solubility Wide range Sparingly soluble
Relative supersaturation Low High
Product morphology Well defined Ill defined
Product crystal size Large Small
Nucleation mechanism Secondary Primary
Nucleation rate Low High
Growth rate Wide range Low
Controllability Controllable Difficult
Characteristic of Crystals
The shape of crystals can be the polyhedrons or plane
faces
The angles are specific for the material
Relative sizes of the faces of a crystal can vary, which is
called a habit.
Crystal habit is influenced by the conditions, particularly
by the impurities present and solvent. Impurites can stunt
the growth of a crystal in certain directions
Characteristic of Crystals

Tabular form Prismatic form Acicular form


Characteristic of Crystals
Nucleation
Nucleation is the step where the solute molecules
dispersed in the solvent start to gather into cluster, on the
nanometer scale, that becomes stable under the current
operating conditions.
The clusters reach a critical size in order to become stable
nuclei. This is dictated by the operating conditions
(temperature, supersaturated)
Total nucleation is the sum effect of two categories of
nucleation: primary and secondary.
Primary nucleation
Primary nucleation is the initial formation of a crystal
where there are no other crystals present or where, if
there are crystals present in the system, they do not have
any influence on the process.
This can occur in two conditions: homogeneous and
heterogeneous nucleation
: number of nuclei formed per unit
volume per unit time
: number of nuclei per unit volume
= = 1 1 : rate constant
: instantaneous solute concentration
: solute concentrationat saturation
: supersaturation
= 3 10
Secondary nucleation
Secondary nucleation is the formation of nuclei
attributable to the influence of the existing microscopic
crystals in the magma.
First type of known secondary crystallization is
attributable to fluid shear, the other due to collisions
between already existing crystals with either a solid
surface of the crystallizer or with other crystals
themselves
2 : rate constant
: suspension density
= = 2
=25
= 1 1.5
Crystals growth
Once the first small crystal, the nucleus, forms it acts as a
convergence point for molecules of solute touching, or
adjacent to the crystal so that it increases its own
dimension in successive layers.
Growth rate is influenced by several physical factors, such
as surface tension of solution, pressure, temperature,
relative crystal velocity in the solution.
Solute concentration
Phase diagram

Nucleation
and growth

Heterogeneous while
crystal growth
Stable region
(homogeneous solution)
Reagent concentration
Solute concentration
Phase diagram

Prismatic form

Reagent concentration
Artificial methods
For crystallization to occur from a solution it must be
supersaturated. This can be achieved by various methods:
Solution cooling
Addition of a second solvent to reduce the solubility of
the solute
Chemical reaction
Solvent evaporation
Mass balances
Crystallization is as the result of supersaturated solution.
Consequently, mass balance is estimated by concentration
of solution and solubility at given temperature. The excess
solute is removed from the solution as crystal form.
=++

1 = 1 + 1 +

Vaporized solvent (if any),

Solution, , Saturated solution (mother liquor), ,


Cooler and Crystallizer

Crystals in solid phase, ,


Example 1
A salt solution weighing 10000 with 30% 2 3 is cooled
to 293 20 . The salt crystallizes as the decahydrate. What will
be the yield of 2 3 102 crystals if the solubility is
21.5 2 3 100 ? Estimate the yield
of the crystallization process for following cases:
a) Assume that no water is evaporated.
b) Assume that 3% of the total weight of the solution is lost by
evaporation of water in cooling?
of water vapor

10000 solution of saturated solution


Cooler and Crystallizer
30% 2 3 21.5 2 3 100

of crystals 2 3 102
Example 1
= 10000
= 0.3

=+
= 3647
a) =0 100 180
0.7 = + = 6353
121.5 286

=++
= 3073
b) = 300 100 180
0.7 = + + = 6627
121.5 286
Energy balances
Solvent vaporization and crystals formation always
accompany to heat effects, which are latent heat of
vaporization and crystallization.

= + + +

Vaporized solvent (if any), ,

Solution, , Saturated solution (mother liquor), ,


Cooler and Crystallizer

Crystals in solid phase, ,


Example 2
A feed solution of 2268 at 327.6 54.4 containing
48.2 4 100 is cooled to 293.2 20 ,
where 4 72 crystals are removed. The solubility of the
salt is 35.5 4 100 . The average heat capacity
of the feed solution can be assumed as 2.93 . The heat of
solution at 291.2 18 is 13310 4 72 .
Calculate the yield of crystals and make a heat balance to
determine the total heat absorbed, , assuming that no water is
vaporized.

2268 solution, 54.4 of saturated solution, 20


Cooler and Crystallizer
48.2 4 100 35.5 4 100

of crystals 4 72
Example 2
= 2268
48.2 4 100

=+
= 1633
Mass balances 100 100 126
= + = 635
148.2 135.5 246
Energy balances = + + = + +
= +
With = = 2.93 54.4 20
= 100.79
Example 2
The heat of solution at 291.2 18 : 13310 4 72
The heat of solution at 20: 13310 4 72
The heat of crystallization at 20: 13310 4 72
= 13310 4 72
= 54.1 4 72

= + = 262949