Revised Study

Material

For

GATE PSU

Chemical Engineering
Process Calculations

GATE Syllabus

Laws of conservation of mass and energy; use of tie

components; recycle, bypass and purge calculations;
degree of freedom analysis.

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TABLE OF CONTENTS
Chapter 1

UNITS AND DIMENSIONS

1.1 Dimensions And System of Units
1.2 Fundamental And Derived Units
1.3 Dimensional Consistency
1.4 Dimensional Equations
1.5 Conversion Factor

2
2
2
5
5
6

Chapter 2

BASIC CHEMICAL CALCULATIONS

2.1 Composition of Mixtures
2.2 Ideal Gas Laws And Its Applications
2.2.1 Dalton Law
2.2.2 Raoults Law
2.2.3 Henrys Law
2.3 Relationship Between Partial Pressure And Mole Fraction of Component Gas to Total
Pressure

8
9
11
13
13
14
14

Chapter 3

MATERIAL BALANCE WITHOUT CHEMICAL REACTION

3.1 Material Balance
3.2 Material Balance Without Chemical Reaction
3.3 Material Balance Around Unit Operations
3.3.1 Distillation
3.3.2 Absorption
3.3.3 Extraction
3.3.4 Drying
3.3.5 Evaporation
3.3.6 Crystallization
3.3.7 Mixing / Blending
3.3.8 Filtration
3.4 Material Balance With Recycle, Bypass And Purge Streams
3.4.1 Recycling
3.4.2 Purging
3.4.3 Bypassing

20
20
20
21
21
22
22
23
23
24
24
25
25
25
26
27

Chapter 4

MATERIAL BALANCE INVOLVING CHEMICAL REACTION

4.1 Concept of Limiting And Excess Reactants

4.2 Conversion And Yield
4.3 Material Balance Involving Reactions

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Chapter 5

ENERGY BALANCE
5.1 Heat
5.2 Heat Capacity
5.2.1 Relationship Between Cv And Cp for an ideal gas
5.2.2 Empirical Equations For Heat Capacity
[Link] Heat Capacities of Gases at Constant Pressure
[Link] Mean Molar Heat Capacities of Gases
[Link] Heat Capacities of Gaseous Mixture
5.3 Phase Transitions
5.4 Enthalpy Changes Accompanied By Chemical Reactions
5.4.1 Heat of Reaction
5.4.2 Heat of Formation
5.5 Hesss Law of Constant Heat Summation

41
41
41
42
43
43
43
44
44
45
45
45
45

Chapter 6

FUELS AND COMBUSTION

50
50
50
50
50
50
51
51
51
52
52
52
53
53
53
54
54
54
54
55
56
57
57
57
58
58

LEVEL 1
LEVEL 2

63
73

6.1 Fuels
6.2 Types of Fuels
6.2.1 Liquid Fuels
[Link] Density
[Link] Specific Gravity
[Link] Viscosity
[Link] Flash Point
[Link] Pour Point
[Link] Specific Heat
[Link] Calorific Value of Fuels
[Link] Sulfur
[Link] Ash Content
[Link] Carbon Content
[Link] Water Content
6.2.2 Solid Fuels
[Link] Coal Classification
[Link] Physical And Chemical Properties of Coal
6.2.3 Analysis of Coal
[Link] Proximate Analysis
[Link] Ultimate Analysis
6.2.4 Gaseous Fuels
6.3 Combustion
6.3.1 Principle of Combustion
6.3.2 3 Ts of Combustion
6.4 Theoretical Oxygen Requirement

Chapter 7

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Chapter 8
UNSOLVED QUESTIONS

88

QUESTIONS (2004 TO 2015)

95
95
97
99
100
101
103
106
106
107
109
110
111

SOLUTIONS

112

Chapter 9
2004
2005
2006
2007
2008
2009
2010
2011
2012
2013
2014
2015

Chapter 10

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CHAPTER
3

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MATERIAL BALANCE WITHOUT CHEMICAL

REACTION

3.1 MATERIAL BALANCE

All material balance calculations are based on the law of conservation of mass, which
states that matter can neither be created nor destroyed during s process (i.e. mass is
conserved). The law of conservation of mass can also be stated as:

The total mass of all substances taking part in a process remains constant.

Within a given isolated system, the mass of the system remains constant,
regardless of the changes taking place within the system.

The total mass of various components remains constant during an unit operation
or a chemical reaction.

According to the law of conservation of mass, we have for any process

Input = Output + Accumulation
For steady state operations / process where in the accumulation of the material is
constant or nil, equation becomes,
Input = Output

Accumulation : It refers to change in mass or moles within the system with

respect to time (i.e. variables are time invariant).

3.2 MATERIAL BALANCE WITHOUT CHEMICAL REACTION

General methods for solving the material balance problems of the system involving no
chemical reactions are:

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Select a suitable basis of calculation.

