Crystallization

LEARNING OUTCOME

At the end of this unit-module, you should be

able to:
• Apply mass and energy balance calculations
to evaluate the performance of evaporators
and crystallizers.
CRYSTALLIZATION

• a unit operation in which solid particles

are formed from a liquid solution
• involves simultaneous heat and mass
transfer
• is a solid – liquid operation used to
separate solutes from solution in the
form of crystals; wherein mass is
transferred from the liquid phase
(solution) to solid phase (crystal
surface).
CRYSTALLIZATION

• Crystallization in process
industry are usually from
solution (plant extracts to
saleable crystals) or melt
(polymerization crystals)
where almost pure product
from relatively impure
solutions in a single
processing step in the form
of crystals of desired size
range are carried out at low
temperatures. Recrystallization Process
Three main stages of Crystallization process

1. Nucleation
- The initial stage where small
clusters of molecules come together
to form a stable nucleus.
2. Crystal Growth
- The nucleus grows as more
molecules join the structure,
expanding the crystal.
3. Aggregation
- Multiple crystals may come
together, influencing the final shape
and size.
ADVANTAGES OF CRYSTALLIZATION

• High purity product

• Requires relatively low temperature operations
(energy requirement is low)
• High yield can be obtained in single processing step
• Convenience in storage (packing and storing)
• Increased shelf - life
DISADVANTAGES

• Purity of product – may inhibit rate of nucleation

• Shape and size of crystals
• Uniformity or size distribution
• Rate of crystal production
• Caking - caused by a small amount of dissolution
occurring at the surface of crystals and subsequent re-
evaporation of the solvent.
PREVENTION OF CAKING

• Crystals must be more spherical

with least point of contacts
• Crystals must be larger in size
with more void and must be of
narrow size distribution
• Crystals must have the highest
possible critical humidity
• Crystals must be coated with
powdery inert material to
prevent absorption of moisture
EQUILIBRIUM SOLUBILTIY
• In crystallization equilibrium is
attained when the solution or
mother liquor is saturated.
• This is represented by a solubility
curve.
• Solubility is dependent mainly upon
temperature.
• Pressure has a negligible effect on
solubility.
EQUILIBRIUM SOLUBILTIY

• Solubility data are given in

the form of curves where
solubilities in some
convenient units are plotted
versus temperature.
EQUILIBRIUM SOLUBILTIY

• Tables of solubilities are

given in Table 2 – 1, and 2
– 125 to 133 of Perry’s
Chemical Engineers
Handbook.
EQUILIBRIUM SOLUBILTIY

• The solubilities of most salts increase slightly or markedly with

increasing temperature
 EQUILIBRIUM SOLUBILTIY

• Unsaturated solution
• the amount of the solute is less
than the maximum amount of
solute that can be dissolved in a
given solvent or solution at a
specified temperature
• Saturated solution
• the amount of the solute is the
maximum amount of solute
that can be dissolved in a given
solvent or solution at a
specified temperature
EQUILIBRIUM SOLUBILTIY

• Supersaturated solution
• the amount of the solute is
more than the maximum
amount of solute that can be
dissolved in a given solvent
or solution at a specified
temperature
EQUILIBRIUM SOLUBILTIY

• Example: At 300C the maximum amount of solute is 30g of solute per 1000ml
of solvent. Determine the solubility of solute when you have (a) 15g ; (b) 30g
and (c) 45g.
EQUILIBRIUM SOLUBILTIY

Given: 30g of solute per 1000ml of solvent @ 300C

Required: solubility of solute when you have (a) 15g
; (b) 30g and (c) 45g
Solution:
(a) 15g < 30g maximum ➔ Unsaturated solution
(b) 30g = 30g maximum ➔ Saturated solution
(c) 45g > 30g maximum ➔ Supersaturated solution
GENERAL FORMS OF CRYSTALS

Hydrous : salt with water

Example: MgSO4∙7H2O

Anhydrous : salt only

Example: MgSO4
HEAT OF SOLUTION

• The amount of energy that is released or absorbed when a solution

is formed.
• The negative of the heat of solution (Hs) at equilibrium is the heat
of crystallization (λc)
TYPES OF CRYSTALLIZATION PROCESSES

• concentration of solution by evaporation

TYPES OF CRYSTALLIZATION PROCESSES

• crystallization by cooling
TYPES OF CRYSTALLIZATION PROCESSES

• combined cooling and evaporation (adiabatic

evaporation)
TYPES OF CRYSTALLIZATION PROCESSES

• Addition of a third component (seeding)

➢ Employed when solubility is very high.
➢ Characterized by rapid creation of very large supersaturation

➢ Methods of seeding:
a. Salting
• The third component may act physically by forming, with
the original solvent, a mixed solvent in which the solubility
is sharply reduced.
TYPES OF CRYSTALLIZATION PROCESSES

