CHAPTER ELEVEN

CRYSTALLISATION

In this chapter, our discussion is restricted to crystallisation from solution.

Crystallisation is an operation in which solid particles are formed from a liquid solution.
It is a solid-liquid operation used to separate a solute from its solution in the form of
crystals. In this operation, mass is transferred from the liquid phase (solution) to a pure solid
crystalline phase.
Crystallisation is an important operation in the chemical industry as the number of
salable products have to be in the form of crystals. This operation gives almost pure product
in the form of crystals of a desired size ranging from relatively impure solutions in a single
processing step. From the energy point of view, crystallisation requires much less energy for
separation as compared to other purification methods (e.g., distillation). It may be carried out
at relatively low temperatures and on a scale ranging from a few grams to thousands of tons
per day.
Crystallisation usually involves : (i) concentration of solution (by evaporating a part of
the solvent) and (ii) cooling of solution until the concentration of solute becomes higher than
its solubility at the prevailing temperature. The solute then comes out of the solution
(i.e., precipitates) in the form of pure crystals.
The performance of crystallisation process is evaluated in terms of size, shape, structure,
yield and purity of crystals. So in commercial crystallisation, the size and shape of crystals
are as important as the yield and purity of crystals.
Solubility :
The solubility of a solute in a given solvent is the concentration of the solute in a
saturated solution at a given temperature.
The concentration of a solute in a saturated solution is called the solubility of the solute
in the solvent.
The solubility of a solute in a given solvent depends on the nature of the solute, the
nature of the solvent and the prevailing temperature (solubility mainly depends on
temperature). Solubility data are generally given as parts by weight of anhydrous solute
material per 100 parts by weight of the solvent, e.g., the solubility of MgSO4 in water at
(11.1)
Unit Operations – II 11.2 Crystallisation

293 K (20o C) is 35.5 kg MgSO4 per 100 kg water. Solubility data are plotted as solubility
curves-curves wherein solubilities are plotted against temperature.
The solubility of the solute in a given solvent is different at different temperatures
and it forms the basis of crystallisation by cooling.
Saturation :
Consider a process of dissolving copper sulphate in water (solvent) at a given
temperature. Initially, when some amount of copper sulphate is added, all of it goes in the
solution (i.e., it dissolves in water). Additional amount can be dissolved further till a stage
comes when no more copper sulphate can be dissolved in a given amount (i.e. a fixed
amount) of the solvent. At this stage, the solution is called a saturated solution.
A saturated solution is defined as the one which is in equilibrium with an excess of solid
solute at a given temperature.
If the temperature of the solution is increased, more solute [CuSO4] can be dissolved.
Therefore, a saturated solution will contain different amounts of the solute dissolved in it at
different temperatures. When a saturated solution at a higher temperature (say at T1) is
cooled to a lower temperature say to T2, then theoretically the amount of the solute
corresponding to the difference in solubilities of the solute at these two temperatures will
come out of the solution in the form of crystals.
Solubility Curves :
A graphical relationship between the solubility of a solute and temperature is termed as
the solubility curve.
The concentration necessary for crystal formation and chemical species that separate can
be determined from solubility curves. Such curves are obtained by plotting the solubility of a
solute as a function of temperature (solubilities against temperature). It shows the effect of
temperature on the solubility of the solute. The solubility of solutes in a given solvent may
increase, decrease, or remains more or less constant with temperature. Solubility curves have
no general shape or slope.
O
Parts solute/100 parts water

. H2
SO4
Fe
2O

FeS

Curve 4
4 .7
H

Curve 1 for KCIO3

4
SO
Solubility

Curve 3 Curve 2 for NaCl

Fe

Curve 3 for FeSO4

Curve 4 for MnSO4 . H2O
(All in aqueous solution)
Curve 2
Curve 1
Temperature

Fig. 11.1 : Solubility curves : Solubilities of salts in water

Unit Operations – II 11.3 Crystallisation

Solubility curves of potassium chlorate, sodium chloride are continuous solubility curves
as they show no sharp breaks anywhere. Sometime, the solubility curve exhibit sudden
changes of direction and these curves are therefore referred to as discontinuous solubility
curves, e.g., that of FeSO4, Na2SO4, etc.
For some substances, their solubility decreases with increase in temperature and
in such cases their solubility curves are called as inverted solubility curves (e.g., that of
MnSO4 · H2O in H2O).
Usually, an increase in temperature of the solution increases the solubility of the solute
when no true compounds are formed between the solute and solvent, e.g., KClO3, KNO3 in
H2O. In case of a hydrated salt, the solubility increases with increase in temperature over a
certain temperature range and then decreases. Fig. 11.1 shows solubility curves for a number
of salts in water. In case of potassium chlorate, the solubility increases with temperature so it
can be readily crystallised by cooling its saturated solution. The solubility of NaCl in water is
almost independent of temperature (a slight increase in the solubility results by a large
increase in temperature), so for crystallisation to occur, some of the solvent should be
evaporated.
Supersaturation :
Consider an equilibrium solution (solid solute + liquid solvent). If we disturb this
equilibrium either by cooling the solution or evaporating a portion of the solvent, then the
quantity of solute will exceed the equilibrium concentration and the system will try to attain
a new state of equilibrium by expelling (precipitating) an excess solute present in it in the
form of crystals. This process of forming crystals is called crystallisation from solution and
the concentration difference driving force is called supersaturation.
Supersaturation : It is the quantity of solute present in a solution (in which crystals are
growing) compared with the quantity of solute that is in equilibrium with the solution
(i.e., the equilibrium solubility at the temperature under consideration). The supersaturation
is expressed as a coefficient, given as
(Parts solute / 100 parts solvent) at prevailing condition
s = (Parts solute / 100 parts solvent) at equilibrium ≥ 1.0
Crystallisation cannot take place/occur (i.e., crystals can neither form nor grow) unless a
solution is supersaturated. The amount of crystals formed however depend upon the
difference in saturation concentration since once the crystallisation begins the extra solute
held in the solution due to supersaturation also comes out of the solution in the form of
crystals.
Mechanism of crystallisation / crystal formation :
A knowledge of the mechanism by which crystals form and grow is required in the
design and operation of an equipment used for crystallisation. The formation of a crystal
from a solution is a two-step process.
The first step is called nucleation (the birth of new small particles or nuclei) and the
second one is called crystal growth (growth of crystals to macroscopic size).
Unit Operations – II 11.4 Crystallisation

