Crystallization

CHEMICAL ENGINEERING AND

CHEMICAL PROCESS TECHNOLOGY –
Heat and Mass Transfer Operations –
Crystallization - J. Ulrich and M.J. Jones
Crystallization is a thermal separation, and
therefore a purification process that yields a
solid product from a melt, from a solution
or from a vapour.
Solutions are normally thought of in terms
of liquids, however, solutions may include
solids suspension. Typically, the term
solution has come to mean a liquid solution
consisting a solvent, which is a liquid, and a
solute, which is a solid, at the conditions of
interest.
The solution to be ready for crystallization
must be supersaturated. A solution in which
the solute concentration exceeds the
equilibrium (saturated) solute concentration
at a given temperature is known as a
supersaturated solution.
As for all thermal separations, non-
equilibrium conditions are required as a
driving force for the process.
Here, evaporation of solvent or temperature
reduction (cooling) are the most frequent
means employed to establish the required
non-equilibrium conditions.
Pressure in principle, can, also be used to
enforce the non-equilibrium state
necessary for a phase change. However,
in industrial applications this parameter is
most frequently kept constant.
There are four main methods to generate
supersaturation that are the following:

• Temperature change (mainly cooling),

• Evaporation of solvent,

• Chemical reaction, and

• Changing the solvent composition (e.g.

salting out).
Water is almost exclusively used as the
solvent for the industrial crystallization of
inorganic substances from solutions.
There are several hundred organic liquids
that are potentially capable of acting as
crystallization solvents, but outside the
laboratory the list can be shortened to a
few dozen selected from the following
groups: acetic acid and its esters, lower
alcohols and ketones, ethers, chlorinated
hydrocarbons, benzene homologues and
light petroleum fractions.
Common binary solvent mixtures that
have proved useful includes alcohol with
water, ketones, ethers, chlorinated
hydrocarbons , benzene homologues etc.
and normal alkanes with chlorinated
hydrocarbons and aromatic hydrocarbons
A second liquid is sometime added to a
solution to reduce the solubility of the
solute, causing its precipitation
/crystallization and maximise the yield of
the product.

The original solvent and the added

precipitant must be completely miscible
with one another in all proportions.
When water is the additional solvent, the
process is called “watering out”. e.g
crystallization of organic substances from
water-miscible organic solvents by
controlled addition of water.
When an organic solvent is added to an
aqueous salt solution, the process is called
“salting out” or “drowning out” or “quench
crystallization.
The term “precipitation” is used when
dealing with very fast, usually hard to
control crystallization during which a large
numbers of seed crystals is formed.
 Precipitation also occurs when one product
of two reacting solutions is a solid with low
solubility. e.g

aq AgNO 3  aq NaCl  AgCl (ppt)  aq NaNO3

When both components of a homogeneous,
binary solution having melting (freezing)
points not far removed from each other, the
solution is referred as melt. Melt is the
technique of separation of a compound in an
acceptably pure form from a mixture with
undesired substances without using a solvent.
 The main feature distinguishing
crystallization from other thermal separation
processes is the fact that it leads to a solid
product. This is one of the key reasons why
it lags behind separation techniques
involving liquid-liquid or liquid-gaseous
phase change processes in terms of research
effort expended and knowledge available.
 In the past chemical engineering has tended
to avoid the solid state as far as possible due
to the problems inherent in solids handling.
Encrustation (the formation of a crust) and
the concomitant (existing or occurring with
something else), heat transfer problems,.
.
generation of hazardous dust and the general
difficulty inherent in solid-liquid separation
are just some of the issues involved.
The positive aspects of the techniques - low
energy consumption and the potential for
high-purity products, are more widely
appreciated.
Crystallization is a highly selective process
and operates at lower temperatures when
compared to a separation by distillation for
the same material. Melt crystallization has
the additional advantage of not requiring a
solvent, although it is not a method
suitable for all materials.
Manifold reasons exist for the growing
importance of crystallization as an
industrial separation process. On the one
hand, many products are solids under
ambient conditions, in particular in the
specialty chemicals sector, in the
pharmaceutical industry and in the
manufacture of foods.
On the other hand, the ability to
manipulate, the macroscopic properties of
crystals such as shape and size by
judicious choice of crystallization
conditions makes the technique a very
attractive option.
 Crystal Habit
When crystals grow, they form polyhedrons
with flat sides and sharp corners (if
unhindered by other surfaces such as
container walls and other crystals)

