CRYSTALLISATION

Introduction

OBJECTIVES
STUDENTS SHOULD BE ABLE TO:

1. Understand the concept of crystallization

2. Perform material & heat balance for
crystallization process

CRYSTALLISATION THEORY
Process where solid particles are formed from
homogeneous phase.
Occur in the:
freezing of water to form ice,
formation of solid particles from liquid melts,
formation of snow particles from vapour or
formation of solid crystals from a liquid solution
(MOST IMPORTANT & COMMERCIALIZED)
3

MECHANISMS
The solution is concentrated and usually cooled
until the solute concentration becomes greater than
its solubility at that temperature.
Then, the solute comes out of the solution, forming
crystals of approximately pure solute.

OBJECTIVE OF CRYSTALLIZATION
1. Good yield

2. High purity
3. Size, shapes

4. Uniformity

WHY UNIFORMITY IS
IMPORTANT???
a) Minimize caking in the package

b) For ease of pouring

c) For ease of washing and filtering

d) Uniform behavior when used

CRYSTAL GEOMETRY

CRYSTALS
A Solid composed of atoms, ions or
molecules which are arranged
ORDERLY and REPETITIVE MANNER.
Appear as polyhedrons, having flat
faces & sharp corners.
The ANGLE between the corresponding faces of
all crystals of THE SAME MATERIAL are
EQUALCHARACTERISTIC OF THE
PARTICULAR MATERIAL.
8

CRYSTAL
Development of different types of faces of crystal
may differ depending on the solute crystallizing.
Eg. NaCl crystallizes from aqueous solution with
cubic faces

NaCl crystallizes from aqueous solution, impurity

present, will have octahedral faces,
BUT BOTH are in the CUBIC system.

SNOWFLAKES
When water freezes into ice, the water molecules
stack together to form a regular crystalline lattice,
and the ice lattice has six-fold symmetry

A hexagonal prism includes two hexagonal "basal"

faces and six rectangular "prism" faces. Hexagonal
prism can be plate-like or columnar, depending on
which facet surfaces grow most quickly.

10

SNOWFLAKES
When snow crystals are very small, they are mostly
in the form of simple hexagonal prisms. But as they
grow, branches sprout from the corners to make
more complex shapes.

11

SNOWFLAKES CRYSTALS

12

EQUILIBRIUM SOLUBILITY IN
CRYSTALLIZATION
ATTAIN EQUILIBRIUM WHEN THE
SOLUTION/MOTHER LIQUOR IS
SATURATED.
Represented by a SOLUBILITY CURVE.
Solubility is dependent mainly on TEMPERATURE.

13

SOLUBILITY CHART
Generally, the
solubilities of most
salts increase with
increasing
temperature.
That is why normally we
cooled down the solution to
get the crystal so that the
concentration exceed the
solubility at that
temperature
14

SOLUBILITY CHART
anywhere on it's solubility curve it is saturated
above the solubility curve, then it's supersaturated
below the solubility curve it's an unsaturated
solution.

16

Some salts, when crystallised from aqueous

solution, incorporate water molecules into the
structure. This is known as 'water of crystallisation',
and the 'hydrated' form of the compound.

e.g. magnesium sulphate MgSO4.7H2O.

17

YIELD, HEAT & MATERIAL BALANCE IN

CRYSTALLIZATION
DURING CRYSTALLIZATION PROCESS, THE
SOLUTION (MOTHER LIQUOR) & THE SOLID
CRYSTALS ARE IN CONTACT FOR ENOUGH TIME TO
REACH EQUILIBRIUM.
At the end of the process, AT FINAL TEMPERATURE T,
the solution is saturated, hence the final concentration of
the solution can be obtained from SOLUBILITY CURVE.

18

YIELD, HEAT & MATERIAL BALANCE IN

CRYSTALLIZATION
THE YIELD OF CRYSTALS CAN BE CALCULATED
FROM:

INITIAL CONCENTRATION OF SOLUTE

FINAL TEMPERATURE &

ITS SOLUBILITY AT THE TEMPERATURE

19

YIELD, HEAT & MATERIAL BALANCE IN

CRYSTALLIZATION
Material balance is straightforward , when
SOLUTES are anhydrous.
When the crystals are hydrated, some of the
water in the solution is removed with the crystals
are hydrate.

20

EXAMPLE 12.11-1
A salt solution weighing 10 000 kg with 30%
Na2CO3 is cooled to 293 K (200C). The salt
crystallizes as the decahydrate. What will be the
yield of Na2CO3 10H2O crystals if the solubility
is 21.5 kg anhydrous Na2CO3/100 kg of total
water? Assume that no water is evaporated.

