CHAPTER 3 :

CRYSTALLIZATION


Ms Noor Rosyidah Binti Sajuni
School of Engineering

rosyidah@ucsi.edu.my
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
Explain theory of crystallization
Describe equipments in crystallization

12.11 INTRODUCTION (page 817)
Crystallization is a solid-liquid process, in which mass
transfer of a solute from the liquid solution to a pure solid
crystalline occurs.
The formation of solid particles within a homogeneous
phase.
It can occurs in:
- the freezing of water to form ice
- the formation of snow particles from a vapor
- the formation of solid particles from a liquid melt
- the formation of solid crystals from a liquid solution
INTRODUCTION
In industrial crystallization from solution, the two phase
mixture of mother liquor and crystals which occupies the
crystallizer is withdrawn as product called magma.

In commercial crystallization, it is important to get good
yield, high purity of crystals and uniform shape and size of
the crystals.

Size uniformity is desirable:
- to minimize caking in the package
- for ease of pouring
- for ease in washing and filtering
- for uniform behavior when used
TYPES OF CRYSTAL GEOMETRY
A crystal is a solid composed of atoms, ions or molecules
which are arranged in an orderly and repetitive manner.
It is highly organized type of matter.
The atoms, ions or molecules are located in 3-dimentional
arrays (space lattices).
Crystals appear as polyhedrons having flat faces and sharp
corners.
TYPES OF CRYSTAL GEOMETRY
The relative sizes of the faces and edges of different crystals of
the same material may differ greatly.

The angles between the corresponding faces of all crystals of
the same material are equal and are characteristic of that
particular material.

Crystals are classified on the basis of these interfacial angles.
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
Triclinic e.g. microcline
Orthorhombic e.g. aragonite
12.11B - EQUILIBRIUM SOLUBILITY IN
CRYSTALLIZATION
Equilibrium is attained when the solution (mother liquor) is
saturated and represented by a solubility curve.
Solubility is dependent mainly on temperature and pressure
has a negligible effect on solubility.
Curve showing solubility as a function of temperature.
Solubility of most salt increase slightly or markedly with
increasing of temperature.
EQUILIBRIUM SOLUBILITY IN
CRYSTALLIZATION
Figure 3.1: Example of solubility curve
A general solubility curve for a solid that forms hydrate (a compound that has one
or more water molecules attached) as it cools is shown in Figure 3.1.
EQUILIBRIUM SOLUBILITY IN
CRYSTALLIZATION
Figure 12.11-1: Solubility of sodium thiosulfate in water
EQUILIBRIUM SOLUBILITY IN
CRYSTALLIZATION
Figure 3.3: Solubility of several solids
12.11C - YIELDS IN CRYSTALLIZATION
In industrial crystallization, the solution (mother liquor) and
the solid crystals are in contact for a long enough time to reach
equilibrium.
The mother liquor is saturated at the final temperature of the
process.
The final concentration of the solute in the solution can be
obtained from the solubility curve.

YIELDS IN CRYSTALLIZATION
The yield of the process can be calculated from the initial
concentration of solute and the solubility at the final
temperature.

When the rate of crystal growth is slow (due to the very
viscous solution or small surface of crystals exposed to the
solution), considerable time is required to reach equilibrium

The final mother liquor may retain supersaturation and the
actual yield will be less than calculated from the solubility
curve.
YIELDS IN CRYSTALLIZATION
If the crystals are anhydrous, the calculation of the yield is
simple.
When the crystals are hydrated, some of the water in the
solution is removed with the crystals as a hydrate.
Solubility data are given either in
- parts by mass of anhydrous material per 100
parts by mass of total solvent
- mass fraction anhydrous solute
These data ignore water of crystallization.
Example 12.11-1 (Geankoplis)
Yields and mass balances in
crystallization

A salt solution weighing 10 000kg with 30wt. % Na
2
CO
3
is cooled to
293 K (20
0
C). The salt crystallizes as the decahydrate. What will be
the yield of Na
2
CO
3
.10H
2
O crystals if the solubility is 21.5 kg
anhydrous Na
2
CO
3
/100 kg of total water? Do this for the 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.