Crystals are never spherical in shape

Law of constant interfacial angles (Hauy, 1784)

The angles between corresponding faces of

all crystals are constant, even though the
crystals vary in size and in the development
of the various faces

The interfacial angles and lattice dimensions

can be measured by X-ray crystallography
Typical magmas from a crystallizer
contain a distribution of crystal sizes and
shapes.

Characteristic crystal dimension for

irregular-shaped particle → sphericity, ψ
 surface area of the sphere with the same volume of the particle

surface area of the particle

For a sphere, ψ = 1;
for all other particles, ψ < 1
Sp   D 2p 6
   
Vp    D 3  Dp
  sphere  p 
 6 
 

6  V p 
 
D p  S p 
particle
 Concentration (g/100g H2O)

Labile

Stable
Metastable

Temperature (0C)

Fig10.1: Ostwald-Miers diagram for a solute/solvent system

The Ostwald-Miers diagram shown in Fig. 10.1.
illustrates the basis of all methods of solution
growth.

The solid line represents a section of the curve for

the solute / solvent system. The upper dashed line
is referred to as the super-solubility line and
denotes the temperatures and concentration where
spontaneous nucleation occurs
` The diagram can be evaluated on the basis of
three zones:
• The stable (unsaturated) zone where
crystallization is impossible,

• The metastable (supersaturated) zone where

spontaneous nucleation is improbable but a
crystal located in this zone will grow and

• The unstable or labile (supersaturated) zone

where spontaneous nucleation is probable and
so the growth.
Crystallization from solution can be thought of as a
two step process. The first step is the phase
separation, (or birth), of a new crystals. The second
is the growth of these crystals to larger size.

These two processes are known as nucleation and

crystal growth, respectively. Analysis of industrial
crystallization processes requires knowledge of
both nucleation and crystal growth.
The birth of a new crystals, which is called
nucleation, refers to the beginning of the phase
separation process. The solute molecules have
formed the smallest sized particles possible
under the conditions present. The next stage of
the crystallization process is for these nuclei to
grow larger by the addition of solute
molecules from the supersaturated solution.
This part of the crystallization process is
known as crystal growth. Crystal growth,
along with nucleation, controls the final
particle size distribution obtained in the
system. In addition, the conditions and rate
of crystal growth have a significant impact
on the product purity and the crystal habit.
An understanding of the crystal growth
theory and experimental techniques for
examining crystal growth from solution are
important and very useful in the
development of industrial crystallization
processes.
 Crystal growth may broadly be discussed
under a few general headings :

• Surface energy theories

• Adsorption layer theories

• Kinematic theories
• Diffusion - reaction theories

• Birth and spread models

Q.1: The concentrate from an evaporation
system is 4466 lb/h of 37.75 MgSO4 at 170 0F
and 20 psia. It is mixed with 9860 lb/h of a
saturated aqueous recycle filtrate of MgSO 4 at
85 0F and 20 psia and sent to a vacuum
crystallizer, operating at 85 0F and 0.58 psia in
the vapour space, to produce water vapour and
a magma of 20.8 wt%
 crystals and 79.2 wt% saturated solution. The
magma is sent to a filter, from which filtrate is
recycled as mentioned above. Determine the lb/h
of water evaporated and the maximum
production rate of crystals in tons/day (dry basis
for 2000 lb/ton). Crystals are MgSO4.7H2O.

