Introduction to crystallization

1. The crystallization is a process in which solid particles are formed from a homogenous
phase.
For example: -
a. Freezing of water in the formation of ice.
b. Formation of snow particles from water vapor.
c. Formation of solid particles from a liquid melt.
d. Formation of solid crystals from a liquid solution.
2. In this module, we are concerned with formation of solid crystals from an aqueous liquid
solution,
3. Thus, we are concerned with crystallization as a unit operation in which a solid phase is
formed out of a liquid phase through transfer of solute from the liquid solution to a pure
solid crystalline phase.
For example: -
Production of sucrose crystals from the aqueous solution of sugar beet.
4. In this operation, the feed solution is heated and then cooled until the concentration of the
solute in the solution becomes greater than the equilibrium solubility of the solute at the
prevailing temperature. Some of the solvent may be evaporated in this process. A typical
crystallization operation is schematically shown in the Figure 1. In this figure, the input
the operation is the feed solution, while the outputs are the crystals, the mother liquor and
the water that may be evaporated.

Figure 1. The unit operation of crystallization

5. Since many of the material handled in chemical industries is in crystalline form,
crystallization is important industrially. The most important features of crystallization
are-
a. The crystals obtained from an impure solution are pure. However, this is not true
when mixed crystals are formed.
 b. The product of crystallization are pure crystals which are ready for packing and
storing.

Equilibrium in crystallization
1. As a solute is dissolved in a solvent, a stage is reached when the resulting solution
becomes saturated. No more solute can be dissolved in the resulting saturated
solution,
2. When we have a saturated solution, equilibrium is achieved and the concentration of
the solute in this saturated solution is said to be the equilibrium solubility of the
solute at the prevailing temperature.
3. Generally, the equilibrium solubility is defined as the grams of solute that could be
dissolved in 100 𝑚𝑙 of a solvent at a given temperature.
4. The equilibrium solubility of a particular solute is dependent on temperature.
However, the pressure has a negligible effect on the equilibrium solubility.
5. When the equilibrium solubility of a solute is plotted against temperature, the
resulting curve is called as the solubility curve. The solubility curve for some salts are
shown in the Figure 2.

Figure 2. Solubility curves for various solutes

6. The soloing points can be noted for the Figure 2.
a. For most of the solutes, the equilibrium solubility increases more or the less
rapidly with the temperature. This behaviour is shown by the solubility curve
for 𝐾𝑁𝑂3. In this case, there is no formation of hydrates.
 b. For some solutes, the equilibrium solubility changes slowly with temperature.
This behaviour is shown the solubility curve for 𝑁𝑎𝐶𝑙
c. For some solutes, the equilibrium solubility decrease with temperature. The
solubility curve for such solutes is called as the inverted solubility curve. The
curve for 𝑀𝑛𝑆𝑂4. 𝐻2𝑂 is one such curve.
7. Many of the inorganic crystals crystalize with water of crystallization. In many cases,
several different hydrates are formed depending on the concentration and
temperature. The solubility curve for 𝑁𝑎2𝑆2𝑂3 is shown in the Figure 3. The solubility
curve rapidly rises with temperature, but there are marked breaks in the curve, which
indicates different hydrates.

Figure 3. Solubility curve for 𝑵𝒂𝟐𝑪𝑶𝟑

Crystallization Theory
1. Understanding the crystallization process is important for designing and operating
crystallizers.
2. There are two basic steps in the process of crystallization.
a. Nucleation.
b. Crystal growth.
3. The driving force for both the above mentioned steps is supersaturation and these steps
will not proceed in saturated or unsaturated solution.
4. Supersaturation is defined as the concentration difference between a supersaturated
solution and a saturated solution. It has to be noted that both the solutions are at the same
temperatures.
5. There are three methods by which supersaturation can be achieved. These are listed below.
a. Cooling
This method is used in case of those solutes whose solublities sharply increases
with increase in the temperature. Many inorganic salts and organic substance
show this kind of behaviour.
b. Evaporation
In this method, some portion of the solvent is evaporated so that the concentration
of the solute becomes greater than its equilibrium solubility at the prevailing
temperature. This method is used for those solutes whose solubility is relatively
independent of temperature.
c. Salting
This method is used in case of those solutes which have very high solubilities. In
this method, a third component is added to the solution. This component forms
combines physically with the parent solvent to form a mixed solvent. The
solubility of the solute is sharply reduced in the mixed solvent.
6. The first attempt to qualitatively explain the process of crystallization was made by Miers
supersaturation theory. The theory is represented in the Figure 4.
 Figure 4. Miers supersaturation theory
7. Following point can be note for the Figure 4.
a. Curve 𝐴𝐵 is the normal solubility curve. Every point on this curve represent a
saturated solution at the given temperature.
b. Consider a liquid solution at point 𝑎 on the Figure 4. If this solution is cooled, it
will first cross the solubility curve 𝐴𝐵, and then will reach point 𝑏, where the
solution will become supersaturated. There are infinite number of points like point
𝑏 on the curve 𝐶𝐷. Therefore, the curve 𝐶𝐷 is called as the super solubility curve.
c. Once the solution becomes supersaturated, the process of crystallization starts
with nucleation. When this happens, the concertation of the solute in the solution
suddenly drops to point 𝑐, which represents a saturated solution
8. After nuclei are formed in the nucleation step, they start growing in the crystal growth
step. Following point can be noted for this step.
a. The crystal growth is a layer by layer process.
b. The crystal growth occurs only at the outer face of the crystal.
c. Therefore, the solute material must be transferred to the face of the crystal from
the bulk solution. This movement of solute is due to diffusion.
9. McCabe had proposed a law for the process of crystal growth. This law is known as the
Δ𝐿′𝑠 law of crystal growth. Following points can be noted for this law.
a. According to this law, all geometrically similar crystals of the same solute grow
at the same rate in the same solution.
 b. The growth is measured in terms of increase in a linear dimension of a crystal per
unit time.
c. Mathematically, this law is given by Eq. (1).
ΔL
=𝐺 (1)
Δt