When the system involves a component material that appears in both the
incoming and outgoing streams, whose quantity does not change during a given
operation, the component is called tie component.

Whenever we are dealing with the system involving an inert chemical species, the
calculation may be simplified by making material balance of the inert chemical
species.

3.3 MATERIAL BALANCE AROUND UNIT OPERATIONS

There are many unit operations used in chemical industries, and their respective simplify
block diagram.

3.3.1 DISTILLATION
This operation is used for the separation of the components of a liquid mixture by
partial vaporization and condensation. Distillation with rectification or (fractional
distillation) gives almost pure product. The product removed from the top is called the
distillate or overhead product and that removed from the bottom is called the bottoms
or bottom product. Material balance is generally based on the more volatile component.
The vapor phase is created by supplying thermal energy to liquid to be distilled and this
method of separation depends on the difference
in vapor pressures of different components at a
given temperature.
Overall material balance :
F =D+B
Where, F = Feed Rate, D = Distillate Rate, W = Bottoms Rate
Material balance of component a :
A in feed = A in distillate + A in bottoms

xF .F xD .D xW .W
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3.3.2 ABSORPTION
This operation is used in the chemical industry for the recovery / removal of a solute gas
component from its mixture with another component gases (called as inert gases with
respect to absorption) with the help of a suitable liquid solvent in which the solute gas is
absorbed. Mathematically agitated vessels, packed columns, etc. are the equipments
commonly used for absorption.
Material balance of inert gas :
Inert gas in gas mixture entering the tower
= Inert gas leaving the tower
Material balance of solute gas :
Solute removed by absorption = Solute in inlet gas Solute in lean gas

3.3.3 EXTRACTION
This operation is used in the chemical industry for the separation of the components of
a liquid mixture with the help of a suitable liquid solvent wherein the solute from the
feed solution is transferred in the solvent yielding the raffinate phase (rich in the feed
solvent) and extract phase (rich in the solvent
used). It does not give a pure product and
needs

further

processing.

Mixer

settlers,

packed columns etc. are used for liquid liquid

extraction.
Overall material balance :
Feed solution + Solvent = Extract phase + Raffinate phase
If A is the solute to be extracted, then the material balance of A for fresh solvent is:
A in feed solution = A in extract phase + A in raffinate phase

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Extraction operation is also carried out for the removal of a soluble constituent of solids
with the help of a suitable liquid solvent. For
example, oil seed extraction or leaching of valuable
metals from mineral ores.
Material balance of solids :
Solids in seeds = Solids in meal
Material balance of oil :
Oil in seeds = Oil in meal + Oil in solvent

3.3.4 DRYING
This operation is carried out in the chemical industry for the removal of residual
moisture (water) or volatile liquid associated with wet solids with the help of hot air, or
inert gas (N2) (drying medium). When the hot air is
circulated over the wet solids, the moisture from
the solids evaporates and gets added in the air. It
is generally the last operation carried out in the
industry. Industrial dryers include tray dryer, spray
dryer, etc.
Material balance of moisture :
Moisture removed from solids = moisture added in air
Initial moisture in wet solids Moisture in dried solids
= Moisture in outlet air moisture in inlet air
Material balance of solids :
Solids in wet feed = Solids in dried product

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3.3.5 EVAPORATION
This operation is used in the chemical
industry to enhance the concentration
of a weak liquor to produce a thick
liquor by evaporating a portion of the
solvent

by

means

of

condensing

steam. It may be carried out in a single

or

multiple

effect

evaporation

system.
Overall Material Balance :
Weak liquor = Water evaporated + Crystallized Product + Thick liquor
Material balance of solids :
Solids in weak liquor = Solids in thick liquor

3.3.6 CRYSTALLIZATION
It is formation of solid particles within a homogeneous liquid phase. Crystallization gives
almost

pure

equipments

used

product.
for

Various

carrying

out

crystallization are stirred tanks, vacuum

crystallizer, Swenson walker crystallizer,
etc. crystallization of dissolved solids from a solution is based on the differences in
solubility at different temperatures. It usually consists of concentration of solution and
cooling of solution until it becomes super saturated.
Overall material balance :
Feed solution = Saturated solution + Crystals
Material balance of solute crystals :
Crystals in feed solution = Crystals obtained + Crystals in saturated solution
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3.3.7 MIXING / BLENDING

This operation is carried out in the chemical industry to obtain a product of the desired
quality by mixing weak and concentrated
streams. For example, preparation of a
desired mixed acid, blending of solids from
various batches to get solids of a specified
quality, etc.
Suppose a product stream is to be obtained by blending streams 1, 2 and 3, then
Overall material balance :
Feed Stream 1 + Feed Stream 2 + Feed Stream 3 = Desired product stream
Component material balance :
A in Feed Stream 1 + A in Feed Stream 2 = A in desired product stream