Data: For the saturated filtrate at 85 0F the weight

fraction of MgSO4 = 28 %
 Ans:
V
4466 lb/h, Mixer F Crystallizer
37.75 % MgSO4
Magma (L+S)
9860 lb/h Solids
FIlter
Recycle filtrate Crystals

F = mixed feed to crystallizers (lb/h)

L = lb/h of liquid in magma,
S = lb/h of solids (crystals in magma)
V = evaporation rate (lb/h)
Material balance around the mixture
Component Feed Recycle Crystallizer
(lb/h) (lb/h) feed (F)

MgSO4 0.3775 x 4466 0.28 x 9860 4466

= 1686 = 2760

H2O 2780 7100 9860

Total 4466 9860 14326
The magma is 20.8% MgSO4.7H2O and
79.2% of 28% aqueous MgSO4 liquid.
Mol Weight of MgSO4.7H2O = 246.4
Mol Weight of MgSO4 = 120.4
therefore, mass fraction of MgSO4 in
crystals = 120.4/246.4 = 0.4886
Making a MgSO4 balance over the
crystallizer
4446 = 0.4886 S + 0.28 L - (1)
and, S = 0.208 (S + L) - (2)
solving (1) and (2)
S = 2856 lb/h
L= 10876 lb/h
By a total material balance over the
crystallizer,
F=V+L+S
14326 = V + 10876 + 2856
V = 594 lb/h
Maximum production rate of crystals
= (2856)(24)/2000 = 34.3 tons/day
Q 2: Oxalic acid is to be crystallized
from a saturated aqueous solution
initially at 100 0 C. To what
temperature does the solution have to
be cooled to crystallize 95% of the
acid as the dihydrate?
 Solubility Data:
T 0C 0 10 20 30 40 60 80 100
Solubility, 3.5 6 9.5 14.5 21.6 44.3 84.4 84.4
g/100 g H2O

Solution:
Basis: 100 g water
Amount of dissolved oxalic acid at 100 0C = 84.4 g
Amount to be crystallize = 0.95 x 84.4 = 80.2 g
Amount of oxalic acid left in the solution = 84.4 – 80.2 = 4.2 g
Molecular weight of oxalic acid = 90
Molecular weight of water = 18
Water of hydration 2 H2O = 2(18)/90
= 0.4 g H2O/g oxalic acid
Water of crystallization = 0.4 (80.2)
= 32.1 g H2O
Liquid water remaining = 100 – 32.1
= 67.9 g
Final solubility must be (4.2/67.9) x 100
= 6.19 g / 100 g H2O

(from Fig.1, or by linear interpolation)

S o lu b ility . g / 1 0 0 g H 2
20

15

10
6.19
5

10.6
0
0 10 20 5
20.5
T 0C
Fig1: Solubility data of Oxalic Acid
Q 3: A salt solution weighing 10000 kg with 30
wt% Na2CO3 is cooled to 293 K. The salt
crystallizes as the decahydrate. What will be
the yield of Na2CO3. 10 H2O crystals if the
solubility is 21.5 kg anhydrous Na2CO3/ 100 kg
of the 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 the water in
cooling?
Solution: W kg H2O

S kg Solution
10000 kg soln Cooler and
Crystallizer 21.5 kg
30 % Na2CO3 Na2CO3/100
kg H2O

C kg crystal Na2CO3.10 H2O

 Molecular weight of Na2CO3, 10 H2O and

Na2CO3. 10 H2O are 106, 180.2 and 286.2.

Making a material balance around the dashed

line box. (a) W = 0
Water
100 180.2
0.70  10000   S C  0 (1)
100  21.5 106  180.2
 Solute
21.5 106
0.30  10000   S C0 (2)
100  21.5 286.2

