*

Crystallization: the formation of solid particles within a

homogeneous phase.
Example:
1.The freezing of water to form ice
2.The formation of snow particles from a vapor
3.The formation of solid particles from a liquid melt
4.The formation of solid crystals from a liquid solution

Types of crystal geometry

Crystal  a solid composed of atoms, ion, or molecules, which
are arranged in an orderly and repetitive manner.

Crystals are divided into seven classes based on the

arrangement of the axes to which the angles are referred
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3
4
Equilibrium Solubility in Crystallization

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Yields and Heat and Material Balances in Crystallization

In crystallization process

solution (mother liquor) and the solid crystals are

in contact for a long enough time to reach
equilibrium

mother liquor is saturated at the final temperature of

the process, and the final concentration of the solute
in the solution can be obtained from the solubility
curve.

By knowing the initial concentration of solute, the

final temperature, and the solubility at this
temperature, the yield of crystals from
crystallization process6 can be calculated.
Example 12.11-1
A salt solution weighing 10000 kg with 30 wt% Na2CO3 is cooled
to 293K (20 oC) 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? 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.

Solution:
W kg H2O

10,000 kg solution Cooler and S kg solution

30% Na2CO3 crystallizer 21.5 kg Na2CO3/100 kg H2O

C kg crystals Na2CO3.10H2O
7
Solution example 12.11-1:
(a) Assume that no water is evaporated  W=0 kg
Material balance for water:
0
100 180.2
0.7(10,000)  S C  xH 2OW (1)
100  21.5 286.2

Material balance for Na2CO3:

0
0.3(10,000) 
21.5
S
106
C  xH 2OW (2)
100  21.5 286.2

Solving Eq. 1 and 2 simultaneously, resulting:

C = 6370 kg of Na2CO3.10H2O crystals
S = 3630 kg solution

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Solution example 12.11-1:
(b) Assume that 3% of the total weight of the solution is lost by
evaporation of water in cooling  W=0.03(10,000) = 300 kg H2O
Material balance for water:
100 180.2
0.7(10,000)  S C  300 (1)
100  21.5 286.2

Material balance for Na2CO3:

0 (no salt in stream W)
0.3(10,000) 
21.5
S
106
C  xH 2O W (2)
100  21.5 286.2

Solving Eq. 1 and 2 simultaneously, resulting:

C = 6630 kg of Na2CO3.10H2O crystals
S = 3070 kg solution

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Heat Effect and Heat Balances in Crystallization

Heat of solution: absorbed heat during the dissolution of

compound due to the increasing of solubility
as temperature increases

In crystallization  Heat of crystallization = - Heat of solution

Total heat absorbed (q) in kJ is:

q  H 2  HV   H1
Enthalpy of water vapor Enthalpy of the entering
solution at the initial
Enthalpy of the final mixture temp
of crystals and mother liquor
at final temp 10
 System System

q (+) q (-)

Example 12.11-2
A feed solution of 2268 kg at 327.6 K (54.4 oC) containing 48.2 kg
MgSO4/100 kg total water is cooled to 293.2 K (20 oC), where
MgSO4.7H2O crystals are removed. The solubility of the salt is
35.5 kg MgSO4/100 kg total water. The average heat capacity of the
feed solution can be assumed as 2.93 kJ/kg.K. The heat of solution
at 291.2 K (18 oC) is -13.31×103 kJ/kg mol MgSO4.7H2O.
 Calculate the yield of crystals and make a heat balance to
determine the total heat absorbed, assuming that no water is
evaporaized! 11
Solution example 12.11-2:
W kg H2O

2268 kg solution Cooler and S kg solution

48.2 kg MgSO4/100 kg total water crystallizer 35.5 kg MgSO4/100 kg total water
T=327.6 K

C kg crystals MgSO4.7H2O
T=293.2 K

Assume that no water is evaporated  W=0 kg

Material balance for water:
0
100
2268  100 S  126 C  xH 2OW (1)
100  48.2 100  35.5 246

Material balance for Na2CO3:

0
48.2
2268  35.5
S
120
C  xH 2OW (2)
100  48.2 100  35.5 246
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Solution example 12.11-2:

Solving Eq. 1 and 2 simultaneously, resulting:

C = 616.9 kg of MgSO4.7H2O crystals
S = 1651.1 kg solution

H1  mc p T Tref
H1  2268(2.93)(327.6  293.2)  228,600kJ

Heat of solution = -13.31×103 kJ/kg mol MgSO4.7H2O

= -13.31×103 /246 = -54 kJ/kg crystals

Heat of crystallization = - Heat of solution

= + 54 kJ/kg crystals
= 54 (616.9) = 33,312 kJ
Assume: heat of crystallization at 291.2 K = heat of
crystalization at 293.2 K 13
Solution example 12.11-2:

0 (No water is vaporized)

q  H 2  HV   H1
0 (Tfinal=Tref)

q = -H1 - heat of crystallization

q = -228,600 – 33,312 = -261,912 kJ

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