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satisfactory condition for packaging and storing

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SOLUBILITY CURVE

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1

SOLUBILITY CURVE

(represented by solubility curve)

• 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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2

YIELD & HEAT & MATERIAL BALANCES

• yield of crystals can be calculated by knowing:

initial concentration of solute

final temperature

solubility at this temperature

• material balances Mass balance :

kg H2O evaporate

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 12.11-1

A salt solution weighing 10 000 kg with 30 wt % Na2CO3 is cooled to 293K (20oC). The salt

crystallized as the decahydrate. What will be the yield of Na2CO3.10H2O crystals if the

solubility is 21.5 kg anhydrous Na2CO3/100 kg of total water?

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

cooling.

Ans: 6370 kg, 6630 kg

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3

EXAMPLE 12.11-1

Solution:

Molecular weights: Na2CO3 = 106.0, 10H2O = 180.2, Na2CO3 •10H2O = 286.2

Na2CO3 balance:

(b) W = 0.03(10000) = 300 kg, water balance:

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EXAMPLE 27.1(McCabe,
Smith & Harriott)

A solution consisting of 30 wt% MgSO
4 is cooled to 60oF. During cooling, 5 %

of the total water in the system evaporates. How kg of crystals are obtained per

1000 kg of original mixture?

Data: Molecular weight of MgSO4 = 120.4

Ans: 261 kg

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4

EXAMPLE (P12.11-3)

of 30 wt% MgSO4 is cooled to 288.8 K (60oF) where crystals of MgSO4.7H2O

are precipitated. The solubility at 288.8 K is 24.5 wt % anhydrous MgSO4 in

the solution. Calculate the yield of crystals obtained if 5 % of the original

water in the system evaporates on cooling.

Data: Molecular weight of MgSO4 = 120.4

Ans: 261 kg

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normally, crystallization is exothermic W kg H2O

HV kJ/kg

hF kJ/kg hS kJ/kg

hC kJ/kg

When Tdatum = 32oF ,

FhF + q = (S + C)hM + WHV

or

FhF + q = ShS + ChC + WHV

When Tdatum = Tequil./sat. , FhF + q = Wλ + ChC = Wλ + CΔH∞crys

#

heat of crystallization, ΔHcrys = - heat of solution at infinite dilution, "H

soln

Heat absorbed, q = + ve ,Heat given off , q = - ve

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5

ENTHALPY-CONCENTRATION DIAGRAM

nH2O system at 1 atm

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ENTHALPY-CONCENTRATION DIAGRAM

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6

EXAMPLE

(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.

Ans: -4260 Btu

nH2O system at 1 atm

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EXAMPLE 12.11-2

(54.4oC) containing 48.2 kg MgSO4/100

kg total water is cooled to 293.2 K (20oC)

where MgSO4.7H2O crystals 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 (18oC) is 13.31 x 103

kJ/kg mol MgSO4.7H2O. Calculate the

yield of crystals and make a heat balance

to determine the total heat evolved and

removed from the crystalliser, q,

assuming that no water is vaporized.

Data: Molecular weight of MgSO4•7H20

is 246.49

Ans: 616.9 kg crystal, -261 912 kJ

Enthalpy-concentration diagram for the MgSO4-

nH2O system at 1 atm

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7

EXAMPLE 12.11-2

Solution:

Molecular weights: MgSO4 = 120.4, 7H2O = 126, MgSO4 •7H2O = 246.4

2268 kg S kg solution

48.2 kg MgSO4/100 kg H2O 35.5 kg MgSO4/100 kg H2O

C kg MgSO4 •7H2O

W = 0, water balance: 2268 # &= S# &+C# &

" 48.2 +100 % " 35.5+100 % " 246.4 %

MgSO4 balance: 2268 # &= S# &+C# &

" 48.2 +100 % " 35.5+100 % " 246.4 %

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EXAMPLE 12.11

Solu&on

Tref. = 293.2K (Tdatum)

Heat balance :

FhF + q = Wλ + ChC = Wλ + CΔH∞crys

Enthalpy of the feed , hF = CpΔT = (2.93)(327.6-293)

Heat of crystallization = -(54.0) = -54.0 kJ/kg crystals

Total heat absorbed, q

2268(2.93)(327.6-293) + q = 631.9(54.0)

q = 631.9(54.0) - 2268(2.93)(327.6-293) = -262 689 kJ

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8

EXAMPLE

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.

Ans: 240 407 kJ

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