Solving (1) and (2), we get

C = 6370 kg of Na2CO3.10 H2O

S = 3630 kg solution
 (b) W = 0.03(10000) = 300 kg

Water
100 180.2
0.70  10000  S C  300 (3)
100  21.5 106  180.2

Equation (2) remains same as there is no salt in

the W stream. Solving (3) and (2), we get

C = 6630 kg of Na2CO3.10 H2O

S=
3070 kg solution
 Solubilities and Phase Diagrams
A saturated solution has a constant
composition that is not changed by the
addition of further amount of the dissolved
material. For a two component system, the
solubility of one component in the other is
dependent on temperature and pressure.
For three and more component systems the
solubility of one component also depends
on the relative amounts of the other
components present. For liquid solutions
the pressure dependence is negligible if the
pressure difference is small
However, the temperature dependence
(and also the pressure dependence
providing the difference is sufficiently large,)
of the solubility can be considerable and it is
therefore important to state the
temperature for which the solubility is
reported even under ‘normal’ conditions.
It is common terminology for solutions of
solids in liquids to denote the liquid
component as the solvent and the solid
component as the solute, even if the
amount of solute in the solution exceeds
the amount of solvent. Various measures of
composition are in use to report solubilities
• Mass of solute per unit mass of solvent (kg/kg)

• Mass of solute per unit mass of solution (kg/kg)

• Mass of solute per unit volume of solvent (kg/m3 or g/L)

• Molar amount of solute per unit volume of solvent (kmol/

m3 or mol/L)

• Mole fractions (dimensionless number)

The solubility of most materials increases
with temperature. However, a number of
examples exist, where the solubility shows
the reverse trend (sodium sulfate, calcium
carbonate, iron sulfate dihydrate, to name a
few).
The dependence of the solubility upon
temperature is best represented graphically
in the form of a solubility curve, which maps
the composition of a solution at the
solubility limit onto the temperature. A
generalized solubility curve is shown in
Figure 10.2.
The solubility is a continuous function of
temperature for a given form of a given
material. Polymorphs of the same material,
solvates and hydrates generally have
different solubilities.
A change in solid form is normally
evidenced by a discontinuity in the solubility
curve, which results from different slope,
that is, temperature dependence, of the
solubility of the respective forms.
 Temperature
Fig. 10.2 : Solubility Diagram
In Figure 10.2 the solubility of a fictitious
substance A that forms three phases, two
hydrates and one anhydrous phase, is
shown. Two discontinuities can be seen
marking the transition points between the
stable regions for the trihydrate and
monohydrate (left) and the monohydrate
and anhydrous phase (right).
The solubilities of the respective stable
phases are indicated by the solid line.

In addition, the solubilities of the different

metastable forms are indicated by the
dotted line.
 The driving force required for nucleation
and crystal growth is the level of
supersaturation in the solution
(supercooling in melts). Crystallization can
only occur at solution compositions where
the amount of solute exceeds the solubility
limit.
 Such solutions are called supersaturated
solutions and the region of phase space
where supersaturated solutions exist is
known as the metastable zone. The driving
force for crystallization (both nucleation and
crystal growth) increases with increasing
supersaturation.
 The Metastable Zone
An important non-equilibrium property of a
supersaturated solution is the width of the
metastable zone. The metastable zone limit
denotes the composition of the solution at a
given set of conditions where the solution
becomes labile and at which point spontaneous
nucleation must occur.
 Since nucleation is a kinetically governed
process and can be induced by different
mechanisms, the metastable zone width is
an ill-defined quantity and depends upon
time, purity of the solution, cooling or
evaporation rate, agitation etc..
The maximum width of the metastable zone
is given by those concentrations where
instantaneous nucleation occurs once the
corresponding temperature has been
reached. In other words it is defined by
those points where the induction time for
nucleation vanishes.
 All points with finite induction times lie
within the metastable zone. The metastable
zone width can be measured by determining
the point at which first crystal nuclei are
detectable. This can be achieved by optical
methods such as turbidity measurements or
 ATR-FTIR (attenuated total reflectance
Fourier transform infrared spectroscopy), by
measurement of acoustic properties of the
solution (ultrasound), or by measuring any
other easily measurable physical parameter
such as density or conductivity.
Unfortunately there is no single analytical
technique that is suitable for all substances;
the best method has to be determined after
careful consideration of the individual
system
Fig.10.3: Stages of stability in solution crystallization
Figure 10.3 shows a generalized solubility
diagram which includes the metastable zone
width for different induction times. The line at
tind = 0 defines the limit of the metastable zone,
at higher concentrations of solute at constant
temperature the solution is labile.
 Phase Diagrams for Melt Crystallization

