Process Calculations

S3CH01

Dr. Sudhir Ranganath

Contact Hours/Week: 3 (Lecture) Credits: 4.0

Contact Hours/Week: 3 (Lecture) + 1 (Study Hour) Credits: 3.0
CIE Marks: 50
Total Lecture Hours: 39 CIE Marks: 50
SEE Marks: 50
Total Hours: 42 (L) SEE Marks: 50
UNIT II
Material balance without reaction for steady and
unsteady operations

Typical steady state material balances for evaporation,

drying, mixing, distillation, absorption, extraction, and
crystallization
Material Balance in Crystallization
Crystallization is a unit operation where solid crystals are produced by
evaporating and/or cooling a saturated solution in a Crystallizer.

Crystallization is one of the last steps of a production process, where in almost

pure product is obtained in the form of crystals. Crystallization occurs when the
solution is concentrated by heating or cooling the solution until the solute
concentration becomes greater than the solubility of the solute at that
temperature. When the solution is saturated, equilibrium is said to have
attained. Therefore, difference in solubility of the solute at different
temperatures is the driving force for crystallization.

Examples include (i) crystallization of all kinds of salts (ii) sugar crystallization
(iii) proteins, etc.

Commonly used industrial dryers include:

Tank crystallizers
Agitated batch crystallizers
Evaporative crystallizers
Swenson-Walker crystallizers
Vacuum crystallizers… and many more
Material Balance in Crystallization
The crystallization equilibrium is
shown in the solubility curve
below.

Solubility of solids in a solvent

generally increases with rise in
temperature, however some show
reduced solubility with increase in
temperature for eg., Ce(SO4)3.
Material Balance in Crystallization

Some salts such as sodium thiosulfate (shown in the image above) have
several breaks in their solubility curve, which indicates that it exists as a
hydrated molecule. The number of molecules of hydration (water) depends on
the temperature. At low temperatures, it can retain more molecules of hydration
and at high temperatures, it starts losing water molecules and finally becomes
anhydrous.
Material Balance in Crystallization
In evaporative crystallization, a feed solution containing the solute is heated
to evaporate the solvent. After it reaches a certain temperature, the
concentration of the solute in the feed will be more than the solubility value,
thus, crystallization begins.

The saturated liquid (mother liquor) and the crystals will be in equilibrium at
that temperature of crystallization. Yield of the crystals can be calculated by
knowing the initial concentration of the solute, final temperature and solubility
of the solute at that temperature.

Water evaporated, 𝑉 kg

Feed solution, 𝐹 kg Evaporative Hydrated crystals, 𝐶 kg

𝑥𝐹 weight fraction of solute Crystallization 𝑥𝑐 weight fraction of solute

Mother liquor, 𝑀 kg
𝑥𝑀 weight fraction of solute
Material Balance in Crystallization
Let 𝐶 kg of hydrated crystals are formed in which the weight fraction of the
solute is 𝑥𝑐 from 𝐹 kg of feed solution containing 𝑥𝐹 weight fraction of solute.

Let 𝑥𝑀 be the solubility of the solute in the solvent (in weight fraction), and 𝑀
be the weight of the mother liquor remaining after crystallization. 𝑉 be the
weight of water evaporated during crystallization.

Total material balance: 𝐹 = 𝑉 + 𝑀 + 𝐶

Solute balance: 𝐹𝑥𝐹 = 𝑀𝑥𝑀 + 𝐶𝑥𝑐

Solvent balance: 𝐹(1 − 𝑥𝐹 ) = 𝑀(1 − 𝑥𝑀 ) + 𝐶(1 − 𝑥𝑐 ) + 𝑉

When the crystals are anhydrous, then 𝑥𝑐 = 1

Material Balance in Crystallization
In cooling crystallization, the feed is cooled to a lower temperature so that
the solubility of the solute decreases and it starts crystallizing. Let 𝐶 kg of
hydrated crystals are formed in which the weight fraction of the solute is 𝑥𝑐
from 𝐹 kg of feed solution containing 𝑥𝐹 weight fraction of solute.
Feed solution, 𝐹 kg Cooling Hydrated crystals, 𝐶 kg
𝑥𝐹 weight fraction of solute Crystallization 𝑥𝑐 weight fraction of solute

Mother liquor, 𝑀 kg
𝑥𝑀 weight fraction of solute

Let 𝑥𝑀 be the solubility of the solute in weight fraction of solute, and 𝑀 be the
weight of the mother liquor remaining after crystallization.

