INTRODUCTION

INTRODUCTION

Types of Crystals
Cubic three equal axes at right angles to each other
Tetragonal three axes at right angles to each other, one axis longer
than the other two
Orthorhombic three axes at right angles to each other, allof
different lengths
Hexagonal three equal axes in one lane at 60 to each other and a
fourth axis at right angles to this plane
Monoclinic three unequal axes, two at right angles in a plane and a third at
some angle to this plane
Triclinic three unequal axes at unequal angles to each other and
not 30, 60 or 90
Trigonal three equal and equally inclined axes

Types of Crystals

Equilibrium Solubility in Crystallization

In crystallization equilibrium is
attained when the solution or
mother liquor is saturated.
Represented by a SOLUBILITY
CURVE.
Solubility is dependent mainly on
temperature.
In general, the solubilities of most
salts increase slightly or markedly
with increasing temperature.

Solubility Curve
anywhere on the solubility curve saturated solid crystals
above the solubility curve supersaturated solid crystals
below the solubility curve unsaturated solution.

Solubility of sodium thiosulfate, Na2S2O3, in water

Solubility increases rapidly with temperature, but there are definite breaks in the
curve which indicate different hydrates.
Up to 50C, the solid crystals formed are Na2S2O35H2O
From 50C to 65C, the solid crystals formed are Na2S2O32H2O
From 65C to 70C, the solid crystals formed are Na2S2O3H2O
Above 70C, anhydrous solid crystals formed are Na2S2O3

Yields and Heat and Material Balances in Crystallization

1)

Material balances in crystallization

The yield of crystals from a crystallization process can be calculated knowing the initial
concentration of solute, the final temperature and the solubility at this temperature.

W kg H2O

F kg feed
(T)

Cooler or
crystallizer

S kg solution

C kg crystals

(T)

2) Heat effects and heat balances in crystallization

When a compound (whose solubility increases as temp. increases) dissolves, there is an
absorption of heat called heat of solution.
At equilibrium, the heat of crystallization is equal to the negative of heat of solution at
the same concentration.
If some evaporation occurs, the enthalpy, Hv of the water vapor is obtained from the
steam tables.
Total heat absorbed, q :
q = H2 + H v - H 1
H1 = enthalpy of the entering solution
H2 = enthalpy of the final mixture of crystals and mother liquor
Hv = enthalpy of the water vapor

If q is positive, heat must be added to the system.

If q is negative, heat is evolved or given off.

Example 12.11-1
A salt solution weighing 10 000 kg with 30% Na2CO3 is cooled to 293 K (200C). The salt crystallizes
as the decahydrate. What will be the yield of Na2CO310H2O crystals if the solubility is 21.5 kg
anhydrous Na2CO3/100 kg of total water?
(a) Assume that no water is evaporated.

V kg H2O
10,000 kg solution
30% Na2CO3

COOLER &
CRYSTALLIZER

S kg solution
21.5 kg Na2CO3/100 kg H2O

70% H2O
C kg crystals, Na2CO3 10H2O

1. Perform material balance for water and Na2CO3

H2O balance:

0.7(10000)

100
180.2
(S )
(C ) 0
100 21.5
286.2

Na2CO3 balance:

0.3(10000)

21.5
106
(S )
(C )
100 21.5
286.2

Molecular Weight: 10H2O = 180.2

Na2CO3 = 106
Na2CO310H2O = 286.2

2. Solving the two equation simultaneously,

C = 6370 kg of Na2CO310H2O crystals
S = 3630 kg solution

(b) Assume that 3% of the total weight of the solution is lost by evaporation of water in cooling.

0.03(10000) 300 kg H 2 O
Balance for water and Na 2 CO 3 :
0.70(10000)

0.3(10000)

100
180.2
(S )
(C ) 300
100 21.5
286.2

21.5
106
(S )
(C ) 0
100 21.5
286.2

Solving the two equation simultaneously,

C = 6630 kg of Na2CO310H2O crystals
S = 3070 kg solution

Example 12.11-2
A feed solution of 2268 kg at 327.6 K (54.4C) containing 48.2 kg MgSO4 / 100 kg total
water is cooled to 293.2 K (20C) where MgSO47H2O crystal are removed. The solubility
of the salt is 35.5 kg MgSO4 / 100 kg total water. The average heat capacity of the feed
solution can be assumed as 2.93 kJ/kg.K. The heat of solution at 291.2 K (18C) is -13.31 x
103 kJ/kg mol MgSO47H2O. Calculate the yield of crystals and make a heat balance to
determine the total heat adsorbed, q assuming no water is vaporized.
W= 0
F=2268kg
(327.6K)

Crystallizer

S (293.2 K)

48.2 kg MgSO4
100 kg H2O
C kg MgSO4 . 7H2O

35.5 kg MgSO4
100kg H2O

1. Perform material balance for water and MgSO4

100
126
100
(S )
(C ) 0
2268
100

48
.
2
100

35
.
5
246
.
49

H2O balance:

MgSO4 balance:

48.2
35.5
120.49
(S )
(C )
2268
100

48
.
2
100

35
.
5
246
.
49

Molecular Weight: 7H2O = 126

MgSO4 = 126
MgSO4 7H2O = 246.49

2. Solving the two equation simultaneously,

C = 616.9 kg of MgSO4 7H2O crystals
S = 1651.1 kg solution

To make heat balance, a datum of 293.2 K will be used.

The enthalpy of feed, H1 = 2268(327.6K - 293.2K)(293) = 228600 kJ
Heat of solution is = - 13.31 x 103 kJ/ kgmol MgSO4

Heat of crystallization, H2 = (- 13.31 x 103 kJ/ kgmol MgSO47H2O) / (246.49 kg/kgmol MgSO47H2O)
= (- 54.0 kJ/kg crystals) x 616.9 kg crystals
= -33312 kJ
Assume value at 291.2 K is the same as at 293.2 K
The total heat absorbed, q:
q = H 2 + Hv - H1
= -33312 - 228600

= -261912 kJ
Since q is ve , heat is evolved or given off.