• salting out process

• A solute can be deposited from solution by the addition of another substance (a soluble
solid, liquid or gas) which effectively reduces the original solute solubility.
CLASSIFICATION OF CRYSTALLIZERS: based on
modes of supersaturation
➢ Methods of seeding:
b. Precipitation
• Used when nearly
complete precipitation
is required.
• A new solute maybe
created chemically
when the third
component will react
with the original solute
and form an insoluble
substance
CLASSIFICATION OF CRYSTALLIZERS: based on
modes of supersaturation
COOLING ALONE
Continuous – Swenson-Walker
Batch – agitated tanks crystallizer (SWC)
CLASSIFICATION OF CRYSTALLIZERS: based on
modes of supersaturation
• ADIABATIC EVAPORATION
AND COOLING
• Vacuum crystallizer
• Principle In a vacuum crystallizer,
supersaturation is obtained by adiabatic
evaporative cooling. When the warm
saturated solution is introduced into the
crystallizer, due to high vacuum the
solution undergoes flashing. A part of the
solvent gets evaporated, thereby causing
the cooling of the solution.
CLASSIFICATION OF
CRYSTALLIZERS: based on
modes of supersaturation
• EVAPORATION
• Krystal crystallizer (Oslo)
• Draft-tube crystallizer
Equations used in Crystallization
 Block Diagram for Crystallizer:

Evaporated solvent, V

Feed, F CRYSTALLLIZER Mother liquor, L

Crystals, C
Equations: Supersaturation by Cooling with
Negligible Evaporation
Equations: Supersaturation by Cooling with
Negligible Evaporation
Equations: Supersaturation by Cooling with
Negligible Evaporation
Equations: Supersaturation with Evaporation
Equations: Seeding
 Sample Problems on Determination of
Solubility, Enthalpies, and Heat of Solution
Crystallization
 Sample Problem
Determine the following:
(a) Find the solubility of soda ash at 300C in g/100g of water
Soda Ash Molecular Formula is Na2CO3∙10H2O

The solubility is 38.8g/100g water

 Sample Problem

(b) Solubility of sal ammoniac at 700C in g/100g water

Sal Ammoniac is ammonium chloride (NH4Cl)

The solubility is 60.2g/100g water

 Sample Problem

(c) Solubility of Epsom salt in equilibrium with the saturated

solution at 100C in g/100g water
Epsom Salt is Magnesium Sulfate (MgSO4)

The solubility is 30.9g/100g water

 Supersaturated
solution
Saturated
solution

Solubility of MgSO4
solution at 50˚F

Unsaturated
solution

500F
@ 100C (500F) The solubility is:
30.9g/100g water

30.9
𝑥𝑠 = = 0.2361
30.9 + 100

500F

0.235
0.24

500F
 Sample Problem

(d) The heat of solution of saltpeter in kg-cal/gmol

Saltpeter is potassium nitrate (KNO3)

The heat of solution is -8.633kcal/mol

 Sample Problem

(e) The heat of solution of hydroxybenzene in g-cal/mol

The heat of solution is -2605cal/mol

Determine the
enthalpy of the
MgSO4 solution

-50

0.235
Determine the
solubility of
NaCl at 40˚C

36g/100g H2O
 Unsaturated
solution

Determine the
enthalpy of a
saturated solution
containing 40.5%
CaCl2.
Saturated
solution
-80 Btu/lb
system

Supersaturated
solution

0.405
Sample Problems on Crystallization
 Problem 1

Calculate the yield of MgSO4.7H2O crystals when 1000 kg of

saturated solution at 353 K is cooled to 303K assuming 10% of
the water is lost by evaporation during cooling.
Data: solubility of MgSO4 at 353K = 64.2 kg/100 kg water
solubility of MgSO4 at 303K = 40.8 kg/100 kg water
 Calculate the yield of MgSO4.7H2O crystals when 1000 kg of saturated solution at 353 K is cooled to 303K
assuming 10% of the water is lost by evaporation during cooling.
Data: solubility of MgSO4 at 353K = 64.2 kg/100 kg water
solubility of MgSO4 at 303K = 40.8 kg/100 kg water

Given:
 Calculate the yield of MgSO4.7H2O crystals when 1000 kg of saturated solution at 353 K is cooled to 303K
assuming 10% of the water is lost by evaporation during cooling.
Data: solubility of MgSO4 at 353K = 64.2 kg/100 kg water
solubility of MgSO4 at 303K = 40.8 kg/100 kg water

Req’d: % yield of MgSO4. 7H2O

Solution

𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 𝑓𝑜𝑟𝑚𝑒𝑑

% 𝑦𝑖𝑒𝑙𝑑 𝑜𝑓 𝑀𝑔𝑆𝑂4 . 7𝐻2 𝑂 = 𝑥 100%
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑓𝑒𝑒𝑑

𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓𝑀𝑔𝑆𝑂4 . 7𝐻2 𝑂

% 𝑦𝑖𝑒𝑙𝑑 𝑜𝑓 𝑀𝑔𝑆𝑂4 . 7𝐻2 𝑂 = 𝑥 100%
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑓𝑒𝑒𝑑
 Solution

𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 𝑓𝑜𝑟𝑚𝑒𝑑

% 𝑦𝑖𝑒𝑙𝑑 𝑜𝑓 𝑀𝑔𝑆𝑂4 . 7𝐻2 𝑂 = 𝑥 100%
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑓𝑒𝑒𝑑
TMB:
𝐹 =𝑉+𝐿+𝐶
1000 = 𝑉 + 𝐿 + 𝐶
But V= 10% of original water
100 𝑘𝑔 𝑤𝑎𝑡𝑒𝑟
𝑉 = 0.10 1000𝑘𝑔
100 + 64.2 𝑘𝑔 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑉 = 60.9013 𝑘𝑔
From TMB:
1000 = 60.9013 + 𝐿 + 𝐶 𝑒𝑞𝑛 1
 Solution

Anhydrous salt bal (MgSO4 bal):

𝑥𝐹 𝐹 = 𝑥𝐿 𝐿 + 𝑥𝐶 𝐶

64.2 𝑘𝑔 𝑀𝑔𝑆𝑂4
𝑥𝐹 = = 0.3910
164.2 𝑘𝑔 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
40.8 𝑘𝑔 𝑀𝑔𝑆𝑂4
𝑥𝐿 = = 0.2898
140.8 𝑘𝑔 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑘𝑔𝑀𝑔𝑆𝑂4
𝑀𝑊𝑀𝑔𝑆𝑂4 120.3
𝑘𝑚𝑜𝑙𝑀𝑔𝑆𝑂4
𝑥𝑐 = = = 0.4884
𝑀𝑊𝑀𝑔𝑆𝑂4.7𝐻2𝑂 𝑘𝑔𝑀𝑔𝑆𝑂4.7𝐻2𝑂
246.3
𝑘𝑚𝑜𝑙 𝑀𝑔𝑆𝑂4.7𝐻2𝑂
Solution

0.3910 1000 = 0.2898𝐿 + 0.4884𝐶 𝑒𝑞𝑛 2

𝐿 = 340.6637 𝑘𝑔
𝐶 = 598.4350 𝑘𝑔 𝑀𝑔𝑆𝑂4.7𝐻2𝑂
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 𝑓𝑜𝑟𝑚𝑒𝑑
% 𝑦𝑖𝑒𝑙𝑑 𝑜𝑓 𝑀𝑔𝑆𝑂4 . 7𝐻2 𝑂 = 𝑥 100%
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑓𝑒𝑒𝑑

598.4350
%𝑦𝑖𝑒𝑙𝑑 = 𝑥 100% = 59.8435%
1000
 Problem 2

A hot solution containing 5000 kg of Na2CO3 and water with a

concentration of 25% by weight Na2CO3 is cooled to 293 K and
crystals of Na2CO3.10H2O are precipitated.
At 293 K, the solubility is 21.5 kg anhydrous Na2CO3 per 100 kg
of water. Calculate the yield of Na2CO3 crystals obtained if 5%
of original water in the system evaporates on cooling.
 A hot solution containing 5000 kg of Na2CO3 and water with a concentration of 25% by weight
Na2CO3 is cooled to 293 K and crystals of Na2CO3.10H2O are precipitated. At 293 K, the solubility
is 21.5 kg anhydrous Na2CO3 per 100 kg of water. Calculate the yield of Na2CO3 crystals obtained
if 5% of original water in the system evaporates on cooling.

Given:
 A hot solution containing 5000 kg of Na2CO3 and water with a concentration of 25%
by weight Na2CO3 is cooled to 293 K and crystals of Na2CO3.10H2O are precipitated.
At 293 K, the solubility is 21.5 kg anhydrous Na2CO3 per 100 kg of water. Calculate
the yield of Na2CO3 crystals obtained if 5% of original water in the system
evaporates on cooling.

• Req’d: : yield of Na2CO3 crystals

Solution
𝑎𝑛ℎ𝑦𝑑𝑟𝑜𝑢𝑠 𝑁𝑎2𝐶𝑂3 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠
% 𝑦𝑖𝑒𝑙𝑑 𝑜𝑓 𝑁𝑎2𝐶𝑂3 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 = 𝑥 100%
𝑁𝑎2𝐶𝑂3 𝑓𝑒𝑑
TMB:
𝐹 =𝐿+𝑉+𝐶
5% water lost during evaporation so 𝑉 = 0.05 0.75 5000 = 187.5 𝑘𝑔
5000 = 𝐿 + 𝐶 + 187.5 𝑒𝑞𝑛 1
Anhydrous salt bal (Na2CO3 balance):
𝑥𝐹 𝐹 = 𝑥𝐿 𝐿 + 𝑥𝐶 𝐶
𝑥𝐹 = 0.25
21.5
𝑥𝐿 = = 0.1770
121.5
𝑀𝑊𝑁𝑎2𝐶𝑂3 106
𝑥𝑐 = = = 0.3706
𝑀𝑊𝑁𝑎2𝐶𝑂3.10𝐻2𝑂 286
Solution
0.25 5000 = 0.1770𝐿 + 0.3706𝐶 𝑒𝑞𝑛 2