Total material balance: 𝐹 = 𝑀 + 𝐶

Solute balance: 𝐹𝑥𝐹 = 𝑀𝑥𝑀 + 𝐶𝑥𝑐

Solvent balance: 𝐹(1 − 𝑥𝐹 ) = 𝑀(1 − 𝑥𝑀 ) + 𝐶(1 − 𝑥𝑐 )

When the crystals are anhydrous, then 𝑥𝑐 = 1

Problem 60
A solution of potassium dichromate in water contains 15% by weight K2Cr2O7.
Calculate the amount of K2Cr2O7 that can be produced from 1500 kg of
solution if 700 kg of water is evaporated and remaining solution is cooled to
293 K. Solubility of K2Cr2O7 at 293 K is 115 kg per 1000 kg water.
Solution: Basis is 1500 kg of feed to the evaporator

Water evaporated, 𝑉 = 700 kg Crystals, 𝐶 kg

Cooling
Evaporator
Feed, 𝐹 kg Thick liquor, 𝐿 kg Crystallizer
𝑥𝐹 = 0.15 𝑥1
Mother liquor, 𝑀 kg
𝑥𝑀

Weight of K2Cr2O7 in the feed solution = 𝐹𝑥𝐹 = 1500 × 0.15 = 225 kg

Weight of water in the feed solution = 𝐹(1 − 𝑥𝐹 ) = 1500 × 0.85 = 1275 kg

Solution to Problem 60
Material balance for water:

Water in M = Water in feed - Water evaporated = 1275 - 700 = 575 kg

1000 kg of water contains 115 kg of K2Cr2O7 (from solubility data)

So, 575 kg water contains 115 x 575/1000 = 66.125 kg

𝑀 = 575 + 66.125 = 641.125 kg

𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 K2Cr2O7 66.125

𝑥𝑀 = = = 0.103
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 (K2Cr2O7 + 𝑤𝑎𝑡𝑒𝑟) (66.125 + 575)

Therefore, M contains 66.125 kg of K2Cr2O7

Material balance for K2Cr2O7: 𝐹𝑥𝐹 = 𝑀𝑥𝑀 + 𝐶

Therefore, 𝐶 = 𝐹𝑥𝐹 − 𝑀𝑥𝑀 = 225 − 66.125 = 158.9 kg

Weight of K2Cr2O7 crystals produced = 158.9 kg

Problem 61
A solution containing 53.8 g MgSO4 per 100 g of water is cooled from 353 K to
323 K when 6% of water is evaporated. How many kg of MgSO4.7H2O crystals
are obtained per 100 kg original solution. At 323 K, the solution contains only
0.3 mass fraction of MgSO4.
Solution: Basis is 100 kg of feed solution at 353 K
Water evaporated, 𝑉 kg

Evaporator
Feed, 𝐹 = 100 kg Crystals, 𝐶 kg
𝑥𝐹 𝑥𝑐

Mother liquor, 𝑀 kg
𝑥𝑀 = 0.3

𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑀𝑔𝑆𝑂4 53.8

𝑥𝐹 = = = 0.3498
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑓𝑒𝑒𝑑 100 + 53.8

Water in the feed = 𝐹 1 − 𝑥𝐹 = 100 1 − 0.3498 = 65 kg of water

Solution to Problem 61
Water evaporated, 𝑉 = 6% 𝑜𝑓 65 𝑘𝑔 = 0.06 × 65 = 3.9 kg

Since, the crystals are made up of MgSO4.7H2O, 𝑥𝑐 may be written as:

Mol wt of MgSO4 120

𝑥𝑐 = = = 0.4878
Mol wt of MgSO4.7H2O 246

Overall material balance:

𝐹 = 𝑉 + 𝑀 + 𝐶 = 100 = 3.9 + 𝑀 + 𝐶 → 𝐶 + 𝑀 = 96.1 …… (1)

MgSO4 balance:

𝐹𝑥𝐹 = 𝑀𝑥𝑀 + 𝐶𝑥𝑐

100 0.3498 = 𝑀 0.3 + 𝐶 0.4878 = 0.3𝑀 + 0.4878 96.1 − 𝑀 = 34.98

𝑀 = 63.31 kg and 𝐶 = 32.79 kg

Problem 62
An aqueous solution of Na2SO4 is saturated at 35 °C. Calculate the percentage
of solute crystallized as Na2SO4.10H2O if it is cooled to 27 °C. Solubility at 27
°C is 23.3% Na2SO4 by weight and at 35 °C is 32.5% by weight.

