Crystallization 2

Learning Outcomes

After this lecture you should be able to…

Solve problems in crystallization

 Equilibrium Solubility
In crystallization, equilibrium is attained when the
solution or mother liquor is saturated.

This is represented by a solubility curve.

Solubility in crystallization is dependent mainly upon

temperature. Pressure has negligible effect on
solubility.

In general, the solubilities of most salts increase slightly

or markedly with increasing temperature.
 Equilibrium Solubility

In solubility plots, the solubility data are ordinarily

given as parts by weight of anhydrous material per
100 parts by weight of total solvent (i.e., water in
many cases).
Solubility Curve
Solubility Curve
 Solubility Table

Table 2-122 page 2-126 to 2-129 8th ed

 QUESTION
What is the solubility of the following compounds at the
given temperature in g/100g water ?
A) Saltpeter at 60°C
B) Potassium thiocyanate at 0°C
C) Soda ash in hot water at 104°C
D) Sal soda in cold water at 0°C
E) Copperas in hot water at 50°C
 Common Names of Compounds

Table 2-1 page 2-7 to 2-27

Perry’s Handbook 8th ed
 QUESTION
What is the solubility of the following compounds at the
given temperature in g/100g water ?
A) Saltpeter at 60°C
KNO3  110 g/ 100 g H2O
B) Potassium thiocyanate at 0°C
KCNS  177 g/ 100 g H2O
C) Soda ash at 0°C
Na2CO3  48.5 g/ 100 g H2O
D) Sal soda in cold water at 0°C
Na2CO3-10H2O  21.5 g/ 100 g H2O
E) Copperas in hot water at 50°C
FeSO4-7H2O  149 g/ 100 g H2O
Old board question
The solubility of soda ash at 30°C in g/100g water is
_______
A. 9.6
B. 21.5
C. 11.1
D. 38.8
Old board question
The solubility of sal ammoniac at 70°C in g/100g
water is______.
A. 116.8
B. 60.2
C. 55.2
D. 126
Seat work
The solubility of epsom salt (magnesium sulfate) in
equilibrium with the saturated solution at 10°C in
g/100g water is _______.
A. 30.90
B. 53.23
C. 59.5
D. 62.9
 A 250 kg saturated solution of NaCl at 30°C is
prepared. Calculate (a) kg of salt (b) kg of water

100 kg of water in a saturated solution of Na2SO4.

at 30°C . Calculate (a) kg of salt (b) kg solution

100 kg of salt in a saturated solution of Na2SO4. at

30°C . Calculate (a) kg of water (b) kg solution
 Learning Objective

19. Calculate the yield of

a particular
crystallization operation
scenario. (CO3, CO4)
 Vapor , V

Crystals , C
Feed, F (anhydrous/hydrated)
(solution) Crystallizer

Mother liquor, L
(saturated solution)
 Material Balance in a Crystallizer

Overall Material Balance: V

C
F=L+C+V F Crystallizer

Where: F – feed
L – mother liquor
C – crystal
L
V – water vapor
Solute Balance:

F (Xf) = L(Xl) + C(Xc)

 MRII reviewer
The solubility of sodium bicarbonate in water is 9.6 g/100
g of water at 20C and 16.4 g/100 g of water at 60C. If a
saturated solution of sodium bicarbonate at 60C is cooled
to 20C, the percentage of dissolved salt that crystallizes
out is
A. 14.5% B. 15.4% C. 41.5% D. 48%
 Seat work
Glaubers salt is made by crystallization by evaporation.
The original solution contains 8.4% sodium sulfate. How
many g of water must be evaporated from 1.00 L solution
with a density of 1.077 g/ml. 80% of original sodium
sulfate will crystallized as decahydrate. The solubility of
sodium sulfate is 19.4 g Na2SO4/ 100 g water.
A. 821 B. 721 C. 850 D. 801
 HW
A saturated solution containing 1500 kg of KCl at 360 K is
cooled in an open tank to 290K. The solubility of KCl per
100kg of water is 53.55 kg at 360K and 34.5 kg at 290K.
Calculate the mass of crystal obtained. Assume no
evaporation.
 HW
1200 lb of barium nitrate is dissolved in sufficient water
to form a saturated solution at 90⁰C. Assuming that 5%
of the original solution evaporates. Calculate the weight
of crystal at 20⁰C. Solubility for barium nitrates is 30.6%
at 90⁰C and 8.6% at 20⁰C.
HW
HW
 HW
How much CaCl2.6H2O (219) must be dissolved in 100 kg
of water at 20°C to form a saturated solution? The
solubility of CaCl2 (111) at 20°C is 6.7 gmol CaCl2 per kg
of water.
A. 500 kg B. 535. kg
C. 550 kg D. 635 kg
 Hydrated Crystals

Example12.11-1. Yield of Crystallization Process.