The generation of a new solid phase (i.e., new small particles) either on an inert material
in the solution or in the solution itself is called nucleation. The increase in size of these
nuclei with a layer-by-layer addition of solute is called crystal growth. Supersaturation is the
common driving force for nucleation and crystal growth. Crystals can neither form nor grow
unless a solution is supersaturated.
The number of nuclei formed and the rate of growth of crystals depend upon the
temperature of operation. The number of nuclei and growth rate of crystals increase with
increase in temperature upto a certain point and then decreases. The temperature
corresponding to a maximum number of nuclei formation is different than the temperature at
which a growth rate is maximum.
If initially a large number of nuclei is formed, then the yield of the process contains many
small or tiny crystals and if a few nuclei are formed initially (at the start), then the yield of
the process contains large size crystals. Slow cooling results in the formation of a less
number of nuclei and hence large size crystals are formed (as the material deposits on a
relatively few nuclei), whereas rapid cooling results in the/leads to the formation of a large
number of nuclei, giving the yield containing a large number of tiny crystals.
Methods of Supersaturation :
Unless a solution is supersaturated, neither nucleation nor crystal growth occurs
(i.e., crystals can neither form nor grow). Thus, for crystallisation to occur, supersaturation
can be generated by any one of the following methods :
(a) By cooling a concentrated, hot solution through indirect heat exchange.
(b) By evaporating a part of the solvent/By evaporating a solution.
(c) By adiabatic evaporation and cooling (i.e., by vacuum cooling) : by flashing of a
feed solution adiabatically to a lower temperature and inducing/causing
crystallisation by simultaneous cooling and evaporation of the solvent.
(d) By adding a new substance (i.e., a third substance) which reduces the solubility of
the original solute, i.e., by salting.
(e) By chemical reaction with a third substance.
When the solubility of the solute increases with increase in temperature, a saturated
solution becomes supersaturated, i.e., supersaturation is generated by cooling and
temperature reduction. This is the case with many inorganic salts and organic substances
(e.g. potassium nitrate, potassium chlorate, oxalic acid, etc.). When the solubility of the
solute is relatively independent of temperature (as is the case with common salt (NaCl) in
H2O), supersaturation is generated by evaporating a part of the solvent. When the solubility
of the solute is very high then neither cooling nor evaporation helps and supersaturation may
be generated by adding a new substance (a third component). The added component may get
mixed physically with the original solvent to form a mixed solvent in which the solubility of
the solute is reduced. This technique is called salting. The third component added may react
with the original solute and form an insoluble substance. This technique is called
precipitation and it is used in wet quantitative analysis. The rapid creation of very large
Unit Operations – II 11.5 Crystallisation

supersaturations is possible by the addition of a third component but it is not common in

industry.
Miers' Supersaturation theory :
According to Miers' theory there is a definite relationship between the concentration and
temperature at which crystals will spontaneously form in a pure solution. This relationship is
represented by the supersolubility curve which is approximately parallel to the solubility
curve. Both the curves are shown in Fig. 11.2. The curve AB is the solubility curve and the
curve PQ is the supersolubility curve. The curve AB represents the maximum concentration
of solutions which can be achieved by bringing solid solute into equilibrium with a liquid
solvent. If a solution having the composition and temperature indicated by point C is cooled
in the direction shown by an arrow, it first crosses the solubility curve AB and we would
expect here crystallisation to start. Actually if we start with initially unseeded solutions,
crystal formation will not begin until the solution is supercooled considerably past the curve
AB. According to the Miers' theory, crystallisation will start in the neighbourhood of point D
and the concentration of the solution then follows roughly along the curve DE. For an
initially unseeded solution, the curve PQ represents the limit at which spontaneous nuclei
formation begin and consequently, crystallisation can start. According to Miers' theory, under
normal conditions, nuclei cannot form and crystallisation cannot then occur in area between
the solubility curve and the supersolubility curve i.e. at any position short of point D along
the line CD.
Miers' theory is useful for discussing the qualitative aspects of nucleation from seeded
and unseeded solutions.
Super
solubility P A
curve Normal
solubility
curve
Concentration

D C

CDE path
Q of solution
on cooling
E
B
Temperature
Fig. 11.2 : The Miers' Supersaturation Theory
Yield of crystallisation process :
Usually, crystallisation processes are carried out slowly and the mother liquor is in
contact with sufficiently large crystals so that at the end of the process, the mother liquor is
saturated at the final temperature. In such cases, the yield of crystallization process is
calculated from the initial solution composition and the solubility of the solute material at the
final temperature. If appreciable evaporation of the solvent occurs during the crystallisation
process, the solvent evaporated must be taken into account in determining the yield.
Whenever crystals are anhydrous, the yield is obtained by taking the difference between the
initial composition of the solution and the solubility of the solute corresponding the final
Unit Operations – II 11.6 Crystallisation

temperature of the process. In cases where material precipitates as a hydrated salt, we have to
take into account the water of crystallisation (in crystals), as this water is not available for
retaining solute in the solution. Under these circumstances, the key to the calculations of
yields is to express all the compositions in terms of hydrated salt and excess water (free
water), as the excess water remains constant during crystallisation operation and the
compositions or amounts thus expressed on the basis of excess water can be deducted in
order to obtain the correct results.
The percentage yield of a crystallisation process is the amount of the solute crystallised/
expressed as a percentage of the amount of the solute present in the feed solution.
Crystal form :
The constituent particles of a crystal are arranged in an orderly and repetitive manner.
The constituent particles may be atoms, molecules or ions. They are arranged in orderly three
dimensional arrays called space lattices. Crystals are classified according to the angle
between the faces and this is the area of the science of crystallography. Different forms of
crystals based upon the angle between faces and lengths of axes are : cubic, tetragonal,
orthorhombic, hexagonal, monoclinic, triclinic and trigonal.
Caking of Crystals :
Caking of crystalline materials is caused by a small amount of dissolution occuring at the
surface of crystals and subsequent re-evaporation of the solvent. Due to caking, the crystals
can get very tightly bonded together.
Since the vapour pressure of a saturated solution of a crystalline solid is less than that of
pure water at a given temperature, condensation can take place on the surface of the crystals
even though the atmospheric relative humidity is less than 100 percent. The solution thus
formed enters into/penetrates into the pack of crystals as a result of capillary action of the
small gaps between the crystals and caking can result due to subsequent evaporation of
moisture when the atmospheric humidity falls. Crystalline materials can also cake at a
constant relative humidity, as the vapour pressure of a solution is less in a small capillary as
compared to it in a large capillary as a result of temperature effect. As condensation occurs,
the small particles get first dissolved and therefore average size of capillaries increases and
the vapour pressure of the solution may increase sufficiently for evaporation to take place.
When the particle size is non-uniform, a crystalline material will cake more rapidly as the
porosity of a bed of particles of mixed sizes is less and fine particles are more readily
soluble. Thus, the tendency of crystalline materials to cake can be reduced by forming
crystals of relatively large and uniform sizes or by adding a water repellent agent, such as
stearic acid.
Magma : It is a two-phase mixture of mother liquor and crystals that occupies the
crystalliser and withdrawn as a product.
In order to reduce the load on a crystalliser, evaporation may be carried out to remove the
excess solvent from a solution. Crystallisation is generally followed by filtration for the
separation of crystals from the mother liquor.
Unit Operations – II 11.7 Crystallisation