In Eq. (1), Δ𝐿 is increase in a linear dimension in time Δ𝑡.

d. The law fails to apply in those cases, where the crystals are treated differently on
the basis of their size.
e. This law is particularly applicable in case of crystals under 0.3 𝑚𝑚 size.

Material balance for the crystallization

1. Consider a crystallization operation as shown in the Figure 5. In the operation weight of
the feed is 𝐹, with 𝑥F mass fraction of solute in it. The mass of water evaporated is 𝑊,
while the mass of crystals produced is 𝐶, and the mass of the mother liquor is 𝑀. 𝑥M is
the mass fraction of the solute in the mother liquor.

Figure 5. Material balance for the crystallization operation

2. Let the crystals produced by hydrated crystals, where 𝑀1 is the molecular weight of the
hydrated crystals and 𝑀2 be the molecular weight of anhydrous crystals.
3. The total material balance for the operation will be written as in Eq. (2)
𝐹=𝐶+𝑀+𝑊 (2)
Before writing the material balance for the solute, the following concepts needs to be
understood.
In 𝑀1 mass of hydrated crystals, the mass of anhydrous crystals (the solute) is 𝑀2
and that of water of crystallization will be 𝑀1 − 𝑀2. Thus, if mass of solute in 𝑀2 is
𝑀1, the
mass of solute in 𝐶 will be M2
𝐶. With this understanding, the material balance for the
M1

solute is written as in Eq. (3).

 M2
𝐹𝑥 = 𝐶+𝑥 𝑀 (3)
F M1 M
If the mass of water in 𝑀 is 𝑀 − 𝑀 , the mass of water in 𝐶 will be M1–M2 𝐶. Therefore,
1 1 2 M1
the balance for water will be written as in Eq. (4).
M1–M2
𝐹( 1 − 𝑥 ) = 𝐶 + (1 − 𝑥
)𝑀 + 𝑊 (4)
F M1 M

Numerical No. 1
A salt solution weighing 10000 𝑘𝑔 with 30 𝑤𝑡 % 𝑁𝑎2𝐶𝑂3 is cooled to 293 𝐾. The salt
crystallizes as the decahydrate. Find the yield of 𝑁𝑎2𝐶𝑂3. 10𝐻2𝑂 crystals if the solubility is
21.5 𝑘𝑔 anhydrous 𝑁𝑎2𝐶𝑂3 per 100 𝑘𝑔 of total water. Do this for the following two cases.
a. Assume that no water is evaporated.
b. Assume that 3 % of the total weight of solution is lost by evaporation of water during the
cooling process.

Given
1. The quantity of feed solution (𝐹) is 10000 𝑘𝑔.
2. The weight percent of 𝑁𝑎2𝐶𝑂3 in the feed is 30 𝑤𝑡 %, 𝑥F = 0.3.
3. The salt crystallizes as the decahydrate (𝑁𝑎2𝐶𝑂3. 10𝐻2𝑂).
4. The solubility is 21.5 𝑘𝑔 anhydrous 𝑁𝑎2𝐶𝑂3 per 100 𝑘𝑔 of total water.
5. The yield of 𝑁𝑎2𝐶𝑂3. 10𝐻2𝑂 crystals to be found out for the following two cases
a. When no water is evaporated.
b. When 3 % of the total weight of solution is lost by evaporation

Solution
Our approach will be
1. Find 𝑥M from the solubility.
2. Use material balance equations to get 𝐶, 𝑀
3. Find the required yields.
Calculation of 𝑥M
𝑥M will be calculated from the given solubility. The solubility is 21.5 𝑘𝑔 anhydrous 𝑁𝑎2𝐶𝑂3 per
100 𝑘𝑔 of total water. This means that there is 21.5 𝑘𝑔 anhydrous 𝑁𝑎2𝐶𝑂3 in a solution
containing 21.5 𝑘𝑔 anhydrous 𝑁𝑎2𝐶𝑂3 and 100 𝑘𝑔 of water. Therefore, 𝑥M, which is fraction of
anhydrous 𝑁𝑎2𝐶𝑂3 in the solution is calculated as-

𝑥M 21.5
= 100+21.5

Therefore, 𝑥M = 0.177

Case a. When no water is evaporated.