21

SOLUTION FOR EXAMPLE 12.11-1

W kg H2O
10,000 KG
SOLUTION

S kg
solution

COOLER &
CRYSTALLIZER

30% Na2CO3

21.5 kg
Na2CO3/100 kg
H2O

C kg crystals,
Na2CO3 10H2O
22

SOLUTION FOR EXAMPLE 12.11-1

1. Perform material balance for water and Na2CO3
Feed = Solution stream + Crystals stream + Other stream
Water

100
180.2
0.7(10000)
(S)
(C ) 0
100 21.5
286.2

Na2CO3

21.5
106
0.3(10000)
(S)
(C ) 0
100 21.5
286.2

Molecular Weight:

10H2O = 180.2

Na2CO3 = 106
Na2CO3 10H2O = 286.2

23

SOLUTION FOR EXAMPLE 12.11-1

2. Solving the two equation simultaneously,
C = 6370 kg of Na2CO3 10H2O crystals
S = 3630 kg solution

Assume that 3% of the total weight of the

solution is LOST by evaporation of water in
cooling.RECALCULATE C& S VALUES.
24

EXERCISE 1
A salt weighing 8,000 kg with 25 wt% Na2CO3 is cooled to 293 K.
The salt crystallized as dehydrate and solubility is 21.5 kg anhydrous
Na2CO3 /100 kg of total water.
Assuming that 3% of the total weight of the solution is lost by
evaporation of water in cooling and no water is evaporated, calculate
the yield of Na2CO3.10H20 crystals.

25

HEAT EFFECT AND BALANCE

26

HEAT EFFECTS AND BALANCE

When a compound (whose solubility increases as
temperature increases) dissolves, there is an absorption
of heat; called the heat of solution.
When a compound (whose solubility decreases as
temperature increases) dissolves, there is an evolution
of heat.
For compounds dissolving whose solubility does not
change with temperature, there is no heat of evolution
or heat of dissolution.

27

HEAT EFFECTS AND BALANCE

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.

28

HEAT BALANCE IN CRYSTALLIZATION

q = (H2 +HV) H1
H1 = enthalpy of the entering solution at the initial
temperature
H2 = enthalpy of the final mixture of crystals and mother
liquor, at the final temperature
HV = enthalpy of water vapor (if evaporation occurs)
q = Total heat absorbed (kJ)
= +ve: heat must be added to the system
= -ve: heat is evolved or given off
29

EQUIPMENT FOR CRYSTALLIZATION

30

CRYSTALLIZATION THEORY
Basic understanding on
Mechanisms crystal form
Crystals growth

The solution FREE from solid particles

Nucleus formation occurs first crystal growth starts

Driving force for nucleation step & growth step is SUPERSATURATION.

(except in saturated & undersaturated solution)

31

NUCLEATION THEORIES

Solubility &
crystal size

Homogenous
nucleation

Contact
nucleation

Nucleation in
commercial
crystallizers

32

SOLUBILITY & CRYSTAL SIZE

Thermodynamic diff between SMALL & LARGE particles/ crystals
(small particles has significant amount of surface energy/mass
while large does not)
Small crystal has greater solubility than larger size.
If larger crystal is also present, the larger crystal will grow and
the smaller will dissolve

33

HOMOGENOUS NUCLEATION
Important for solution with high super saturation & NO agitation

The molecules associate into cluster (rapid random fluctuations of

molecules)- loose aggregate quickly disappear
Supersaturation large- particles associate to form nucleus grow
and oriented into fixed lattice to form crystal

34

CONTACT NUCLEATION
Intensity of agitation is important factor

2 types of contact nucleation

Formation of new nuclei due to interference of the contacting
agent (walls of a container/ agitator blades) with clusters of
solute molecules becoming organized into the existing crystals and
by actual breakage of microscopic growths on the surface of
growing crystals
Formation of new nuclei occurs in collisions between crystals.

35

NUCLEATION IN COMMERCIAL
CRYSTALLIZERS
Supersaturation is LOW
To keep the crystal suspended- agitation is used
At low super saturation- the crystal growth rate is at
optimum for uniform crystal.
Predominant mechanism = contact nucleation.
Least apply mechanism = homogenous nucleation due to
agitation & low supersaturation
36

REFERENCES
Books
1.
Geankoplis C. J., Transport Processes and Separation Process
Principles, 4th Edition, Prentice Hall, 2003.
2.
McCabe W. M., Smith J. C. and Harriott P., Unit Operations
of Chemical Engineering, 7th Ed., McGraw Hill, 2005.
Websites:
http://www.its.caltech.edu/~atomic/snowcrystals/primer/primer.htm

http://www.sciencemag.org/content/322/5909/1802.full
http://www.seas.upenn.edu/~chem101/sschem/solidstatechem.html

37

THANK YOU.

38