Effect of impurities on crystal formation :

(i) Soluble impurities may get adsorbed on the surface of the nuclei or crystals
nucleation sites and hinder the rate of nucleation and crystal growth.
(ii) The shape of crystal may get modified as the adsorption of impurities may occur
preferentially on a particular face.
The impurities may decrease the rate of crystal growth. In some cases it is desirable, e.g.,
addition of a small quantity of glue or tannin to boiler feed water prevents nucleation and
growth of calcium carbonate crystals and thus reduces scaling.
Classification of Crystallisers :
Crystallisers may be classified on the basis of mode of operation. These may be operated
batch wise or continuously.
1. Batch crystalliser : stir-tank crystalliser
2. Continuous crystalliser : Swenson-Walker crystalliser.
Crystallisers may also be classified according to the method by which supersaturation is
achieved. Thus, agitated tank crystalliser, Swenson Walker crystalliser are examples of
crystallisers wherein supersaturation is achieved by cooling (or temperature distribution)
which is a usual practice for materials of which the solubility decreases with decrease in
temperature. Krystal crystalliser is an example of evaporative crystalliser wherein
supersaturation is achieved by evaporating a part of the solvent and is a usual practice for
materials whose solubility remains almost constant with variation in temperature. Vacuum
crystalliser is an example of crystalliser wherein supersaturation is achieved by adiabatic
evaporation and cooling which is most suitable for heat sensitive materials. This is used for
large scale production in which supersaturation is achieved by introducing the hot solution
into a vacuum in which pressure is less than the vapour pressure of the solvent at the
temperature at which it is fed, the solvent thus flashes or evaporates and the solution is
cooled adiabatically. Salting out with the help of a third substance is not in use and at
present, deliberate introduction of a foreign substance to decrease the solubility is rarely
found.
Classification based on the method of achieving supersaturation :
1. Supersaturation by cooling alone :
(a) Batch – Agitated tank crystallisers
(b) Continuous – Swenson-Walker crystalliser
2. Supersaturation by adiabatic evaporation and cooling :
(a) Vacuum crystallisers with and without external classifying seed bed
3. Supersaturation by evaporation :
(1) Krystal crystallisers
(2) Draft-tube crystallisers.
Crystallisers are also classified according to the method of suspending the growing
crystals : (a) where the suspension is agitated in a tank, (b) where the suspension is circulated
through a heat exchanger, e.g., vacuum crystalliser and Oslo crystalliser, (c) where the
suspension is circulated through a scraped surface exchanger.
Unit Operations – II 11.8 Crystallisation

Agitated Tank Crystalliser :

It is also known as a stir-tank crystalliser or agitated batch crystalliser. This is the
simplest and perhaps the most economical unit. In this crystalliser, supersaturation is
generated by cooling so it is a cooling crystalliser.
This type of crystalliser is commonly used in small scale production or batch processing
due to several advantages, such as low initial cost, simple in construction and flexibility.
These are having capacities more than tank crystallisers.
Construction : Agitated tank crystalliser consists of a cylindrical tank provided with a
low speed agitator and a cooling coil. The tank is having a conical bottom through which the
product is withdrawn. The agitator improves the heat transfer rate, keeps the temperature of
the solution uniform and keeps the fine crystals in suspension which is essential for uniform
growth of the crystals.
Feed
Coolant out
Coolant in

Cooling coil

Vessel

Paddle

Crystal + Mother liquor

Fig. 11.3 : Agitated tank crystalliser

Working : A known quantity of hot solution is charged to the crystalliser, cooling is
applied by circulating a coolant through the coil and agitator is started. The mass in the
crystalliser cools due to heat transfer to the circulated coolant and as the temperature
decreases, crystals are formed due to decrease in the solubility of the solute. The mass is
cooled to a predecided temperature and finally a product stream containing crystals plus
mother liquor is withdrawn from the bottom of the crystalliser.
The disadvantages of this crystalliser include : the solids deposited on the surface of the
coil add resistance to heat transfer so that it ceases to function efficiently, difficulty in
controlling nucleation and size of crystals, frequent washing and scrapping of the cooling
surface and high labour costs.
Unit Operations – II 11.9 Crystallisation

This type of crystalliser is used to produce fine chemicals, pharmaceutical products and
dye intermediates.
Scrapped surface crystalliser :
(i) Swenson-Walker crystalliser and (ii) Double pipe crystalliser.
Swenson-Walker Crystalliser :
The Swenson-Walker crystalliser is a cooling type, continuous, jacketed trough
crystalliser. It is an example of the scrapped surface crystalliser and is probably the most
widely used crystalliser.
Construction :
It consists of a long open rectangular trough with a semi-cylindrical bottom,
i.e., U-shaped trough, of width 0.6 m and length 3 to 6 m. The trough is jacketed externally
for circulating the coolant during operation. A spiral agitator rotating at about 7 rpm is
incorporated in the trough in such a way that it is as close to the bottom of the trough as
possible. The capacity of this crystalliser can be increased by arranging a number of units in
series (four troughs of 3 metre length each may be arranged). At one end of the crystalliser,
an inlet for the hot solution is provided and at the other end of the crystalliser, an overflow
gate for the crystals and mother liquor discharge is provided. The functions of the spiral
agitator are : (i) to scrap the crystals from the cooling surface (i.e., to prevent accumulation
of the crystals on the heat transfer surface), (ii) to lift and shower the crystals through the
solution so that the crystals will be held in suspension and thereby the crystals of uniform
size can be obtained (as deposition occurs mainly by build up on previously formed crystals)
and (iii) to convey the crystals from one end of equipment to the other end.
The trough is formed out of metal sheets welded to an angle-iron frame at the top.
A jacket is usually made of mild steel. The spiral agitator is supported at either ends outside
the trough. A stuffing box assembly is attached to the cover on either ends that prevents
leakage of the liquor from the opening provided for a shaft. The shaft is driven by belt, etc.
Jacket Spiral agitator Feed