3.3.8 FILTRATION
This operation is carried out in the industry for
the separation of solids from a suspension in a
liquid. Wet solids are the product of this
operation. Various equipments used for this
purpose are: centrifuge machines, drum filter
press, etc.
Overall material balance :
Feed slurry

= Wet solids + Filtrate

Material balance of solids :

Solids in slurry

25

= Solids in wet solids product + Solids in filtrate

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3.4 MATERIAL BALANCE WITH RECYCLE, BYPASS AND PURGE STREAMS

3.4.1 RECYCLING
In recycling operation, Recycling is returning back a portion of stream leaving the
process unit to the entrance of a process
unit for further processing. This operation
is carried out under steady state.

overall conversion =

A in fresh feed A in net product

A in fresh feed

single pass conversion =

A in mixed feed A in gross product

A in mixed feed

Recycle Ratio : It is the ratio of the quantity of recycle stream to the quantity of
fresh feed stream.
Recycle Ratio =

R
F

Combined Feed Ratio : It is the ratio quantity of mixed feed stream to the
quantity of fresh feed stream.
Combined Feed Ratio =

26

M
F

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3.4.2 PURGING
Purge stream is the fraction of recycled
stream which is continuously taken off in
order to avoid an accumulation of inerts in
the recycle loop.

At steady state,

Inerts in purge = Inerts in fresh feed

Purge Ratio =

P
R

3.4.3 BYPASSING
A stream that skips one or more stages of the process and goes directly to another
downstream stage.

Example 3.1 A single effect evaporator is fed with 10000 kg / h of weak liquor
containing 15 % caustic by weight and is concentrated to get thick liquor
containing 40 % by weight caustic. Calculate:
(a) kg / h of water evaporated and
(b) kg / h of thick liquor
Solution:

Basis: 10000 kg / h of weak liquor.

Let x be the kg / h thick liquor obtained and y be the kg / h water evaporated.

27

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Overall Material balance:

Total mass Input = Total mass output
kg / h weak liquor = kg / h water
evaporated + kg / h thick liquor
10000 = x + y
Material Balance of NaOH:
NaOH in the liquid stream = NaOH in output stream
NaOH in the weak liquor = NaOH in thick liquor
0.15 10000 0.40 x
x 3750 kg / hr
Hence,
y 6250 kg / hr

Water evaporated = 6250 kg / h

Thick liquor obtained = 3750 kg / h

Example 3.2 The waste acid from a nitrating process contains 30 % H2SO4, 35 %
HNO3 and 35 % H2O w/w. the acid is to be concentrated to contain 39 % H2SO4
and 42% HNO3 by addition of concentrated sulfuric acid containing 98% H2SO4
and concentrated Nitric acid containing 72 % HNO3. Calculate the quantities of
three acids to be mixed to get 1000 kg of desired mixed acid.
Solution:

Basis: 1000 kg of desired mixed acid.

Let x, y and z be the kg of waste acid, conc. Sulfuric acid and conc. Nitric acid required
to make 1000 kg desired acid.

Overall Material Balance:

x + y + z = 1000..(i)

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Material Balance of H2SO4:

0.3x + 0.98y = 0.39 1000

0.3x + 0.98y = 390 ..(ii)

0.35x + 0.72y = 420..(iii)

Material Balance of HNO3:

0.35x + 0.72z = 0.42 1000
From equations (i), (ii) and (ii), we get
x = 90.1 kg,

y = 370.4 kg, z = 539.5 kg

Thus,
Amount of waste acid required = 90.1 kg
Amount of conc. Sulfuric acid required

= 370.4 kg

Amount of conc. Nitric acid required

= 539.5 kg

Example 3.3 Fresh juice contains 15% solids and 85 % water by weight and is to be
concentrated to contain 40 % solids by weight.
In a single evaporation system, it is found that volatile constituents of juice
escape with water leaving the concentrated juice with a flat taste. In order to
overcome this problem, part of the fresh juice bypasses the evaporator. The
operation is shown schematically in figure given below:

Calculate:
(a) The fraction of juice that bypasses the evaporator.
(b) The concentrated juice produced (containing 40 % solids) per 100 kg of
fresh juice fed to the process.

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Solution:

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Basis: 100 kg of fresh juice fed to the process.

Let x and y be the kg of juice fed to the evaporator and p be the kg of the concentrated
juice obtained.