𝐿 = 2755.7464 𝑘𝑔
𝐶 = 2056.7536 𝑘𝑔
𝑘𝑔
106 𝑁𝑎2𝐶𝑂3
2056.7536 𝑘𝑔 𝑁𝑎2𝐶𝑂3.10𝐻2𝑂 𝑘𝑚𝑜𝑙
𝑘𝑔
286 𝑁𝑎2𝐶𝑂3.10𝐻2𝑂
% 𝑦𝑖𝑒𝑙𝑑 = 𝑘𝑚𝑜𝑙 = 60.9835%
0.25(5000)
 Sample Problem 3

A hot solution containing 2000 kg of MgSO4 and water at 330K

and with a concentration of 30% by weight MgSO4 is cooled to
293 K and MgSO4.7H2O crystals are formed. The solubility at 293
K is 35.5 kg MgSO4/100 kg water. The average heat capacity of
the feed solution is 2.93 kJ/kg.K. The heat of solution at 293 K
is –13.31 x 103 kJ/kmol MgSO4.7H2O. calculate the yield of
crystals and make the heat balance. Assume no water is
vaporized.
 A hot solution containing 2000 kg of MgSO4 and water at 330K and with a concentration of 30% by
weight MgSO4 is cooled to 293 K and MgSO4.7H2O crystals are formed. The solubility at 293 K is
35.5 kg MgSO4/100 kg water. The average heat capacity of the feed solution is 2.93 kJ/kg.K. The
heat of solution at 293 K is – 13.31 x 103 kJ/kmol MgSO4.7H2O. calculate the yield of crystals and
make the heat balance. Assume no water is vaporized.

• Req’d: : Yield of crystals, Qloss

Solution
𝑎𝑚𝑡 𝑜𝑓 𝑀𝑔𝑆𝑂4.7𝐻2𝑂 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 𝑓𝑜𝑟𝑚𝑒𝑑
%𝑌𝑖𝑒𝑙𝑑 = 𝑥100%
𝑎𝑚𝑡 𝑜𝑓 𝑓𝑒𝑒𝑑
TMB:
𝐹 =𝐿+𝐶
2000 = 𝐿 + 𝐶 𝑒𝑞𝑛 1
Anhydrous salt bal (MgSO4 balance):
𝑥𝐹 𝐹 = 𝑥𝐿 𝐿 + 𝑥𝐶 𝐶
𝑥𝐹 = 0.30
𝑀𝑊𝑀𝑔𝑆𝑂4 120.3
𝑥𝑐 = = = 0.4884
𝑀𝑊𝑀𝑔𝑆𝑂4.7𝐻2𝑂 246.3
35.5
𝑥𝐿 = = 0.2620
135.5
 Solution
0.30 2000 = 0.2620𝐿 + 0.4884𝐶 𝑒𝑞𝑛 2
𝐿 = 1664.3110 𝑘𝑔
𝐶 = 335.6890 𝑘𝑔𝑀𝑔𝑆𝑂4.7𝐻2𝑂
335.6890
𝑌𝑖𝑒𝑙𝑑 = 𝑥 100% = 16.7845%
2000
For Heat Loss Computation:
Heat Balance:
𝑄𝑙𝑜𝑠𝑠 = 𝑚𝐹 𝐶𝑝𝐹 𝑇𝐹 − 𝑇𝐿 + 𝐶𝜆𝑐 − 𝑉𝜆𝑣
Since there is no vapour formed, Vλv=0
𝜆𝑐 = −ℎ𝑒𝑎𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
3
𝑘𝐽
𝜆𝑐 = 13.31 𝑥 10
𝑘𝑚𝑜𝑙 𝑀𝑔𝑆𝑂4.7𝐻2𝑂
𝑘𝐽 𝑘𝐽 𝑘𝑚𝑜𝑙 𝑀𝑔𝑆𝑂4 .7𝐻2 𝑂
𝑄𝑙𝑜𝑠𝑠 = 2000 𝑘𝑔 2.93 330 − 293 𝐾 + 335.6890 𝑘𝑔𝑀𝑔𝑆𝑂4 . 7𝐻2 𝑂 13.31 𝑥 103
𝑘𝑔.𝐾 𝑘𝑚𝑜𝑙 𝑀𝑔𝑆𝑂4 .7𝐻2 𝑂 246.3𝑘𝑔𝑀𝑔𝑆𝑂4 .7𝐻2 𝑂
𝑄𝑙𝑜𝑠𝑠 = 234960.5627 𝑘𝐽
Problem 4