Trough
Crystal
+ Mother liquor

Shaft Trough Jacket

Fig. 11.4 : Swenson - Walker Crystalliser

Unit Operations – II 11.10 Crystallisation

Working :
A hot concentrated solution is fed at one end of the open trough and flows slowly
towards the other end of the trough. Water is fed to the jacket in such a way that it flows in a
counter current fashion with respect to the solution. The solution while flowing through the
trough cools by heat transfer to water. Once the solution becomes supersaturated, crystals
start forming and building. A spiral agitator keeps the crystals in suspension so that
previously formed crystals grow instead of formation of new crystals and ultimately the two
phase mixture of crystals and liquor leaves the crystalliser through an overflow gate.
Advantages of this crystalliser include : saving in floor space, in material in process and
saving in labour.
This crystalliser is suitable only when supersaturation can be achieved by cooling alone.
Double pipe scrapped surface crystalliser :
Less common type of continuous scrapped surface crystalliser that is somewhat similar to
the jacketed trough crystalliser, i.e., Swenson-Walker crystalliser is a double pipe
crystalliser. It consists of a concentric double pipe, the outer pipe acting as a jacket. Cooling
water flows through the annular space between the two pipes and a long pitch spiral agitator
rotates in the inner pipe at 5 to 30 rpm. These are also arranged in series (3 pipes each of 3 m
long). The other constructional features and the method of operation is the same as of the
Swenson-Walker crystalliser.
It is used in crystallising ice cream and plasticizing margarine.
Vacuum Crystalliser :
In this crystallizer, supersaturation is achieved by adiabatic evaporative cooling. A hot
solution (feed) is introduced into a vessel wherein a vacuum is maintained that corresponds
to the boiling point of the solution lower than the temperature of the feed solution.
Evaporation will result due to flashing. The energy needed for vaporisation is taken from the
feed (sensible heat), so that the temperature of a liquor-vapour mixture after flashing
becomes much lower than the temperature of the liquor before flashing.
Vacuum crystallisers often operated continuously but they can also be operated batch-
wise. These crystallisers are very simple and contain no moving parts and therefore, they can
be constructed out of corrosion resistant materials or lead or rubber lined mild steel.
Construction :
A continuous vacuum crystalliser consists of a tall vertical cylindrical vessel with a
conical bottom, a circulating pump (screw pump) of low head and a vertical tubular heater on
the shell side of which, steam is condensing. A low pressure (i.e., vacuum) in the vertical
cylindrical vessel (crystallising body) is maintained by a condenser, usually with the help of a
steam jet ejector. A tangential inlet is provided on the cylindrical vessel for introducing a hot
solution into it and a vapour outlet is provided on the top. A discharge connection for mother
liquor and crystal is provided on a down-pipe just above the feed connection.
Unit Operations – II 11.11 Crystallisation

Barometric condenser

Crystalliser body

Steam
Magma

Heater

Motherliquor
Product Drips
Bleed
Centrifuge

Pump
Feed
Fig. 11.5 : Continuous Vacuum Crystalliser / Circulating magma vacuum crystalliser
Working :
The magma from the bottom of a cylindrical vessel goes to a pump via a down-pipe and
is pumped through a vertical tubular heater where it is heated by means of condensing steam
and finally a hot stream enters the cylindrical vessel tangentially just below the level of the
magma surface. Flash evaporation of the solution takes place and produces rapid cooling,
resulting into supersaturation, which is the driving force for nucleation and growth. Fresh
solution enters the down pipe just before the suction of the circulating pump and a
suspension of crystals is continuously taken out from a discharge pipe located above the feed
inlet in the down pipe. The suspension of crystals is fed to a centrifuge machine, the crystals
are taken out as a product, and the mother liquor is recycled to the down-pipe with a small
part of it continuously bled.
It is used for the production of large crystals.
Krystal or Oslo Crystalliser :
It is used whenever large quantities of crystals of controlled size are to be produced.
In this crystalliser, a supersaturated solution is passed upward through a bed of crystals
which are maintained in a fluidised state whereby uniform temperature is maintained and the
crystals segregate in the bed with large ones at the bottom and small ones at the top.
Unit Operations – II 11.12 Crystallisation

Oslo Cooler Crystalliser :

In this crystalliser, supersaturation is generated by indirect cooling. It consists of a
crystallising chamber, a circulating pump, and a external cooler for cooling the solution. It is
a circulating liquid cooling crystalliser.
The solution to be crystallised is fed from the top. Mother liquor from a crystallising
chamber is withdrawn near a feed point 'A' with the help of a circulating pump and it is then
admitted to a cooler (E) wherein supersaturation is achieved by cooling. The supersaturated
solution from the cooler is finally fed back to the bottom of the crystallising chamber through
a central pipe (P). Usually, nucleation takes place in the bed of crystals in the crystallising
chamber. The nuclei formed circulate with mother liquor and once they grow sufficiently
large, they will be retained in the fluidised bed. Once the crystals grow to a required size,
they are removed as product from the bottom of the crystallising chamber through a valve 'V'
as these cannot be retained in the fluidised bed by the circulation velocity.
Crystallising chamber

Feed

Coolant out A

P
Cooler
E

Coolant in

V
Pump

Fig. 11.6 : Oslo / Krystal Cooling Crystalliser

Oslo Evaporative Crystalliser :
In this crystalliser, supersaturation is generated/achieved by evaporation. It is a
circulating liquid evaporative crystalliser.
It consists of a crystallising chamber containing a bed of forming and growing crystals, a
circulating pump, an external heater for heating the solution with the help of condensing
steam and a vapour - head wherein reduced pressure is maintained by a vacuum generating
equipment. The heater is maintained under sufficient hydrostatic head to avoid the boiling on
the heating surface.
It is used for the production of small and uniform crystals.
Unit Operations – II 11.13 Crystallisation
Vapours to vacuum
generating unit

Vapour head

Steam
Heater

Feed
Drips

Pump
Central duct

Crystallising
chamber

Product

Fig. 11.7 : Oslo/Krystal Evaporative Crystalliser

The solution from the crystallising chamber is pumped by a circulating pump on the
suction side of which the feed solution forming a small part of the total circulating liquid is
introduced into a heater, where it is heated by means of condensing steam (on the shell side
of the heater) and then fed to a vapour head wherein some of the solution flashes into vapour
resulting into some degree of supersaturation. The supersaturated solution is then returned to
the bottom of the crystallising chamber through a central duct prolonged from the vapour
head into the crystallising chamber. Nucleation takes place in the crystal bed which is
maintained in a fluidised state by means of a upward flowing stream of liquid through the
duct. The nuclei formed circulate with the mother liquor and once they grow sufficiently
large they will be retained in the fluidised bed. When the crystals grow to a required size,
they will be withdrawn as a product from the bottom of the crystallising chamber as they
will not be maintained in the fluidised bed by the circulation velocity.
Material balances of crystalliser
Material balances are used to calculate the yield of crystallisation operation which is the
mass of crystals obtained from a given mass of solution.
Unit Operations – II 11.14 Crystallisation
Evaporated solvent (V)