A melt is normally understood to be a liquid

close to its solidification point. In industrial
crystallization it encompasses any
homogeneous liquid mixture where all
major components as individual entities
would solidify above ambient temperature.
The only distinction between a solution
and a melt is then the fact that, for the
solution, at least one major component
(the solvent) is liquid under ambient
conditions.
In melt crystallization instead of
solubilities, solid-liquid phase diagrams
are the more appropriate point of
reference. In principle, solubility curves
are part of the solid-liquid phase diagram
and therefore contain the same
information.
For a binary system only three parameters are

required to define the state of the system,

pressure, temperature and composition. A

temperature-composition (T-x) diagram is more

useful, given the fact that the pressure

dependence of the solid-liquid equilibrium is

usually negligible under ambient conditions.

However, at high pressures pressure can

be used to direct a crystallization process

in much the same manner as temperature

at lower pressures.
In the case of the T-x diagram, the
equilibrium temperature is plotted against
the composition of the solid and the liquid
phase, usually expressed in terms of mole
fractions. Figure 10.4 shows a generalized
ideal temperature composition diagram.
T Liquidus line 1 phase T F
L L
2 phase Tα
S-L tie line
R C
Tω
T

1 phase S
S
Solidus line
A B A B
XA,S XA,l XS,α XS,ω XF=Xl,α Xl,ω
XA

(a) (b)

Figure 10.4: Solid-liquid temperature-

composition (T-x) phase diagram for an ideal
binary system.
For an ideal binary system where solid and
liquid are in equilibrium, the T-x diagram
consists of two lines separating three regions
in phase space. One of these lines represents
the composition of the solid phase (solidus),
the other the composition of the liquid phase
(liquidus).
The region below the solidus line is the region
where the solid phase is stable and no liquid
phase exists. The region above the liquidus line
is the region of stability of the liquid phase.
Both phases coexist only in the region
circumscribed by the solidus and liquidus lines.
The composition of the respective phases in
equilibrium with each other at any given
temperature is determined by the end
points of the tie line (Figure 10.4.a). The tie
line is a horizontal line (that is a line at
constant temperature) that connects the
liquidus and the solidus lines.
For a crystallization process, the composition of
the product at a given final temperature of the
process is independent of the starting point. In
this example, any melt with a composition in the
range between xAs and xAl will lead to a solid
product enriched in component A with
composition xAs and a liquid enriched with
component B with the composition xAl
From figure 10.4.b, starting from a composition
xF the temperature is lowered to Tα
corresponding to point of solidification at the
initial composition of the melt. The
corresponding solid composition is determined
by the intersection of the tie-line at Tα with the
solidus line and is represented by xSα .
At the final temperature Tω , the
composition of the solid is given by x Sω and
the composition of the liquid phase is xlω .
The relative proportions of solid and liquid
is given by the ratio of the lengths of the
lines R and C.
Figure 10.5 shows a simple eutectic phase
diagram. The eutectic phase diagram is
characterized by four regions, the
homogeneous liquid, two regions of
coexistence, and an inhomogeneous two-
phase solid consisting of pure
component A and pure component B.
 F1 F2 F3
T T
1 phase T3α
T1α
L

2 phases 2 phases
S1-L S2-L S1-L S2-L
1 phase 1 phase
S1 S1 S2
S2 TEU
EU EU
2 phases
S1-S2 S1-S2
B A B
A
xA xF1 xEU xF3
xA

Figure 10.5: Simple eutectic phase diagram.

