CRYSTALLIZATION

important industrially because:

i) a crystal formed from an impure solution and itself pure
ii) Practical method of obtaining pure chemical substances in a
satisfactory condition for packaging and storing

solid-liquid separation process

yield , purity, sizes & shapes of crystals important

crystals - uniform in size

formation of 1,4-naphthoquinone crystals from a liquid solution

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 SOLUBILITY CURVE

equilibrium is attained when the solution or mother liquor is saturated

(represented by solubility curve)
solubility dependent mainly on temperature
solubilities of most salts increase slightly or markedly with temperature

Solubility curve for some typical salts in water Solubility curve for sodium thiosulfate

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 SOLID-LIQUID PHASE DIAGRAM

Solid-liquid phase diagram for the MgSO4-nH2O system at 1 atm

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 YIELD & HEAT & MATERIAL BALANCES
yield of crystals can be calculated by knowing:
initial concentration of solute
final temperature
solubility at this temperature
material balances
kg H2O evaporate Mass balance :
Water balance : Input = Output
Solute balance : Input = Output
F kg Hot solution S kg solution

X1 kg solute/ X2 kg solute/
100 kg H2O 100 kg H2O

C kg Crystal
solute crystals are anhydrous - simple water & solute material balances
crystals are hydrated - some water in the solution is removed with crystals
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 EXAMPLE

A batch of 1500 kg of saturated potassium chloride solution is cooled from

360K to 290K in an unagitated tank. If the solubities of KCI are 53 and 34
kg/100 kg water at 360K and 290K, respectively and water losses due to
evaporation may be neglected, what is the yield of crystals?

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 EXAMPLE

A salt solution weighing 10000 kg with 30 wt. % Na2CO3 is cooled from 333K
to 293K. The salt crystallizes as the decahydrate. What will be the yield of
Na2CO3.10H2O crystals if the solubility is 21.5 kg anhydrous Na2CO3/100kg
water?
a) Assume that no water is evaporated.
b) Assume that 3% of the total weight of the solution is lost by evaporation of
water in cooling.

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 EXAMPLE

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 HEAT BALANCES IN CRYSTALLIZATION
normally, crystallization is exothermic W kg H2O
HV kJ/kg

F kg Hot solution S kg solution

hF kJ/kg hS kJ/kg

Total heat absorbed, q (kJ): C kg Crystal

hC kJ/kg
When Tdatum = 32oF ,
FhF + q = (S + C)hM + WHV
or
FhF + q = ShS + ChC + WHV
When Tdatum = Tequil./sat. , FhF + q = W + ChC = W + CHcrys

heat of crystallization, Hcrys = - heat of solution at infinite dilution, H
soln
Heat absorbed, q = +ve ,Heat given off , q = -ve

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 ENTHALPY-CONCENTRATION DIAGRAM

Enthalpy-concentration diagram for the

MgSO4-nH2O system at 1 atm

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 EXAMPLE

A 32.5% solution of MgSO4 at 120oF (48.9oC) is cooled, without appreciable

evaporation to 70oF (21.1oC) in a batch-cooled crystallizer. How much heat
must be removed from the solution per 100 Ib of the feed solution? The
average heat capacity of the feed solution is 0.72 Btu/Ib oF and the heat of
solution at 18oC is 23.2 Btu/Ib of MgSO4.7H20.

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 EXAMPLE

A solution of 500 kg of Na2SO4 in 2500 kg water is cooled from 333K to 283K in

an agitated mild steel vessel. At 283K, the solubility of the anhydrous salt is 8.9
kg/100kg water and the stable crystalline phase is Na2SO4.10H2O. At 291K, the
heat of solution is -78.5 MJ/kmol and the specific heat capacity of the solution
is 3.6 kJ/kg.K. If, during cooling, 2% of the water initially present is lost by
evaporation, estimate the heat which must be removed.

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