Feed
Crystalliser Mother liquor (L)
solution
(F, X'F)
Crystals (C)
Fig. 11.8
Consider the crystallisation process carried out under steady state conditions and shown
in Fig. 11.8.
Let
F be the mass flow rate of feed solution in kg/h
X' be the weight fraction of anhydrous solute in the feed solution
F

C be the kg/h of crystals obtained

V be the mass flow rate of evaporated solvent in kg/h
X' be the solubility of the solute at the final temperature of operation
expressed as a weight ratio of anhydrous salt to solvent
M1 be the molecular weight of anhydrous solute salt
M2 be the molecular weight of hydrated salt
L' be the kg/h of solvent in the mother liquor
L be the kg/h of mother liquor leaving the crystalliser
Overall material balance :
F = C+L+V … (11.1)
Material balance of solvent :
Solvent in feed = Solvent evaporated + Solvent in mother liquor
+ Solvent in hydrated crystals
M2 – M1
∴ F (1 – X'F) = V + L' +  M  C … (11.2)
 2 
Rearranging the above equation, we get
M2 – M1
L' = F (1 – X'F ) – V –  M  C … (11.3)
 2 
Material balance of solute :
Solute in feed = Solute as product crystals + Solute in mother liquor
M1  M2 – M1 
F · X'F = C · M + F (1 – X'F) – V –  M  C X' … (11.4)
2   2  
If the crystals obtained are anhydrous then above equation takes the following form :
F X' = C + [F (1 – X' ) – V] X'
F F
… (11.5)
Unit Operations – II 11.15 Crystallisation

If no evaporation takes place and anhydrous salts are crystallised, then

V = 0 and Equation (10.5) becomes
F · X' = C + [F (1 – X' )] X'
F F
… (11.6)
C – kg/h of crystal obtained (anhydrous/hydrated) and is the yield of the process.
Amount of solute crystallised
% yield crystals = Amount of solute in feed solution × 100
Energy balances :
Energy balance calculations in a crystallisation process are essential to determine the
cooling requirements or to determine the final conditions. In these calculations, heat of
crystallisation is important and it is the latent heat evolved when crystals are formed from a
solution. Generally, the crystallisation process is exothermic and heat of crystallisation varies
with temperature and concentration. Heats of crystallisation are not available, but heat of
solution data are available. The process of crystallisation is the reverse of dissolution.
Therefore, the heat of solution (i.e., the heat of dissolution) with a reverse sign is taken as
heat of crystallisation (heat of crystallisation = – heat of solution). In case of a cooling
crystalliser with no evaporation, the heat balance is
Heat to be removed = Q = F CpF ∆T + C λc
When specific heat data are available for the initial feed solution over a range of
temperature, then the heat to be removed is equal to the heat to be removed to cool the feed
from the initial temperature (T1) to the final temperature (T2, such that T1 > T2) without any
crystal precipitating plus the heat liberated/evolved due to formation of crystals from the
supersaturated solution at the final temperature.
Heat with solution at T1 + Heat liberated due to crystallisation =
= Heat with solution at T2 + Heat to be removed
F Cp T1 + Cλc = F Cp T2 + Q
∴ Q = FCpT1 – FCpT2 + CλC = FCp∆T + CλC
(valid for crystallisation by cooling and with no evaporation)
where ∆T = cooling range (T1 – T2), where T1 > T2
Cp = specified heat of feed solution, kJ/(kg·K)
F
F = feed or feed rate, kg or kg/h
C = crystal formed, kg or kg/h
λC = heat of crystallisation, kJ/kg
.
Q = U A ∆Tlm = m c · Cp (t2 – t1)
c
.
where m c is the mass flow rate of the coolant and Cp is the specific heat of the coolant,
c
t1 and t2 are the inlet and outlet temperatures of the coolant.
(T1 – t2) – (T2 – t1)
∆Tlm = ln [(T – t ) / (T – t )]
1 2 2 1
Unit Operations – II 11.16 Crystallisation

SOLVED EXAMPLES
Example 11.1 : A solution of sodium nitrate in water contains 48 % NaNO3 by weight at
313 K (40o C) temperature. Calculate the percentage yield of NaNO3 crystals that may be
obtained when the temperature is reduced to 283 K (10o C). Also, calculate the quantity of
NaNO3 crystals obtained from 100 kg of the solution.
Data : Solubility of NaNO3 in water at 283 K (10o C) is 80.18 kg NaNO3 per 100 kg
water.
Solution : Basis : 100 kg feed solution.
F = 100 kg
48
X'F = 100 = 0.48 weight fraction of NaNO3 in the feed
C = yield of crystals (kg of NaNO3 crystals obtained)
X' = solubility of NaNO3 at 283 K
= 80.18 kg/100 kg water
L' = kg of solvent in mother liquor
Water (solvent) balance :
Solvent in feed = Solvent in mother liquor
F (1 – X'F) = L'
100 (1 – 0.48) = L'
∴ L' = 52 kg
NaNO3 balance – (Anhydrous salt as crystal) :
NaNO3 in feed = NaNO3 obtained as crystals + NaNO3 in mother liquor

X'F · F = C + L' · X'

X'F F = C + [F (1 – X'F)] X'

0.48 × 100 = C + [100 (1 – 0.48)]  100 

80.18
 
C = yield of crystals
= 6.3 kg … Ans.
kg of NaNO3 crystallised
% yield of crystals = kg of NaNO in feed solution × 100
3

6.3
= 48 × 100
= 13.12 % … Ans.
Unit Operations – II 11.17 Crystallisation

Example 11.2 : Find the yield of Na2S2O3. 5H2O crystals when 100 kg of 48% Na2S2O3
solution is cooled to 293 K (20o C). Also calculate the percentage yield of the hydrated
crystals. (At. Wt. : Na = 23, S = 32, O = 16, H = 1)
Data : Solubility of Na2S2O3 is 70 parts per 100 parts water at 293 K (20o C).
Solution : Basis : 100 kg of feed solution.
It contains 48 kg of Na2S2O3 and 52 kg of water. Let 'C' be the yield of crystals.
M1 = Molecular weight of Na2S2O3 = 158
M2 = Molecular weight of Na2S2O3 · 5 H2O = 248

X'F = weight fraction of solute in the feed solution

weight % 48
= 100 = 100 = 0.48
Material balance of water :
Water in feed = Water of crystallisation in crystals + Water in mother liquor
M2 – M1
52 = C · M2 + L'

C [248 – 158]
L' = 52 – 248
Material balance of solute :
Solute in feed = Solute in crystals produced + Solute in mother liquor

0.48 × 100 = C 248 + 52 –  248  C X'

158 248 – 158
     
X' –Solubility expressed as weight ratio of solute to solvent at 293 K.