The two regions of coexistence are
separated by the eutectic point, which is
defined by the minimum in the liquidus
curve and where the solid and the liquid
have the same composition.
The coexistence region to the left of the
eutectic point describes a system consisting
of pure solid A (S1) and the liquid phase, the
region to the right of the eutectic point,
conversely, describes a system consisting of
pure solid B (S2) and the liquid phase.
 The right-hand diagram indicates the different
outcomes of crystallization from different starting
points. For a liquid of composition F1 one obtains
pure A and a solid with eutectic composition, for a
liquid of composition F3 pure B is obtained together
with the eutectic solid. In the case of a liquid with
composition F2, no purification is achieved as the
liquid and the solid have the same composition
 NUCLEATION AND CRYSTAL GROWTH

NUCLEACTION

PRIMARY SECONDARY

HOMOGENEOUS HETEROGENOUS

CONTACT SHEAR FRACTURE ATTRITION

Nucleation
Given a sufficient driving force, that is
supersaturation in the case of solutions or
supercooling in the case of a melt, a liquid-
to-solid phase transformation commences
with the initial formation of clusters, ordered
collections of the crystallizing species.
 These clusters, or nuclei, are precursors to
the crystals eventually formed. In order to
grow into a macroscopically detectable
crystal, these nuclei have to reach a certain,
critical, size.
The critical nucleus size is governed by the
excess free energy ΔG of the nucleus which,
in turn, is given by the sum of the surface
excess free energy ΔGS and the volume
excess free energy ΔGV of the particle
(Figure 10.6).
Figure 10.6: Gibbs free energy versus radius of the nucleus
 The surface excess free energy is
proportional to the square of the radius of
the particle and is a positive quantity, the
volume excess free energy is a negative
quantity and is proportional to r3.
Below the critical radius redissolution of the
nucleus is energetically favourable, above
the critical radius growth is more favourable.
Different nucleation mechanisms exist and
the discussion above applies to primary
 homogeneous nucleation, which will

occur if the system is free of impurities,

mechanically undisturbed and when

the thermodynamic non-equilibrium is

at or beyond the metastable limit.

Under normal circumstances there are always

 impurities in the solution or melt.

 Mechanical disturbances result from agitation of

the solution or vibrations from ancillary

equipment.

 Surface roughness of the equipment

The more realistic situation is therefore the

case of primary heterogeneous nucleation

which occurs at a much lower

supersaturation and where impurities or

rough vessel walls function as nuclei.

The most frequently observed nucleation

mechanism is called secondary nucleation.

The Phenomenon of formation of new

crystals from the existing ones is called

secondary nucleation.
Secondary nucleation requires the presence of

crystals of the material to be crystallized and

occurs at much lower supersaturation than

primary nucleation. As a rule, secondary

nuclei are formed by the removal of

structured assemblies from the surface of the

crystals.
 There are different mechanisms which lead
to secondary nuclei, these are:
• initial breeding: nuclei result from simply
placing crystals into a supersaturated
solution or supercooled melt via the washing
off of dust particles from the surface of the
crystals
 • collision breeding: nuclei result from
fragments of existing crystals which are
broken off due to mechanical impact on
crystal faces due to crystal-crystal, crystal-
wall, or crystal-stirrer (-pump) collisions
• fluid shear: nuclei result from clusters or
outgrowths being forced from the solid-
liquid boundary layer due to shear forces
resulting from liquid motion. A prerequisite
for this behavior is that the growing crystal
already has a size larger than the critical
nucleus
 Collision breeding is the most frequently
observed and dominant secondary
nucleation mechanism, at least in the
majority of industrial, mass production,
crystallization processes.
 Crystal growth

Crystal growth occurs, only if there is a

driving force, as a result of non-equilibrium
thermodynamic conditions. Growth rates
depend upon:
• the temperature, pressure and composition
of the mother liquor
• supersaturation (under cooling),
• fluid flow conditions,
• history of the crystals,
• the nature of the surfaces of crystals
• presence or absence of additives (impurities)
in the mother liquor.
 Industrial experience suggests that a
solution crystallization process should best
be operated at the centre of the metastable
zone. If the process operates close to the
upper limit of the metastable zone, a small
fluctuation in the process variable is
sufficient to induce nucleation.
 This would result in a reduction of the
crystal size distribution and facilitate
oscillations in the crystallization process
with respect to the output of crystal size
distributions. Conversely, if the process is
operated close to the solubility limit,
insufficient mass per time is produced.
McCabe ‘∆L law’

“Crystal growth rate G is independent of

crystal size L”

(dG/dL) = 0

Not all systems obeys McCabe ∆L Law.