Solution: Basis is 100 kg of feed solution at 35 °C

Cooling
Feed, 𝐹 = 100 kg Crystallizer Crystals, 𝐶 kg
𝑥𝐹 = 0.325 𝑥𝑐

Mother liquor, 𝑀 kg
𝑥𝑀 = 0.233

𝑥𝐹 = 0.325 and 𝑥𝑀 = 0.233

Since, the crystals contain Na2SO4.10H2O, hence, 𝑥𝑐 may be written as:

Mol wt of Na2SO4 142

𝑥𝑐 = = = 0.441
Mol wt of Na2SO4.10H2O 322
Solution to Problem 62
Overall material balance: 𝐹 = 𝑀 + 𝐶 = 100 …… (1)

Na2SO4 balance: 𝐹𝑥𝐹 = 𝑀𝑥𝑀 + 𝐶𝑥𝑐

100 0.325 = 𝑀 0.233 + 𝐶 0.441 = 0.233𝑀 + 0.441 100 − 𝑀 = 32.5

𝑀 = 55.76 kg and 𝐶 = 44.23 kg

Wt of Na2SO4 crystals formed 𝐶𝑥𝑐

% 𝑌𝑖𝑒𝑙𝑑 = × 100 = × 100 = 60%
Wt of Na2SO4 in the feed 𝐹𝑥𝐹
Problem 63
A tank holds 10000 kg saturated solution of NaHCO3 at 60 °C. It is required to
crystallize 500 kg NaHCO3 from this solution. To what temperature the solution
must be cooled? Solubility data is given below:
Temperature (°C) 60 50 40 30 20 10
Solubility (g NaHCO3/100 g water) 16.4 14.45 12.7 11.11 9.6 8.15

Solution: Basis is 10000 kg of saturated solution of NaHCO3

Cooling
Feed, 𝐹 = 10000 kg Crystallizer Crystals, 𝐶 = 500 kg
𝑥𝐹 𝑥𝑐 = 1

Mother liquor, 𝑀 kg
𝑥𝑀
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 NaHCO3 16.4
𝑥𝐹 = = = 0.141
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑓𝑒𝑒𝑑 100 + 16.4

Overall material balance: 𝐹 = 𝑀 + 𝐶 = 1000 = 𝑀 + 500 → 𝑀 = 9500 kg

NaHCO3 balance: 𝐹𝑥𝐹 = 𝑀𝑥𝑀 + 𝐶𝑥𝑐

Solution to Problem 63
10000 0.141 = 9500𝑥𝑀 + 500 → 𝑥𝑀 = 0.09578

Let the solubility of NaHCO3 be 𝑆 in the mother liquor. Then we can write:

𝑆 𝑔 𝑁𝑎𝐻𝐶𝑂3
𝑥𝑀 = 𝑆+100 = 0.09578 → 𝑆 = 10.59 100 𝑔 𝑤𝑎𝑡𝑒𝑟

To find the temperature to which the feed should be cooled is obtained by

plotting temperature vs solubility.
18
Solubility (g Sodium bicarbonate / 100 g water)

16

14

12

10

4
From graph, the
2
temperature corresponding
0
to 𝑆 = 10.59 is 25 °C
10 20 30 40 50 60
Temperature (degree Celsius)
Problem 64
150 kg of saturated solution of AgNO3 at 100 °C is cooled to 20 °C. The
crystals are filtered out. Wet filter cake contains 80% solid crystals and 20%
saturated solution by mass which is sent to a dryer. Calculate the amount of
water that must be removed to get a moisture-free product. Also, calculate the
weight of dry AgNO3 obtained. Solubility of AgNO3 at 100 °C is 952 g per 100 g
water and at 20 °C is 222 g per 100 g water.

Solution: Basis is 150 kg of saturated solution of AgNO3 at 100 °C

Feed, Cooling
Dryer
𝐹 = 150 kg Crystallizer Wet crystals, 𝐶 kg Dry crystals
𝑥𝐹 𝑥𝑐 = 0.8 𝐷 kg

Mother liquor, 𝑀 kg Water removed, 𝑊 kg

𝑥𝑀

𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 AgNO3 952

𝑥𝐹 = = = 0.9051
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑓𝑒𝑒𝑑 100 + 952

𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 AgNO3 222

𝑥𝑀 = = = 0.689
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑀 100 + 222
Solution to Problem 64
Overall material balance on the crystallizer: 𝐹 = 𝑀 + 𝐶 = 150

Solute balance on the crystallizer:

AgNO3 in feed = AgNO3 in mother liquor + AgNO3 in wet crystals

AgNO3 in wet crystals = Dry AgNO3 crystals + AgNO3 in the mother liquor
adhering to the crystals

𝐹𝑥𝐹 = 𝑀𝑥𝑀 + 𝐶𝑥𝑐 + 𝐶(1 − 𝑥𝑐 )𝑥𝑀

150 0.9051 = 0.689𝑀 + 0.8𝐶 + 0.2𝐶 0.689 → 𝐶 = 130.226 kg

Therefore, weight of dry crystals in 𝐶 = 0.8𝐶 = 104.181 kg

AgNO3 in the mother liquor adhering to crystals in 𝐶 = 0.2𝐶 0.689 = 17.95 kg

Total dry crystals obtained after drying 𝐷 = 104.181 + 17.95 = 122.13 kg

Water to be evaporated 𝑊 = 𝐶 − 𝐷 = 130.226 − 122.13 = 8.1 kg

Thank you