48 = 0.637 C + [52 – 0.363 C] × 100

70
 
= 0.637 C + 36.4 – 0.254 C
∴ C = 30.3 kg
Yield of Na2S2O3 · 5 H2O crystal = 30.3 kg … Ans.
248
Na2S2O3 · 5 H2O in the feed solution = 48 × 158 = 73.34 kg

hydrated crystals obtained

% yield of hydrated crystals = hydrated crystals in feed solution × 100

30.3
= 73.34 × 100 = 41.31 … Ans.
Unit Operations – II 11.18 Crystallisation

Example 11.3 : Calculate the yield of MgSO4 · 7 H2O crystals when 1000 kg saturated
solution of MgSO4 at 353 K (80o C) is cooled to 303 K (30o C) assuming 10 % of the water is
lost by evaporation during cooling.
Data : Solubility of MgSO4 at 353 K (80o C) = 64.2 kg/100 kg water
Solubility of MgSO4 at 303 K (30o C) = 40.8 kg/100 kg water
At. Wt. : Mg = 24, S = 32, H = 1 and O = 16
Solution : Basis : 1000 kg of solution at 353 K (80o C)
∴ F = 1000 kg

XF' = weight fraction of MgSO4 in the feed

64.2
= 164.2 = 0.391

Water in the feed solution = F (1 – X'F )

= 1000 (1 – 0.391) = 609 kg
V = kg of water evaporated during cooling
= 609 × 0.1 = 60.9 kg
X' = solubility of MgSO4 at 303 K = 40.8 kg/100 kg water
M1 = Molecular weight of MgSO4 = 120
M2 = Molecular weight of MgSO4, 7 H2O = 246
C = Yield of MgSO4 · 7 H2O crystals from feed solution
M2 – M1 = water of crystallisation
= 246 – 120 = 126 kg
Material balance of MgSO4 :
M1  M2 – M1
X'F F = C · M + F (1 – X'F) – V – C  M  X'
2   2 
MgSO4 in feed = MgSO4 in hydrated crystal
+ MgSO4 in mother liquor at 303 K

0.391 (1000) = C 246 + 1000 (1 – 0.391) – 60.9 – 246  100

120 C (126) 40.8
∴
   
391 = 0.488 C + [609 – 60.9 – 0.512 C] (0.408)
MgSO4 · 7 H2O yield = C = 599.7 kg … Ans.
Unit Operations – II 11.19 Crystallisation

Example 11.4 : A hot solution containing 25 % by weight Na2CO3 is cooled to

293 K (20 oC) and crystals of Na2CO3 · 10 H2O are precipitated. At 293 K (20 oC), the
solubility is 21.5 kg anhydrous Na2CO3 per 100 kg of total water. Calculate the yield of
hydrated Na2CO3 crystals obtained if 5 % of the original water in the system evaporates on
cooling and the quantity of mother liquor based on 5000 kg of the hot solution.
At. Wt. : Na = 23, C = 12, O = 16, H = 1.
Solution : Basis : 5000 kg of hot solution of Na2CO3.
It contains :
Na2CO3 = 0.25 × 5000 = 1250 kg
Water = 0.75 × 5000 = 3750 kg
M1 = Mol. Wt. of Na2CO3 = 106
M2 = Mol. Wt. of Na2CO3 · 10 H2O = 286
M2 – M1 = water of crystallisation = 10 H2O = 180
∴ F = 5000 kg
X'F = weight fraction of Na2CO3 in the feed solution
25
= 100 = 0.25

Given : 5% of water is evaporated. Therefore,

V = kg of water evaporated during cooling
= 0.05 × 3750 = 187.5 kg
Material balance of water :
Water in feed = Water of crystallisation
+ Water in mother liquor + Water evaporated
M2 – M1
0.75 (5000) = C  M  + L' + 187.5
 2 

3750 = C  286  + L' + 187.5

286 – 106
 

3562.5 = C 286 + L'

180
 

L' = 3562.5 – C 286

180
 
Material balance of solute :
Solute in feed = Solute in crystals produced + Solute in mother liquor
M1
X'F F = C M + L' X'
2
Unit Operations – II 11.20 Crystallisation

where, C = yield of hydrated crystals

L' = kg of solvent water in mother liquor
X' = solubility of anhydrous solute as kg solute/kg solvent.
M1
X'F F = C M + 3562.5 – C 286 × X'
180
2   

0.25 × 5000 = C 286 + 3562.5 – C 286 100

106 180 21.5
  
1250 = 0.37 C + [3562.5 – 0.629 C] 0.215
1250 = 0.37 C + 765.94 – 0.135 C
0.235 C = 484.06
C = 2059.83 kg
∴ yield of Na2CO3 · 10 H2O crystals = 2059.83 kg … Ans.
Quantity of mother liquor obtained = kg of feed – kg of crystals – kg water evaporated
= 5000 – [2059.83 + 187.5]
= 2752.67 kg … Ans.
Example 11.5 : 2000 kg of a hot solution at 330 K (57 oC) containing 30 wt. % MgSO4 is
cooled to 293 K (30 oC) and MgSO4 · 7H2O crystals are removed from it. The solubility at
293 K (30 oC) is 35.5 kg MgSO4 per 100 kg water. Calculate the yield of crystals. Assume
that no water is evaporated.
At. Wt. : Mg = 24, S = 32, O = 16, H = 1.
Solution : Basis : 2000 kg hot solution
∴ F = 2000 kg
The solution contains 30% MgSO4. Therefore,
30
X'F = 100 = 0.30 … weight fraction of MgSO4 in the solution
M1 = Mol. Wt. of MgSO4 = 120
M2 = Mol. Wt. of MgSO4 · 7 H2O = 246
Material balance of water :
Water in feed = Water of crystallisation + Water in mother liquor
M2 – M1
(1 – X'F) F = C  M  + L'
 2 
(1 – 0.30) 2000 = C  246  + L'
246 – 120
 
126
L' = 1400 – 246 C = 1400 – 0.5122 C
where C is the yield of hydrated crystals.
Unit Operations – II 11.21 Crystallisation

Material balance of solute :