A solution containing 500 kg of Na2SO4 and 2500 kg of water is

cooled from 333K to 283 K in an agitated mild steel vessel weighing
750 kg. At 283 K, the solubility of anhydrous salt is 8.9 kg per 100 kg
of water. Na2SO4 crystallizes as Glauber’s salt.
If 2% of the original water is lost by evaporation during cooling,
calculate the heat that must be removed and yield of hydrated
crystals in kg.
heat capacity of solution = 3.6 kJ/kg.K
heat capacity of mild steel = 0.5 kJ/kg.K
heat of solution = - 78.5 MJ/kmol
latent heat of vaporization of water = 2395 kJ/kg
A solution containing 500 kg of Na2SO4 and 2500 kg of water is cooled from 333K to 283 K in an agitated mild steel vessel weighing 750 kg. At 283
K, the solubility of anhydrous salt is 8.9 kg per 100 kg of water. Na2SO4 crystallizes as Glauber’s salt.
If 2% of the original water is lost by evaporation during cooling, calculate the heat that must be removed and yield of hydrated crystals in kg.
heat capacity of solution = 3.6 kJ/kg.K
heat capacity of mild steel = 0.5 kJ/kg.K
heat of solution = - 78.5 MJ/kmol
latent heat of vaporization of water = 2395 kJ/kg

• Req’d: : Qremoved, yield of hydrated crystals in kg

Solution
TMB:
𝐹 =𝐿+𝐶+𝑉
V= 2% of original water= 0.02(2500)=50 kg
(500 + 2500) = 𝐿 + 𝐶 + 0.02 2500 𝑒𝑞𝑛 1
Anhydrous salt bal (Na2SO4 balance):
𝑥𝐹 𝐹 = 𝑥𝐿 𝐿 + 𝑥𝐶 𝐶
8.9
𝑥𝐿 = = 0.0817
108.9
Glauber’s salt is Na2SO4. 10H2O
𝑀𝑊𝑁𝑎2𝑆𝑂4 142
𝑥𝐶 = = = 0.4410
𝑀𝑊𝑁𝑎2𝑆𝑂4.10𝐻2𝑂 322
500 = 0.0817 𝐿 + 0.4410 𝐶 𝑒𝑞𝑛
𝐿 = 2229.1957 𝑘𝑔
𝐶 = 720.8043 𝑘𝑔 𝑁𝑎2 𝑆𝑂4 . 10𝐻2 𝑂
 Solution
Heat Balance:
𝑄𝑙𝑜𝑠𝑠 = 𝐹𝐶𝑝𝐹 𝑇𝐹 − 𝑇𝐿 + 𝐶𝜆𝑐 − 𝑉𝜆𝑣 + 𝑚𝑣𝑒𝑠𝑠𝑒𝑙 𝐶𝑝𝑣𝑒𝑠𝑠𝑒𝑙 (𝑇𝐹 − 𝑇𝐿 )
**Since weight and specific heat of vessel is given, then it is considered in the heat
balance. Also, heat used in heating the vessel is considered Qloss
But,
𝜆𝑐 = −ℎ𝑒𝑎𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝜆𝑐 = 78500𝑘𝐽/𝑘𝑚𝑜𝑙
3.6𝑘𝐽 𝑘𝐽 𝑘𝑚𝑜𝑙 𝑘𝐽 𝑘𝐽
𝑄𝑙𝑜𝑠𝑠 = 3000𝑘𝑔 333 − 283 𝐾 + 720.8043 𝑘𝑔 78500 − 50𝑘𝑔 2395 + 750𝑘𝑔 0.5 333 − 283 𝐾
𝑘𝑔.𝐾 𝑘𝑚𝑜𝑙 322𝑘𝑔 𝑘𝑔 𝑘𝑔.𝐾

𝑄𝑙𝑜𝑠𝑠 = 614724.0297 𝑘𝐽
Problem 5

• An adiabatic vacuum crystallizer is to be used to

produce 10 tons/h of copperas crystals. The feed is a
solution containing 38.9 parts FeSO4 per 100 H2O and
enters at 343K. The crystallizer vacuum is such that
it produces crystallization temperature of 299.7K.
Find the feed rate to the crystallizer. The saturated
solution at 299.7K contains 30.2 FeSO4 per 100 H2O.
The following enthalpy data are available:
• hL = - 5.57 kJ/kg hF = 108.9 kJ/kg
• hC = - 211 kJ/kg hv= 2546 kJ/kg
 An adiabatic vacuum crystallizer is to be used to produce 10 tons/h of copperas crystals. The feed is a solution
containing 38.9 parts FeSO4 per 100 H2O and enters at 343K. The crystallizer vacuum is such that it produces
crystallization temperature of 299.7K. Find the feed rate to the crystallizer. The saturated solution at 299.7K
contains 30.2 FeSO4 per 100 H2O. The following enthalpy data are available:
L = - 5.57 kJ/kg F = 108.9 kJ/kg
C = - 211 kJ/kg V= 2546 kJ/kg

