CHAPTER 5

CRYSTALLIZATION
OPERATIONS

By:
In. Nurul Hasyimah Mohd Amin
OBJECTIVES

 At the end of this lesson, students should be

able to:
 Define crystallization process
 Explain the equilibrium solubility in crystallization
 Describe the supersaturation in crystallization
 Determine the yield and size of crystal
INTRODUCTION

Liquid crystallization crystalline

the process where the

atom/molecule/ion
arranged themselves in a
repeating pattern and in
homogenous phase
 CRYSTAL GEOMETRY

classified located in 3-D

based on arrays
the .

..polyhedrons
..having flat
faces and
The  between sharp corners
the corresponding
faces are equal
CRYSTAL GEOMETRY

7 classes of crystals depending on the arrangement of

the axes to which the angles are referred:
1. Cubic system
2. Tetragonal system
3. Orthohombic system
4. Hexagonal system
5. Monoclinic system
6. Triclinic system
7. Trigonal system
EQUILIBRIUM SOLUBILITY IN
CRYSTALLIZATION

 Equilibrium is attained when the solution (mother liquor)

is saturated and represented by a solubility curve.

 Saturated solution  cooled  crystals

 Solubility is dependent mainly on temperature and

pressure has a negligible effect on solubility.
EQUILIBRIUM SOLUBILITY IN
CRYSTALLIZATION

Figure 1: Example of solubility curve

EQUILIBRIUM SOLUBILITY IN
CRYSTALLIZATION

Figure 2: Solubility of several solids

YIELDS IN CRYSTALLIZATION

 The yield of the process can be calculated from the

initial concentration of solute and the solubility at the
final temperature.
Example 3.1
A salt solution weighing 10 000 kg with 30 wt%
Na2CO3 is cooled to 293 K. The salt crystallizes
as the decahydrate. Calculate the yield of
Na2CO3.10H2O crystals if the solubility is 21.5 kg
anhydrous Na2CO3/100 kg of total water if there is
no water is evaporated.
SUPERSATURATION IN
CRYSTALLIZATION
 In order for crystallization to take place, a solution must
be ‘supersaturated’

 Supersaturation is refers to a state in which the liquid

(solvent) contains more dissolved solids (solute) than
can ordinarily be accommodated at that temperature.
SUPERSATURATION IN CRYSTALLIZATION

By cooling

Supersaturation

By
By salting
evaporation
ENTHALPY BALANCES

 In heat balances calculation, the heat of crystallization is

important.

 The heat of crystallization is varies with temperature and

concentration.

 It is equal to the heat absorbed by crystals dissolving in

a saturated solution.
ENTHALPY BALANCES

 The total heat absorbed is

q  ( H 2  H v )  H1 (3.1)
 Where H1 is the enthalpy of entering solution
at the initial temperature
H2 is the enthalpy of the final mixture of
crystals and mother liquor at the final
temperature.
Hv is the enthalpy of vaporization
CRYSTALLIZATION THEORY:
Introduction

supersaturated

crystallization

Nucleation Crystal
(nuc formation) growth
Nucleation

 The rate of nucleation is the number of new particles

formed per unit time per unit volume of magma or solid
free mother liquor.
 This quantity is the first kinetic parameter controlling the
crystal size distribution (CSD)
Nucleation

• High
Homogen supersaturation
eous
• No agitation

Nucleation

• Low
Heterege supersaturation
neous
• With agitation
Primary (Homogeneous) Nucleation

 The solubility of a substance is related to its

particle size by Kelvin equation:
4VM 
ln  
RTL (3.2)
Where
L = crystal size

 = ratio of concentration of supersaturated and

saturated solutions
VM = molar volume of crystal

 = average interfacial tension between solid and

liquid
 = number of ions per molecule of solute
Rate of Nucleation

 The rate of nucleation is given by:

Homogeneous:  16  VM N a 
3 2
B  C exp  2
o
2
 3 ( RT ) 3
(ln  )  (3.3)

Heterogeneous:
16  V 2
N  3

B  10 exp 
o 25 M a a
3 2 2 
(3.4)
 3( RT )  s 
Rate of Nucleation

Where Bo
Nucleation rate, number/cm3.s
Na
Avogadro constant, 6.0222 x 1023
molecules/gmol
R Gas constant, 8.314 x 107 ergs/gmol.K
C Frequency factor
B o  2.23  10 25 nuclei / cm 3 .s
B o  2.23  10 25 nuclei / cm 3 .s

Example 3.3

 Estimate the primary homogeneous nucleation

rate of KCl from an aqueous solution if the
supersaturation ratio,  at 25oC is 2.0. Given:
Molecular weight of KCl = 74.6 kg/kmol
Density of KCl = 1980 kg/m3
Average interfacial tension = 0.028 J/m2
 To obtain a desired predominent size Lpr in the
population, nucleation rate is:
(3.16)
9C
B 
o

2acVc L3pr
Where C
Mass production rate of crystals
a Shape factor
c Molar density of crystal
Vc Total volume of liquid in crystallizer
Example 3.4

 If the desired production rate in the crystallizer is

4200 kg/hr of MgSO4.7H2O, the volume of liquid
in the crystallizer is 7.7 m3 and the nucleation
rate is 2.7 x 109 nuclei/m3.hr, estimate the
predominant crystal size if the density is 1681.9
kg/m3 (assume a = 1).

B o  2.23  10 25 nuclei / cm 3 .s
B o  2.23  10 25 nuclei / cm 3 .s