MgSO4 in feed = MgSO4 in crystals produced + MgSO4 in mother liquor
M1
X'F F = C M + L' X' … (1)
2

where X' = solubility of MgSO4 as kg MgSO4/kg solvent

35.5
= 100 = 0.355

M1 = 120
M2 = 246

X'F = 0.3 F = 2000 kg

Substituting the values of various terms, Equation (1) becomes

0.3 (2000) = C 246 + [1400 – 0.5122 C] 0.355

120
 
600 = 0.488 C + 497 – 0.182 C
C = 336.6 kg
Yield of MgSO4 · 7 H2O crystal = 336.6 kg … Ans.
Example 11.6 : Find the per cent yield of Glauber salt (Na2SO4 · 10 H2O) if a pure 32 %
solution is cooled to 293 K (20o C) without any loss due to evaporation ?
Data : Solubility of Na2SO4 in water at 293 K (20o C) is 19.4 g per 100 g water.
At. Wt. : Na = 23, S = 32, O = 16, H = 1.
Solution : Basis : 100 kg of original solution
It contains 32 kg of Na2SO4 and 68 kg of water
F = 100 kg
X' = weight fraction of Na SO in the feed
F 2 4

= 32/100 = 0.32
M1 = Mol. Wt. of Na2SO4 = 142
M2 = Mol. Wt. of Na2SO4 · 10 H2O = 322
Material balance of water :
Water in feed = Water of crystallisation + Water in mother liquor
(M2 – M1)
0.68 × 100 = C M2 + L'

68 = C  322  + L'
322 – 142
 
68 = 0.559 C + L'
L' = 68 – 0.559
Unit Operations – II 11.22 Crystallisation

Material balance of solute :

Solute in feed = Solute in crystals produced + Solute in mother liquor
M1
X'F F = C M + L' X' … (1)
2

C = yield of hydrated solute

L' = kg of solvent in mother liquor
X' = solubility of anhydrous solute as kg solute/kg solvent
19.4
= 100 = 0.194

Substituting the values, Equation (1) becomes

0.32 × 100 = C 322 + L' × 0.194

142
 
32 = 0.441 C + 0.194 L'
We have, L' =
68 – 0.559 C
32 =
0.441 C + 0.194 (68 – 0.559 C)
32 =
0.441 C + 13.192 – 0.1084 C
0.3326 C =
18.808
C =
56.55
322
Na2SO4 · 10 H2O in the feed solution = 32 × 142 = 72.56

56.55
% yield of Glauber salt = 72.56 × 100 = 77.93 … Ans.

Alternate method :
Basis : 100 kg free water
100 kg of the original solution contain 32 kg Na2SO4 and 68 kg water.
Water associated with Mol. Wt. of 10 H2O
32 kg Na2SO4 in 100 kg solution = Mol. Wt. of Na SO × 32
2 4

(10 × 18)
= 142 × 32 = 40.56 kg

Free water in 100 kg original solution = 68 – 40.56 = 27.44 kg

Glauber salt (Na2SO4 · 10 H2O) 100
present in 100 kg of free water = (32 + 40.56) × 27.44
At 293 K, the final liquor contains 19.4 kg Na2SO4 in 100 kg water.
Water associated with Na2SO4 180
in the final solution = 142 × 19.4 = 24.6 kg
Unit Operations – II 11.23 Crystallisation

Free water in the final solution = 100 – 24.6 = 75.4 kg

(19.4 + 24.6)
Glauber salt present in 100 kg water = 75.4 × 100

Yield of Glauber salt per 100 kg

free water = 264.43 – 58.35
= 206.08 kg Na2SO4 · 10 H2O
206.08
% yield of Glauber salt = 264.43 × 100 = 77.93 … Ans.

Example 11.7 : A crystalliser is charged with 7500 kg of an aqueous solution at 377 K

(104o C), 29.6 % by weight anhydrous sodium sulphate. The solution is cooled. During the
cooling operation, 5 % of the initial water is lost by evaporation. As a result, crystals of
Na2SO4 · 10 H2O crystallises out. If the mother liquor is found to contain 18.3 % by weight
anhydrous Na2SO4, calculate the yield of crystals and the quantity of mother liquor.
At. Wt. : Na = 23, S = 32, O = 16, H = 1.
Solution : Basis : 7500 kg aqueous solution
M1 = Mol. Wt. of Na2SO4 = 142
M2 = Mol. Wt. of Na2SO4 · 10 H2O = 322
F = 7500 kg
Amount of MgSO in the feed = X' F
4 F
29.6
= 100 × 7500 = 2220 kg

Amount of water in the feed = (1 – X'F) F

= (1 – 0.296) 7500 = 5280 kg
5
V = Amount of water lost by evaporation = 100 × 5280 = 264 kg
Material balance of water :
M2 – M1 
(1 – XF' ) F = C  M  + L' + V
 2 

5280 = C  322  + L' + 264

322 – 142
 
5016 = 0.56 C + L'
L' = 5016 – 0.56 C
where C is the yield of hydrated crystals.
Mother liquor contains 18.3 % by weight Na2SO4. Therefore,
0.183
X' = kg Na2SO4/kg water (solvent) = 1 – 0.183 = 0.224
Unit Operations – II 11.24 Crystallisation

Material balance of Na2SO4 :

M1
X'F F = C M + L' X'
2

142
2220 = 322 C + 0.224 L'

2220 = 0.441 C + 0.224 L'

We have L' = 5016 – 0.56 C
∴ 2220 = 0.441 C + 0.224 (5016 – 0.56 C)
Solving, we get C = 3474.5 kg
Overall material balance :
Feed = Hydrated crystals + Mother liquor + Water evaporated
7500 = 3474.5 + Mother liquor + 264
∴ Amount of mother liquor = 3761.5 kg
Yield of Na2SO4 · 10 H2O crystals = 3474.5 kg … Ans.
Example 11.8 : A saturated solution of MgSO4 at 353 K (80o C) is cooled to 303 K
(30o C) in a crystalliser. During cooling, 4 % solution is lost by evaporation of water.
Estimate the quantity of the original saturated solution to be fed to the crystalliser per
1000 kg of MgSO4 · 7 H2O crystals.
Data : Solubility of MgSO4 at 303 K (30o C) = 40.8 kg/100 kg water
Solubility of MgSO4 at 353 K (80o C) = 64.2 kg/100 kg water
At. Wt. : Mg = 24, S = 32, O = 16, and H = 1.0
Solution : Basis : 100 kg of feed solution
M1 = Mol. Wt. of MgSO4 = 120
M2 = Mol. Wt. of Mg SO4 · 7 H2O = 246
M2 – M1 = Mol. Wt. of 7 H2O = 126
Solubility of MgSO4 at 353 K = 64.2 kg/100 kg water
Solubility of MgSO4 at 303 K = 40.8 kg/100 kg water
64.2
MgSO4 in the feed solution = 164.2 × 100 = 39.1 kg