• Req’d: : Feed rate

 Solution
Basis: 1 hr steady state operation Heat balance (enthalpy bal):
TMB: **Enthalpy bal is done since enthalpy data is available
𝐹 =𝐿+𝑉+𝐶 𝐹𝐻𝐹 = 𝐿𝐻𝐿 + 𝑉𝐻𝑉 + 𝐶𝐻𝐶
𝐹 = 𝐿 + 𝑉 + 10 𝑒𝑞𝑛 1 𝐹 108.9 = 𝐿 −5.57 + 𝑉 2546 + 10 −211 𝑒𝑞𝑛 3
Anhydrous salt (FeSO4) solution: Solving simultaneously,
𝑥𝐹 𝐹 = 𝑥𝐿 𝐿 + 𝑥𝐶 𝐶 𝑡𝑜𝑛𝑠
𝐹 = 50.5690
38.9 ℎ𝑟
𝑥𝐹 = 𝑡𝑜𝑛𝑠
138.9 𝐿 = 37.4952
30.2 ℎ𝑟
𝑥𝐿 = Copperas is FeSO4. 7 H2O 𝑡𝑜𝑛𝑠
130.2
𝑉 = 3.0738
𝑀𝑊𝐹𝑒𝑆𝑂4 151.85 ℎ𝑟
𝑥𝐶 = =
𝑀𝑊𝐹𝑒𝑆𝑂4.7𝐻2𝑂 277.85
Substituting,
38.9 30.2 151.85
𝐹= 𝐿+ 10 𝑒𝑞𝑛 2
138.9 130.2 277.85
Problem 6

• A solution containing 23 per cent by mass of sodium

phosphate is cooled from 313 to 298 K in a Swenson-Walker
crystallizer to form crystals of Na3PO4.12H2O. The solubility
of Na3PO4 at 298 K is 15.5 kg/100 kg water, and the
required product rate of crystals is 0.063 kg/s. The mean
heat capacity of the solution is 3.2 kJ/kg K and the heat of
crystallization is 146.5 kJ/kg. If cooling water enters and
leaves at 288 and 293 K, respectively, and the overall
coefficient of heat transfer is 140 W/m2 K, what length of
crystallizer is required?
A solution containing 23 per cent by mass of sodium phosphate is cooled from 313 to 298 K in a Swenson-
Walker crystallizer to form crystals of Na3PO4.12H2O. The solubility of Na3PO4 at 298 K is 15.5 kg/100 kg
water, and the required product rate of crystals is 0.063 kg/s. The mean heat capacity of the solution is
3.2 kJ/kg K and the heat of crystallization is 146.5 kJ/kg. If cooling water enters and leaves at 288 and
293 K, respectively, and the overall coefficient of heat transfer is 140 W/m2 K, what length of crystallizer
is required?
 Solution
Assume: 1 m2 / m length of crystallizer
𝑡𝑜𝑡𝑎𝑙 𝑎𝑟𝑒𝑎
𝑡𝑜𝑡𝑎𝑙 𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟 = 1 𝑚2
𝑚 𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟
Heat bal:
ℎ𝑒𝑎𝑡 𝑟𝑒𝑚𝑜𝑣𝑒𝑑 𝑖𝑛 𝑓𝑒𝑒𝑑 = ℎ𝑒𝑎𝑡 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟𝑒𝑑 𝑖𝑛 𝑡ℎ𝑒 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟 𝑒𝑞𝑢𝑖𝑝𝑚𝑒𝑛𝑡
𝐹𝐶𝑝𝐹 𝑇𝐹 − 𝑇𝐿 + 𝐶𝜆𝑐 = 𝑈𝐴∆𝑇𝐿𝑀
To solve for F,
TMB:
Note: For TMB, no need to include cooling water since its amount does not change
𝐹 =𝐿+𝐶
𝐹 = 𝐿 + 0.063 𝑒𝑞𝑛 1
 Solution
Anhydrous salt (Na3PO4) bal:
𝑥𝐹 𝐹 = 𝑥𝐿 𝐿 + 𝑥𝐶 𝐶
15.5 164
0.23𝐹 = 𝐿+ 0.063 𝑒𝑞𝑛 2
115.5 380
𝑘𝑔
𝐹 = 0.1956
𝑠
𝑘𝑔
𝐿 = 0.1326
𝑠
∆𝑇2 −∆𝑇1
∆𝑇𝐿𝑀 = ∆𝑇2
ln
∆𝑇1

298 − 288 − (313 − 293)

∆𝑇𝐿𝑀 = = 14.4270𝐾
298 − 288
ln
313 − 293
 Solution
Substituting in heat balance,
𝐹𝐶𝑝𝐹 𝑇𝐹 − 𝑇𝐿 + 𝐶𝜆𝑐 = 𝑈𝐴∆𝑇𝐿𝑀
𝑘𝑔 𝑘𝐽 𝑘𝑔 𝑘𝐽 𝑊
0.1956 3.2 313 − 298 𝐾 + 0.063 146.5 = 140 2 𝐴 (14.4270𝐾)
𝑠 𝑘𝑔. 𝐾 𝑠 𝑘𝑔 𝑚 .𝐾
𝐴 = 9.2180 𝑚2
𝑡𝑜𝑡𝑎𝑙 𝑎𝑟𝑒𝑎
𝑡𝑜𝑡𝑎𝑙 𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟 =
1 𝑚2
𝑚 𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟
9.2180 𝑚2
𝑡𝑜𝑡𝑎𝑙 𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟 = = 9.2180 𝑚
1𝑚2
𝑚
Problem 7

