crystallization

MEWAR UNIVERSITY

SUBMITTED TO:- SUBMITTED

M ALAM SIR BY:-
ASSISTANT PROFESSOR RAHUL RAGHAV
BTECH
( ChemE)
SEM 4 , MT(unit
4)
 CONTENTS
Crystallization
Purity of product
Importance of crystal size
Crystal geometry
Crystal systems
Invariant crystals
Supersaturation
Nucleation and its types
Growth of crystals
 CRYSTALLIZATION
Crystallization is the formation of solid particles within a
homogeneous phase.
Occurence :- formation of solid particles in a vapour,
Solidification from a liquid melt,
Crystallization from liquid solution

Crystallization from solution has two advantages:-

A crystal formed from an impure solution is itself pure
( Unless mixed crystals occur).
It is a practical method of obtaining pure chemical
Substances in a satisfactory condition for packaging
And storing.

Magma :-the two phase mixture of mother liquor and crystals of all
size , which is withdrawn as product, is called a magma.
 PURITY OF PRODUCT
A well formed crystal is nearly pure.

A crystal can retain mother liquor when separated from magma.

When retained mother liquor of low purity is dried on the product,

Contamination results.

The extent of contamination depends on the amount and degree

Of impurity of mother liquor retained by the crystals.

The retained mother liquor is separated from the crystals by

Filtration or centrifuging.

The balance is removed by washing with fresh solvent.

The effectiveness of these purification steps depends on the size

And uniformity of crystals.
 IMPORTANCE OF CRYSTAL
SIZE

main objective of crystallization is good yield and high purity.

ppearance and size range is also important.

urther processing, reasonable size and size uniformity are

irable for filtering , washing, reacting with chemicals,
nsporting and storing of chemicals.

e crystals are to be marketed as final product, they must be

ng , nonaggregated, uniform in size, noncaking in the packets.

hese reasons, crystal size distribution (csd) must be under

trol.
CRYSTAL GEOMETRY
Crystals are made of infinite number of unit
cells.
Unit cell is the smallest unit of a crystal, which, if
repeated, could generate the whole crystal.

A crystals unit cell dimensions are defined by six

numbers, the lengths of the 3 axes, a, b, and c,
and the three interaxial angles, , and .
 CRYSTAL SYSTEMS
BIC:- Cu, KCl
NOCLINIC :- monoclinic sulphur, CaSO4 .2H2 O
THORHOMBIC:- AgBr, KNO3
TRAGONAL:- SnO2 , TiO2
CLINIC:- H3 PO3 , NaHSO4
GONAL:- Sb , Bi
XAGONAL:- Mg ,Cd

HEXA
MONOCLI ORTHO TRIGONAL
TETRA TRICLINIC GONAL
CUBIC NIC RHOMBIC
GONAL
 INVARIANT CRYSTALS

Under ideal conditions, a growing crystal maintains geometric similarity

During growth. Such a crystal is called invariant.

The size of a crystal is specified by characteristic length l.

L= s dp =6vp /sp

s =sphericity
Dp =diameter of crystal
V p = VOLUME OF CRYSTAL
Sp = TOTAL SURFACE AREA OF CRYSTAL

Different faces of a growing crystal have different translational

Velocities.
Overlapping principle:- faces with low translational velocities can
Dominate the growth process to the extent that faces with high velocities
Diminish and ultimately disappear.
 SUPERSATURATION
AL FORMATION STEPS:-
cleation:- birth of new particles.
wth:- to macroscopic size.
e driving potential for nucleation and growth rate is
persaturation.
 HOW TO ACHIEVE
SUPERSATURATION?
1) If solubility of solute increases strongly with increase in temp., A
Saturated soln. Becomes supersaturated by cooling and temp.
Reduction.

2) If the solubility is relatively independent of temp, supersaturation occurs

By evaporating a portion of solvent.

3) when solubility is very high, neither cooling nor evaporation is desirable

,Supersaturation occurs by adding a third component.

A) the third component can form a mixed solvent with original solvent
In which the solubility of solute is greatly reduced.
This process is called salting.

b) If a nearly complete precipitation is required, a new solute may be

Created chemically by adding a third component that will react with
The original solute and form an insoluble substance.This process
Is called precipitation.
 DEFINITION OF
SUPERSATURATION
Supersaturation can be defined as the conc. Difference between that of the
Supersaturated solution in which the crystal is growing and that of a
Solution in equilibrium with the crystal.