Loss of solution by evaporation = 0.04 × 100 = 4 kg

Solute balance for hydrated salt :
M1  M2 – M1 
F · X'F = C · M + F (1 – X'F) – V –  M  C X'
2   2  
Unit Operations – II 11.25 Crystallisation

where F = 100 kg
X'F = 39.1/100 = 0.391
V = 4 kg
40.8
X' = 100 = 0.408

100 × 0.391 = 246 C + 100 (1 – 0.391) – 4 –  246  C × 0.408

120 246 – 120
   
39.1 = 0.4878 C + [60.9 – 4 – 0.512 C] × 0.408
0.2788 C = 15.89
C = 56.99 kg yield of crystals
C is the kg of hydrated crystals obtained.
For 56.99 kg of crystals, 100 kg of feed solution is required.
For a yield of 1000 kg crystals‚ 100
∴ the charge to the crystalliser = 56.99 × 1000
(i.e., quantity of the feed solution) = 1754.56 kg … Ans.
Example 11.9 : A solution of sodium nitrate in water contains 48% NaNO3 by weight at
313 K temperature. Calculate the percentage yield of NaNO3 crystals that may be obtained
when temperature is reduced to 283 K. Solubility of NaNO3 at 283 K is 80.18 kg/100 kg
water.
Solution : Basis : 100 kg of feed solution.
Instead of using notation for various streams and the other terms as used before, we will
solve this problem by writing material balances and solving them simultaneously.
Let x be the kg of NaNO3 crystals obtained and y be the kg of mother liquor obtained.
Overall material balance :
Feed solution = crystals + mother liquor
100 = x + y … (1)
Feed solution contains 48% by weight NaNO3.
The solubility of NaNO3 at 283 K is 80.18 kg per 100 kg water.
It means that 180.18 kg (100 + 80.18) mother liquor contains 80.18 kg NaNO3.
Material balance of NaNO3 :
NaNO3 in feed solution = NaNO3 crystals + NaNO3 in mother liquor
80.18
0.48 × 100 = x + 180.18 y

48 = x + 0.445 y … (2)
Unit Operations – II 11.26 Crystallisation

Solving Equations (1) and (2) simultaneously gives

x+y = 100
x = 100 – y
48 = x + 0.445 y
48 = (100 – y) + 0.445 y
∴ 0.555 y = 52
y = 93.7 kg
x + 93.7 = 100
x = 6.3 kg
Yield of NaNO3 crystals from 100 kg solution = 6.3 kg
NaNO3 in the feed solution = 48 kg
6.3
% yield of NaNO3 crystals = 48 × 100

= 13.12 … Ans.
Note : You can adopt the same procedure to solve the previous problems.
Example 11.10 : Calculate the yield of MgSO4 · 7H2O crystals when 1000 kg saturated
solution of MgSO4 at 353 K is cooled to 303 K assuming 10% of water is lost by evaporation
during cooling.
Data : Solubility of MgSO4 at 353 K = 64.2 kg/100 kg water
Solubility of MgSO4 at 303 K = 40.8 kg/100 kg water
Mol. Wt. of MgSO4 = 120, Mol. Wt. of MgSO4 · 7 H2O = 246
Solution : Basis : 1000 kg of saturated solution at 353 K.
Let us solve this problem without using notation.
Let x be the kg of MgSO4 · 7 H2O crystals obtained, y be the kg of mother liquor
obtained.
Saturated solution = 1000 kg
Solubility at 353 K = 64.2 kg/100 kg water
i.e., 164.2 kg (100 + 64.2) of saturated solution contains 64.2 kg of MgSO4 and 100 kg of
water.
100
Water in the saturated solution = 164.2 × 1000

= 609 kg
MgSO4 in the saturated solution = 1000 – 609 = 391 kg
Water lost by evaporation = 10% of original water
Water lost by evaporation = 0.10 (609) = 60.9 kg
Unit Operations – II 11.27 Crystallisation

Overall material balance :

Feed solution = crystals + mother liquor + water lost by evaporation
1000 = x + y + 60.9
x+y = 939.1 … (1)
Solubility of MgSO4 at 303 K = 40.8 kg/100 kg water
i.e., 140.8 kg of mother liquor contains 40.8 kg of MgSO4 and 100 kg water.
We have :
1 kmol MgSO4 · 7H2O ≡ 1 kmol MgSO4
246 kg MgSO4 · 7H2O ≡ 120 kg MgSO4
i.e., 246 kg MgSO4 ⋅ 7H2 contain 120 kg MgSO4.
Material balance of MgSO4 :
MgSO4 in feed solution = MgSO4 in crystals + MgSO4 in mother liquor
120 40.8
391 = 246 × x + 140.8 y

391 = 0.488 x + 0.2898 y … (2)

Solving Equations (1) and (2) simultaneously gives
x + y = 939.1
y = 939.1 – x
391 = 0.488 x + 0.2898 (939.1 – x)
∴ x = 599.64 kg (crystals obtained)
599.64 + y = 939.1 ∴ y = 339.46 kg
Yield of MgSO4 · 7 H2O crystals = 599.64 kg … Ans.

EXERCISE
1. Fill in the blanks :
(a) ............ and ........... are the phases involved in crystallisation. Ans. Liquid, solid
(b) In crystallisation from solution, simultaneous ................ and mass transfer takes
place. Ans. heat
(c) In crystallisation, mass transfer occurs from the solution to ....... phase. Ans. solid
(d) ............... is the driving force for crystallisation. Ans. supersaturation
(e) For common salt (NaCl) ...... is independent of variation in temperature.
Ans. solubility
(f) Solubility is generally expressed as parts by weight ......... per ......... parts by weight
solvent. Ans. solute, 100
Unit Operations – II 11.28 Crystallisation

(g) For solutes whose solubility increases within increase in temperature, supersaturation
is achieved by .......... alone. Ans. cooling
(h) For solutes whose solubility remains more or less constant with temperature,
supersaturation is achieved by .......... of a part of the solvent. Ans. evaporation
(i) Vacuum crystalliser is used for ........... sensitive materials. Ans. heat
(j) ............ and crystal growth are the two basic steps in the overall process of
crystallisation. Ans. Nucleation.
2. Define the following terms :
(a) crystallisation (b) solubility (c) nucleation
(d) crystal growth (e) supersaturation.
3. Explain in brief solubility curves.
4. State various methods of generating supersaturation.
5. Give the classification of crystallisers.
6. Discuss in brief crystal formation.
7. Explain in brief with a neat sketch Swenson-Walker crystalliser.
8. Explain with a neat sketch Oslo-cooling crystalliser.
9. Draw a neat sketch of agitated tank crystalliser.
10. Draw a neat sketch of vacuum crystalliser and explain its construction.
❐❐❐