• A Swenson-Walker crystallizer has to produce 800 kg/h of

Glauber’s salt. The saturated solution enters the
crystallizer at 49°C and the slurry leaves at 27°C. Cooling
water enters the crystallizer jacket at 15°C and leaves at
21°C. The overall heat transfer coefficient has been
estimated to be 175 kcal/hr·m2·°C. There are 1.3m2 of
cooling surface per meter length of crystallizer. (a)
estimate the cooling water requirement in kg/h and (b)
determine the number of crystallizer sections if each will
be 3m long. The specific heat of the initial solution is 0.5
kcal/kg °C and the heat of crystallization is 18.5 kcal/kg.
A Swenson-Walker crystallizer has to produce 800 kg/h of Glauber’s salt. The saturated solution enters
the crystallizer at 49°C and the slurry leaves at 27°C. Cooling water enters the crystallizer jacket at
15°C and leaves at 21°C. The overall heat transfer coefficient has been estimated to be 175
kcal/hr·m2·°C. There are 1.3m2 of cooling surface per meter length of crystallizer. (a) estimate the
cooling water requirement in kg/h and (b) determine the number of crystallizer sections if each will be
3m long. The specific heat of the initial solution is 0.5 kcal/kg °C and the heat of crystallization is 18.5
kcal/kg.
Solution

From handbook:
Solubility at 490C: Solubility at 270C:
T, 0C solubility T, 0C solubility
40 48.8 20 19.4
50 46.7 30 40.8
49 46.91 27 34.38

46.91 𝑔 𝑁𝑎2 𝑆𝑂4 34.38 𝑔 𝑁𝑎2 𝑆𝑂4

𝑆𝑜𝑙𝑢𝑏𝑖𝑙𝑖𝑡𝑦 @ 49℃ = 𝑆𝑜𝑙𝑢𝑏𝑖𝑙𝑖𝑡𝑦 @ 27℃ =
100 𝑔 𝐻2 𝑂 100 𝑔 𝐻2 𝑂
 Solution
a. Cooling water requirement, 𝑚𝐻2𝑂
ሶ in kg/hr
From heat balance around whole system:
ℎ𝑒𝑎𝑡 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 𝑏𝑦 𝑐𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟 = ℎ𝑒𝑎𝑡 𝑟𝑒𝑚𝑜𝑣𝑒𝑑 𝑖𝑛 𝑡ℎ𝑒 𝑓𝑒𝑒𝑑
𝑚ሶ 𝐻2𝑂 𝐶𝑝𝐻2𝑂 𝑡2 − 𝑡1 = 𝐹𝐶𝑝𝐹 𝑇𝐹 − 𝑇𝐿 + 𝐶𝜆𝑐
Assume CpH2O= 1 kcal /kg.°C
𝑘𝑐𝑎𝑙 𝑘𝑐𝑎𝑙 𝑘𝑔 𝑘𝑐𝑎𝑙
𝑚ሶ 𝐻2𝑂 1 21 − 15 ℃ = 𝐹 0.5 49 − 27 ℃ + 800 18.5 𝑒𝑞𝑛 1
𝑘𝑔.℃ 𝑘𝑔.℃ ℎ𝑟 𝑘𝑔
Note: For TMB, no need to include cooling water since its amount does not change
TMB:
𝐹 =𝐶+𝐿
Glauber’s salt is Na2SO4. 10H2O
𝐹 = 800 + 𝐿 𝑒𝑞𝑛 2
Anhydrous salt ( Na2SO4) bal:
𝑥𝐹 𝐹 = 𝑥𝐿 𝐿 + 𝑥𝐶 𝐶
Solution

From handbook:
Solubility at 490C: Solubility at 270C:
T, 0C solubility T, 0C solubility
40 48.8 20 19.4
50 46.7 30 40.8
49 46.91 27 34.38