The two phases are very nearly at the same temperature.

y = y-ys

c = c-cs

y = supersaturation , mole fraction of solute

Y= MOLE FRACTION OF SOLUTE IN SOLUTION
Y s= MOLE FRACTION OF SOLUTE IN SATURATED SOLUTION

c= molar supersaturation, moles per unit volume

C= MOLAR CONCENTRATION OF SOLUTE IN SOLUTION
Cs = MOLAR CONCENTRATION OF SOLUTE IN SATURATED SOLUTION
The above two supersaturation equations are related by

c = M y-s ys

M = MOLAR DENSITY OF SOLUTION

S = MOLAR DENSITY OF SATURATED SOLUTION

since supersaturations in crystallizers are small,

M =s
c = M y

THE CONCENTRATION RATIO

AND THE FRACTIONAL SUPERSATURATION s ARE DEFINED BY
= c/cs = 1+c/cs =y/ys =1+y/ys =1+s

The quantity 100s is the percentage of supersaturation.

 NUCLEATION AND ITS
TYPES
The rate of nucleation is the number of new particles formed per unit time
Per unit volume of magma or solids free mother liquor.

PRIMARY NUCLEATION

HOMOGENEOUS
HETEROGENOUS

SECONDARY NUCLEATION

FLUID SHEAR NUCLEATION CONTACT

NUCLEATION
HOMOGENOUS NUCLEATION:-

CLUSTER EMBRYO NUCLEUS CRYSTAL

The solubility of small crystals(<micrometer size) is greater than
Large crystal.
KELVIN EQUATION :- THE SOLUBILITY OF A SUBSTANCE IS RELATED
TO ITS PARTICLE
SIZE AS
ln = 4VM / RTL

RATE OF NUCLEATION:-
B= C exp[-(16 3(VM )2 Na)/32 (RT)3 (ln )2 ]
L= CRYSTAL SIZE
= RATIO OF CONCENTRATIONS OF SUPERSATURATED AND SATURATED
SOLUTIONS
VM = MOLAR VOLUME OF CRYSTAL
= AVERAGE INTERFACIAL TENSION BETWEEN SOLID AND LIQUID
= NO OF IONS PER MOLECULE OF SOLUTE
B= NUCLEATION RATE, number/cm3 s
C= frequency factor
Na= AVOGADROS NUMBER
ergs/
R= GAS CONSTANT, 8.3143*107 g mol. k
 HETEROGENEOUS NUCLEATION :- When solid particles of foreign substances
Do influence the nucleation process by catalyzing an increase of nucleation
Rate at a given supersaturation or giving a finite rate at a supersaturation
Where homogeneous nucleation would occur only after a vast time.

RATE OF NUCLEATION:-
B= 1025 exp[-(16 a 3(VM )2 Na)/3 (RT)3 ( s)2 ]
a = apparent interfacial tension

NDARY NUCLEATION:- The formation of nuclei attributable to the

nce of the existing macroscopic crystals in the magma is called
dary nucleation.
UID SHEAR NUCLEATION :- EX:- SUCROSE, MgSO4 .H2 O
ONTACT NUCLEATION :- Most common type of nucleation in industrial
allizers.
Occurs at low supersaturations where the growth rate of crystals
Is optimum for good quality.
= B SS+BE +BC
RATE OF HOMOGENEOUS NUCLEATION DUE TO SUPERSATURATION
NUCLEATION RATE FROM CONTACT OF CRYSTALS WITH IMPELLER
NUCLEATION RATE FROM CRYSTAL- CRYSTAL CONTACT
 GROWTH OF CRYSTALS
al growth is a diffusional process, modified by the effect of solid
ces on which the growth occurs.

e molecules or ions reach the growing faces of a crystal by

sion through the liquid phase.

aching the surface, the molecules or ions must be accepted by the

al and organized into the space lattice.

/ 3 a L2 M

wth rate
molal growth rate
olar density
stant
racteristic length
 SUMMARY
derstand the process of crystallization

Know the purity of product and importance of crystal size

Know the crystal geometry and crystal systems

derstand the invariant crystals

de aware of concept of supersaturation , nucleation and its

pes, and growth of crystals.
 REFERENCES

Warren l. Maccabe, Julian c. Smith , Peter Harriot, Unit Operations of Chemical Engineering,
Macgraw Hill Book Co. , Fifth edition 1995 :P903-922

P c Jain & Monika Jain , Engineering chemistry, Dhanpat rai publications 2010:P 797-802