McCabe showed that all crystals that are
geometrically similar and of the same
material in the same solution grow at the
same rate.
Growth is measured as the increase in length
∆L, in mm, in linear dimension of one
crystal. This increase in length is for
geometrically corresponding distances on all
crystals. This increase is independent of the
initial size of the crystals, provided that all
the crystals are subject to the same
environmental conditions.
Mathematically, it can written as –
L
G
t

where, ∆t is time in hour and growth rate G

is constant in mm/h.
Problem: Mother liquor after crystallization
has a solute content of 49.8 kg CaCl2 per
100 kg of H2O. Find out the weight of this
solution needed to dissolve 100 kg of
CaCl2.6H2O at 25 0C. Solubility at 25 0C is
81.9 kg of CaCl2/100 kg of H2O.
Solution:

Let x = weight of H2O in the quantity of solution needed.

Molecular weight of CaCl2 = 111

Molecular weight of CaCl2.6H2O = 219

water present in 100 kg of CaCl2.6H2O

= (108/219) x 100 = 49.315 kg

CaCl2 present in 100 kg of CaCl2.6H2O

= (111/219) x 100 = 50.68 kg

Total CaCl2 entering for solubility

= 50.68 + 0.498x

Total H2O used for solubility

= x + 49.315

Total CaCl2 after solubility

= 81.9(x + 49.315)/100
Material balance for CaCl2:

50.68 + 0.498x = 81.9(x + 49.315)/100

→ 50.68 + 0.498x = 0.819x + 40.3767

→ 0.312 x = 10.3033

→ x = 32.0975
weight of CaCl2 in mother liquor
corresponding to the wt of 32.0975 kg H2O

= (49.8/100) x 32.0975
= 15.98 kg.

Total amount = 15.98 +32.0975

= 48.082 kg.
Problem: Sodium nitrate solution at 500C
contains 45% by weight of sodium nitrate.

a) Find out the percentage saturation of this

solution

b) Find out the weight of sodium nitrate crystal

formed if 1000 kg of this solution is cooled to
100C.
c) Find out the % yield of this process.
Data:

solubility at 500C = 104.1 kg NaNO3/100 kg of H2O.

solubility at 100C = 78 kg NaNO3/ 100 kg of H2O.

Solution:

(a) NaNO3 at % saturated solution at 500C

= (104.1/204.1) x 100% = 51%

% saturation at 500C = (45/55)/(51/49) x 100%
= 78.6%
(b) let, x be the wt of NaNO3 crystals formed after
crystallization.

Writing the material balance for NaNO3

1000 x 0.45 = x + (1000 – x) 78/178

450 = x + 438.20 – 0.43820x

0.5618 x = 11.8
X = 21 kg
(c) Yield = Wt. of NaNO3 crystal formed
Wt. of NaNO3 in original solution

= (21/450) x 100% = 4.66%

Problem: A saturated solution of potassium
sulfphate is available at a temperature of 700C.
Calculate the temperature to which this should
be cooled to crystallize 50% of potassium.
Data: solubility at 700C = 19.75 / 100 g of H2O
500C = 16.5 / 100 g of H2O
300C = 12.97 / 100 g of H2O
200C = 9.22 / 100 g of H2O
00C = 7.34 / 100 g of H2O
 Solution:

Basis: 1000 kg of saturated solution.

Wt of K2SO4 in original solution

= 1000 x (19.75/119.75)= 164.42 kg

Therefore, wt of H20 in original solution

= 1000 – 164.42 = 835.08 kg

After crystallization, wt of K2SO4 in solution

= 164.92 x 0.5 = 82.46 kg

Wt % of K2SO4 in solution after crystallization

= [82.46/ (82.46 + 835.08)] x 100%

= 8.98 %

linear interpolation between 00C to 200C

 9.22

8.89

7.34

0 x 20

(8.98 – 7.34) / (x – 0) = (9.22 – 7.34)/(20 – 0)

x = 1.64 x 20 / 1.88

X = 17.4470C.