A salt solution weighing 10,000 kg with 30 wt% Na2CO3 is
cooled to 293 K. The salt crystallizes as the decahydrate.
What will be the yield of Na2CO3. 10H20 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.

Christie J. Geankoplis page 739

 Seatwork

Crystallization of MgSO4-7H2O.
A hot solution containing 1000 kg of MgSO4 and water
having a concentration of 30 wt% MgSO4 is cooled to
288.8K, where crystals of MgSO4-7H2O are precipitated.
The solubility at 288.8 K is 24.5 wt% anhydrous MgSO4 in
the solution. Calculate the yield of crystals obtained if 5% of
the original water in the system evaporates on cooling.

C.J. Geankoplis, End of Chapter Exercise

Hydrated Crystals

Perry’s Handbook
Figure 18-63
(8th Edition)
 HW

Example 27.1. McCabe and Smith

A solution consisting of 30% MgSO4 and 70% H2O is cooled to
60F. During cooling, 5% of the total water in the system
evaporates. How many kilograms of crystals are obtained per
1000 kilogram of original mixture.

Ans: 261. 11 kg
 Hydrated Crystals

A solution of 1000 kg at 200F consisting of 40% MgSO4 is

cooled to 120F. How many kilograms of crystals are obtained?
(a) No evaporation
(b) During cooling, 5% of the total water in the system
evaporates.
 Hydrated Crystals

Sample Problem
A 1000 kg/h solution at 140F consisting of 30% MgSO4 is
cooled to 80F. How many kilograms of crystals are obtained?
(a) No evaporation
(b) During cooling, 3% of the total water in the system
evaporates.
 Coulson 1
Consider the evaporative cooling of a 1000 lb of water in
a solution containing NaCl and KCl. Initially the solution
contains 27.0 g NaCl per 100 g of water and 34.3 g KCl
per 100 g of water at 100°C. Applying vacuum results to
boiling of solution at lower temperature of 40°C. The
solution now has a concentration of 28.4 g NaCl per 100
g of water and 20.4 g KCl per 100 g of water. Calculate
the amount of KCl that precipitates. Assume all NaCl
remains in the solution.

Answer: 149 lb KCl

 MRII reviewer
If an aqueous solution of 25% MgSO4 at 140F is
cooled to 30F the type of crystal formed is
A. MgSO4.12H2O
B. MgSO4.2H2O
C. MgSO4.7H2O
D. MgSO4.10H20
P18.40 8th ed. Perry
 MRII reviewer
The mother liquor concentration will be ____% MgSO4.
A. 10
B. 18
C. 24
D. 4
P18.40 8th ed. Perry
Hand book problem
Example 2: Yield from a Crystallization Process A
10,000-lb batch of a 32.5 percent MgSO4 solution at
120°F is cooled without appreciable evaporation to
70°F. What weight of MgSO4⋅7H2O crystals will be
formed (if it is assumed that the mother liquor leaving
is saturated)?From the solubility diagram in Fig. 18-56
at 70°F the concentration of solids is 26.3 lb MgSO4
per 100-lb solution.
The mole weight of MgSO4 is 120.38.
The mole weight of MgSO4⋅7H2O is 246.49.
 “supersaturation”
The term used to refer to the difference in
concentration between a supersaturated and saturated
solution.
Coulson 3
 nucleation
cluster→embryo→nucleus→crystal
 Kelvin Equation

α is ratio of concentration of supersaturated solution

and saturated solution.
L is the crystal size.
v is number of ions per molecule.
Vm is the molar volume in cc/mol.
R is gas constant used 8.314 X 10 7 ergs/mol.K.
T is temp in K.
σ is interfacial tension in ergs/cm2.
McCabe 27.3
Assuming that the rate of nucleation of potassium
chloride is consistent with interfacial tension of 2.5
ergs/cm2, determine the size of the nucleus at 300 K.
The molar mass of KCl is 74.56 g/mol and its crystal
density is 2.000 g/cm3. The ratio of concentration
of supersaturated solution and saturated
solution is 1.029.
Answer: 2.60 nm
McCabe 27.4
What would be the size of a nucleus in equilibrium with
a fractional supersaturation of 0.029, under the same
condition as example 27.3.

Answer: 2.63 nm