The total material balance for this case will be written in the following way.
𝐹=𝐶+𝑀+𝑊
But since 𝑊 = 0 𝐹=𝐶+𝑀
Therefore, 10000 = 𝐶 + 𝑀 (A)

The material balance for the solute will be written in the following way
M2
𝐹𝑥 = 𝐶+𝑥 𝑀
F M1 M

In the above equation, 𝑀1 is the molecular weight of 𝑁𝑎2𝐶𝑂3. 10𝐻2𝑂 and 𝑀2 is the molecular
weight of 𝑁𝑎2𝐶𝑂3.
Therefore, 𝑀1 = 286 and 𝑀2 = 106. With these, the material balance for the solute becomes
106
10000 × 0.3 = 𝐶 + 0.177𝑀
286

Therefore, 3000 = 0.37𝐶 + 0.177𝑀 (B)

With Eq. (A), 𝑀 = 10000 − 𝐶 and use this in Eq. (B)
Therefore, 3000 = 0.37𝐶 + 0.177(10000 − 𝐶)
Therefore, 3000 = 0.37𝐶 + 1770 − 0.177𝐶
Therefore, 3000 = 0.193𝐶 + 1770
3000–1770
Therefore, 𝐶=
0.193

Therefore, 𝐶 = 6373.06 𝑘𝑔
And finally, 𝑀 = 10000 − 𝐶
Therefore 𝑀 = 10000 − 6373.06
Therefore, 𝑀 = 3626.94 𝑘𝑔
Now, the % yield of the crystals is calculated as-
 % 𝑌𝑒𝑖𝑙𝑑 = 𝑁𝑎2𝐶𝑂3 𝑖𝑛 𝐶
× 100
𝑁𝑎2𝐶𝑂3 𝑖𝑛 𝐹
M
( 2)C
Therefore, % 𝑌𝑒𝑖𝑙𝑑 = M1

xF F
106
( )×6373.06
Therefore, % 𝑌𝑒𝑖𝑙𝑑 = 286 × 100
0.3×10000

Therefore, % 𝑌𝑒𝑖𝑙𝑑 = 78.73

Case b. When 3 % of the total weight of solution is lost by evaporation

Since, 3 % of the total weight of solution is lost by evaporation
𝑊 = 0.03 × 10000
Therefore, 𝑊 = 300 𝑘𝑔
The total material balance for this case will be written in the following way.
𝐹=𝐶+𝑀+𝑊
Therefore, 10000 = 𝐶 + 𝑀 + 300
Therefore, 𝐶 + 𝑀 = 9700 (A)
The material balance for the solute will be written in the following way
M2
𝐹𝑥 = 𝐶+𝑥 𝑀
F M1 M
106
10000 × 0.3 = 𝐶 + 0.177𝑀
286

Therefore, 3000 = 0.37𝐶 + 0.177𝑀 (B)

With Eq. (A), 𝑀 = 9700 − 𝐶 and use this in Eq. (B)
Therefore, 3000 = 0.37𝐶 + 0.177(9700 − 𝐶)
Therefore, 3000 = 0.37𝐶 + 1716.9 − 0.177𝐶
Therefore, 3000 = 0.193𝐶 + 1716.9
3000–1716.9
Therefore, 𝐶=
0.193

Therefore, 𝐶 = 6648.19 𝑘𝑔
And finally, 𝑀 = 10000 − 𝐶
Therefore 𝑀 = 10000 − 6648.19
Therefore, 𝑀 = 3351.81 𝑘𝑔
Now, the % yield of the crystals is calculated as-
 % 𝑌𝑒𝑖𝑙𝑑 = 𝑁𝑎2𝐶𝑂3 𝑖𝑛 𝐶
× 100
𝑁𝑎2𝐶𝑂3 𝑖𝑛 𝐹
M
( 2)C
Therefore, % 𝑌𝑒𝑖𝑙𝑑 = M1

xF F
106
286 (
)×6648.19
Therefore, % 𝑌𝑒𝑖𝑙𝑑 = × 100
0.3×10000

Therefore, % 𝑌𝑒𝑖𝑙𝑑 = 82.13