MW Na
2
CO
3
=106.0 kg/kg mol
MW 10H
2
O = 180.2







Mass balance :
Water balance : Input = Output
Solute balance : Input = Output
10 000 kg Hot solution
30% Na
2
CO
3
C kg Crystals, Na
2
C0
3
.10H2O
21.5 kg Na
2
C0
3
/100 kg H
2
O
S kg solution
W kg H
2
O evaporate
Solution
12.11C HEAT BALANCE IN CRYSTALLIZATION

When a solubility of compound increases as temperature increases during
dissolving, an absorption of heat is called heat of solution.

When a solubility of compound decrease as temperature increases during
dissolving, an evolution of heat occurs.

When a solubility of compound does not changes as temperature increases
during dissolving, there is no neat of evolution on dissolution.

In crystallization the opposite of dissolution occurs. At equilibrium, the heat
of crystallization is equal to the negative of the heat of solution at the same
concentration in solution.

The most satisfactory method of calculating heat effects during a
crystallization process is to use the enthalpy-concentration chat. However
only a few charts are available.
ENTHALPY BALANCES IN
CRYSTALLIZATION
In heat balances calculation, the heat of crystallization is
important.

This is the latent heat evolved when solid forms a solution.

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 IN
CRYSTALLIZATION
The total heat absorbed is


Where
q = total heat absorbed (kJ)
H
1
= enthalpy of entering solution at the initial temperature (kJ/Btu)
H
2
= enthalpy of the final mixture of crystals and mother liquor at the
final temperature (kJ/Btu)
H
v
=enthalpy of vaporization
Hs = heat of solution (kJ/kg mol)

If q (+ ve) = heat must added to the system
q (-ve) = heat is evolved or given off.

1 2
) ( H H H q
v
(12.11-4)
T
c
H
2
O
T
c
,
H
v
(enthalpy of evaporation) kJ

Hot solution
T
f
(Initial temperature)

H
1
(enthalpy of entering solution ) kJ
Solute/solvent
T
c
, H
3
Total Heat Absorbed
q = (H
2
+ H
3
+ H
v
) H
1
Product
T
c
(final temperature)
H
2
(enthalphy of the final mixture of crystals and
mother liquor) kJ

Example 12.11-2
A feed solution of 2268 kg at 327.6 K (54.4
0
C) containing 48.2 kg
MgSO
4
/100 kg total water is cooled to 293.2 K (20
0
C), where
MgSO
4
.7H
2
O crystals are removed. The solubility of the salt is 35.5
kg MgSO
4
/100 kg total water (P1). The average heat capacity of the
feed solution can be assumed as 2.93 kJ/kg.K (H1). The heat of
solution at 291.2 K (18
0
C) is -13.31 x 10
3
kJ/kg mol MgSO
4
.7H
2
O
(P1). Calculate the yield of crystals and make a heat balance to
determine the total heat absorbed, q, assuming that no water is
vaporized.

MW MgSO4 = 120.35 kg/kgmol
MW 7H2O = 126.14 kg/kgmol
Solution
Make a water and a MgSO
4
balances.

solutions kg 1664 S
crystals kg 617 C
usly, simultaneo equations the Solve
0.262
0.488C 737.1
S 2, From
2 0.488C 0.262S ) 2268(0.325
C
246.49
120.35
S
100 35.5
35.5
) 2268(0.325
balance MgSO
1 0.5117C 0.735 1530.4
C
246.49
126.14
S
100 35.5
100
) 2268(0.674
balance O H
0.674 fraction Water
0.325
48.2 100
48.2
fraction Crystal
4
2

MW MgSO4 = 120.35 kg/kgmol

MW 7H2O = 126.14 kg/kgmol