46.91 𝑔 𝑁𝑎2 𝑆𝑂4 34.38 𝑔 𝑁𝑎2 𝑆𝑂4

𝑆𝑜𝑙𝑢𝑏𝑖𝑙𝑖𝑡𝑦 @ 49℃ = 𝑆𝑜𝑙𝑢𝑏𝑖𝑙𝑖𝑡𝑦 @ 27℃ =
100 𝑔 𝐻2 𝑂 100 𝑔 𝐻2 𝑂
46.91 34.38 𝑀𝑊𝑁𝑎2𝑆𝑂4 142
𝑥𝐹 = 𝑥𝐿 = 𝑥𝑐 = =
146.91 134.38 𝑀𝑊𝑁𝑎2𝑆𝑂4.10𝐻2𝑂 322
Substituting,
46.91 34.38 142
𝐹= 𝐿+ (800) 𝑒𝑞𝑛 3
146.91 134.38 322
 Solution
Solving eqns 1,2,3 simultaneously,
𝑘𝑔
𝐹 = 2333.7464
ℎ𝑟
𝑘𝑔
𝐿 = 1533.7463
ℎ𝑟
𝑘𝑔
𝑚ሶ 𝐻2𝑂 = 6745.2017
ℎ𝑟
a. Number of crystallizer sections if, L=3m
𝑡𝑜𝑡𝑎𝑙 𝑆𝐴 𝑓𝑜𝑟 ℎ𝑒𝑎𝑡𝑖𝑛𝑔
𝑛𝑜 𝑜𝑓 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟 𝑠𝑒𝑐𝑡𝑖𝑜𝑛𝑠 = 𝑆𝐴 𝑜𝑓 𝑒𝑎𝑐ℎ 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟
𝑚 𝑜𝑓 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟
𝑚 𝑜𝑓 𝑒𝑎𝑐ℎ 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟
 Solution
Solving eqns 1,2,3 simultaneously,
𝑘𝑔
𝐹 = 2333.7464
ℎ𝑟
𝑘𝑔
𝐿 = 1533.7463
ℎ𝑟
𝑘𝑔
𝑚ሶ 𝐻2𝑂 = 6745.2017
ℎ𝑟
a. Number of crystallizer sections if, L=3m
𝑡𝑜𝑡𝑎𝑙 𝑆𝐴 𝑓𝑜𝑟 ℎ𝑒𝑎𝑡𝑖𝑛𝑔
𝑛𝑜 𝑜𝑓 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟 𝑠𝑒𝑐𝑡𝑖𝑜𝑛𝑠 = 𝑆𝐴 𝑜𝑓 𝑒𝑎𝑐ℎ 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟
𝑚 𝑜𝑓 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟
𝑚 𝑜𝑓 𝑒𝑎𝑐ℎ 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟
 Solution
For total surface area
ℎ𝑒𝑎𝑡 𝑟𝑒𝑚𝑜𝑣𝑒𝑑 𝑖𝑛 𝑓𝑒𝑒𝑑 = ℎ𝑒𝑎𝑡 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟𝑒𝑑 𝑖𝑛 𝑡ℎ𝑒 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟 𝑒𝑞𝑢𝑖𝑝𝑚𝑒𝑛𝑡
𝑞 = 𝐹𝐶𝑝𝐹 𝑇𝐹 − 𝑇𝐿 + 𝐶𝜆𝑐 = 𝑈𝐴∆𝑇𝐿𝑀
𝑘𝑔 𝑘𝑐𝑎𝑙 𝑘𝑔 𝑘𝑐𝑎𝑙
𝑞 = 2333.7464 0.5 49 − 27 𝑑𝑒𝑔𝐶 + 800 18.5
ℎ𝑟 𝑘𝑔. 𝑑𝑒𝑔𝐶 ℎ𝑟 𝑘𝑔
𝑘𝑐𝑎𝑙
𝑞 = 40471.2104
ℎ𝑟

∆𝑇2 − ∆𝑇1
∆𝑇𝐿𝑀 =
∆𝑇2
ln
∆𝑇1
27 − 15 − (49 − 21)
∆𝑇𝐿𝑀 = = 18.8836℃
27 − 15
ln
49 − 21
 Solution
Substituting
𝑞 = 𝑈𝐴∆𝑇𝐿𝑀
𝑘𝑐𝑎𝑙 𝑘𝑐𝑎𝑙
40471.2104 = 175 𝐴 18.8836℃
ℎ𝑟 ℎ𝑟. 𝑚2 . ℃
𝐴𝑡𝑜𝑡𝑎𝑙 = 12.24.68 𝑚2

𝑡𝑜𝑡𝑎𝑙 𝑆𝐴 𝑓𝑜𝑟 ℎ𝑒𝑎𝑡𝑖𝑛𝑔

𝑛𝑜 𝑜𝑓 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟 𝑠𝑒𝑐𝑡𝑖𝑜𝑛𝑠 =
𝑆𝐴 𝑜𝑓 𝑒𝑎𝑐ℎ 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟
𝑚 𝑜𝑓 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟
𝑚 𝑜𝑓 𝑒𝑎𝑐ℎ 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟
12.24.68 𝑚2
𝑛𝑜 𝑜𝑓 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟 𝑠𝑒𝑐𝑡𝑖𝑜𝑛𝑠 =
1.3𝑚2
3 𝑚 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟
𝑚 𝑜𝑓 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟
𝑛𝑜 𝑜𝑓 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟 𝑠𝑒𝑐𝑡𝑖𝑜𝑛𝑠 = 3.14 ≈ 4 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟𝑠

Note: Always round up number of crystallizers to ensure that the desired product will be achieved
A crystallizer is charged with 7500 kg of an
aqueous solution at 377K, 29.6% by weight of
which is anhydrous sodium sulfate. The solution
is cooled where 5% of the initial water is lost
by evaporation. Decahydrate crystals were
formed as a result. Calculate the yield of
crystals and the quantity of mother liquor if it
is found to contain 18.3% by weight anhydrous
Na2SO4.
A solution of barium nitrate at 40°C.
Find out the crystal yield of 2000kg of
original solution if it is cooled to 10°C.