Crystallization

What is Crystallization
Formation of solid particles within a homogenous phase
e.g. formation of solid NaCl from salt solution
Formation of ice, snow from water vapor
Natural minerals, e.g. gemstones, diamonds
Significance of study of crystallization:
Crystals are very pure form of materials
Crystals formed from impure solution are still pure
Very practical method of obtaining very high purity
Rock salt crystals
material
in satisfactory condition for storage

Natural diamond crystal

Snow flakes

Terms
Magma: two phase mixture of mother liquor and crystals of all sizes
Mother liquor: the part of a solution left over after crystallization
Supersaturated solution: solution with concentration greater
than equilibrium concentration

Invariant crystal: the crystal maintains geometric similarity

Characteristic length: definition of size of crystal
L

6v
s
p

sp is surface area of the crystal

vp is the volume of the crystal

Overlapping principle: different faces of crystal grow at a different

rate and later the shape and appearance of the crystal
Faces with low velocity survive crystal growth

Equilibrium Curve

Solubility

KNO3

NaCl

MnSO4

Temperature
Solubility-supersolubility
diagram

Solubility is usually a strong function of temperature, e.g. KNO3, MnSO4

Most inorganic substances crystallize with water of crystallization
In some systems several hydrates might be formed

Fundamental driving force for crystallization is change in chemical potential but

mostly expressed as concentration driving force

Supersaturation
From
solutions
solution with concentration greater than equilibrium concentration
Generated using
Temperature change (cooling or heating)
Evaporating the solvent
Addition of third component (salting out, precipitation)

Degree of supersaturation is given by

c y c c
Saturation ratio is given by S c
*

Relative supersaturation: c S 1
c

Example
At 293 K, a supersaturated solution of sucrose contains 2.45 kg sucrose/kg water. If
the equilibrium saturation value is 2.04 kg/kg water, what is the supersaturation
ratio in terms of kg/kg water and kg/kg solution?

Formation of Crystals
Rupture of existing crystals
Nucleation
Primary nucleation (homogenous nucleation)
Solute molecules clustering to form aggregates or embryos that grow into
nuclei

Secondary nucleation (heterogeneous nucleation)

Contact nucleation
Breakage of dendritic growths on the crystals
Catalytic effect of solid particles in the supersaturated solution

Fluid shear nucleation

Sonication, shear due to impellers, etc

Formation of Crystals
Caking
Frequently cake or cement together on storage
Depend on crystal size, shape, moisture content, storage
conditions
Minimized by airtight packing, deposition of inert dust on crystals

Washing

To remove mother liquor content and for removal of impurities

Crystals are separated using filtration, centrifugation
Cake is washed with another insoluble liquid
Multiple washing stages might be required

Crystal Growth

Design of crystallizers
Set supersaturation limit in the crystallizer
Calculate solution recirculation rate from material balance
Estimate maximum growth rate assuming cubic crystals for given
supersaturation
Calculate crystal growth for different desupersaturations
Mass of crystals in suspension and the suspension volume are
calculated assuming a value for the voidage which is often about 0.85
Solution up-flow velocity is calculated for very small crystals
Usually measured exerimentally

Crystallizer area and diameter are calculated, and height is estimated

using (volume of suspension/cross-sectional area)

Equipment
Cooling Crystallizers
Agitated vessels
Scraped surface crystallizers

Evaporating crystallizers
Vacuum cooling crystallizers

Equipment
Cooling Crystallizers
Agitated vessels
Scraped surface crystallizers

Evaporating crystallizers
Vacuum cooling
Forced circulation

Forced circulation Swenson crystallizer

Equipment
Cooling Crystallizers
Agitated vessels
Scraped surface crystallizers

Evaporating crystallizers
Vacuum cooling
Forced circulation
Fluidized bed

Oslo fluidized bed crystallizer