Material balance over the separation of bypass stream

x + y = 100(i)
Material balance of solids over Evaporator:
0.15x = 0.55z(ii)
Overall material balance after Evaporator:
z + y = p(iii)
Material balance of solids after Evaporator:
0.55z + 0.15 y = 0.40p(iv)
From equation (i), (ii), (iii) and (iv), we get
x = 85.94 kg,

y = 14.06 kg, z = 23.44 kg, p = 37.5 kg

Fraction of juice that bypass evaporator in %,

y
14.06
100
100 = 14.06 %
100
100

Quantity of concentrated juice obtained finally

p = 37.5 kg

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Example 3.4 In a particular drying operation, it is required to have the moisture

content of feed to a calciner at 15 % by weight in order to prevent lumping and
sticking. This is achieved by mixing the feed having 30 % by weight moisture with
a recycle stream of dried material having 3% by weight moisture. The drying
operation is shown in figure. Find the fraction of the dried product that must be
recycled.

Solution:

Basis: 100 kg of fresh feed.

It contains 70 kg solids and 30 kg moisture.

Let F, R and M be the kg of fresh feed, recycle feed and mixed feed respectively.
M=F+R
Weve,

F = 100 kg

Material balance of moisture:

0.15 M = 0.30 (100) + 0.03 R = 30 + 0.03 R
Weve M = 100 + R
0.15 (100 + R) = 30 + 0.03 R
R = 125 kg
And

M = 100 + 125 = 225 kg

Let x be the kg of the product leaving the calciner. The solid balance about the calciner
gives
0.97 = 0.85 225
x = 197.2 kg
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Fraction of the dried product that must be recycled

R
125

0.634
x 197.2

= 63.4 %
Water removed from the calciner = 225 197.2 = 27.8 kg
Product obtained (P) = x R
Product obtained (P) = 197.2 125 = 72.2 kg

Example 3.5 A solution of potassium dichromate in water contains 15% w/w

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 293K.
Data: Solubility of K2Cr2O7 at 293 K is 115 kg per 1000 kg of water.
Solution:

Basis: 1500 kg of solution.

K2Cr2O7 content of solution

Water in 15 % solution

0.15 1500

225 kg

1500 225

1275 kg

Water evaporated

Water in final

M.B. of Water:
Water in 15 5 solution

solution

Water in final solution

1275 700

Solubility of K2Cr2O7 at 293 K

115 kg / 1000 kg water

Amount of K 2Cr2O7 at 293 K

115
575
1000

575 kg

66.125 kg

M.B. of K2Cr2O7:

K 2Cr2O7 in

feed solution
32

K 2Cr2O7 in

K 2Cr2O7 produced

solution at 293 K
as crystals

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Amount of K 2Cr2O7 crystals produced

=

225

66.125 =

158.875 kg

Example 3.6 A mixture of NaCl and KCl was treated with H2SO4 and 1.175 kg of
mixed sulphate (Na2SO4 and K2SO4) was obtained. If the original sample is 1 kg.
estimate the % of Cl2 in the sample.

Solution:

Basis: 1 kg of sample containing NaCl and KCl.

2NaCl H 2SO4
Na2SO4 2HCl
2KCl H 2SO4
K 2SO4 2HCl
Molecular weight : KCl = 74.5,

NaCl = 58.5,

Na2SO4 = 142,

K2SO4 = 174

In 1 kg mixture, let there be m kg of NaCl.

=

1 m kg

Na2SO4 produced by rxn (1)

142m
1.214m kg
2 58.5

K2SO4 formed by rxn (2)

174
(1 m ) 1.168(1 m ) kg
2 74.5

1.175 kg

KCl in the mixture

The weight of mixture

Thus,
1.214m

1.168(1 m) =

1.175

0.152 kg

Amount of NaCl

0.152 kg

Amount of KCl

0.152

0.848 kg

Therefore,

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Cl in NaCl

35.5
0.152
58.5

0.092 kg

Cl in KCl

35.5
0.848
74.5

0.404 kg

Total Cl in the sample

0.092 + 0.404 =

0.496 kg

0.496
100
1

49.6 %

% of Cl in sample

Example 3.7 A gas mixture containing 15 mol % A and 85 mol % inerts is fed to an
absorption tower where it is connected with liquid solvent B which absorbs A.
the mole ratio of solvent to gas entering tower is 2 : 1. The gas leaving the
absorber contains 2.5 % A, 1.5 % B and rest inerts (on mole basis). Find:
(a) The % recovery of solute A and
(b) The fraction of solvent B fed to column loast in gas leaving the tower.
Note that during the process, some solvent evaporates and gets added in the gas
leaving the tower.
Solution:

34

Basis: 100 kmol of gas entering the absorber per unit time.

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Mole ratio of solvent to gas entering is 2 : 1.

Solvent fed to tower per unit time

2
100
1

Inerts in gas entering tower

0.85 100

= 200 kmol

M.B. of inerts :
Inerts in outlet gas

85 kmol /

time
Let n be the kmol of gas leaving the tower per unit time.
Mole % inerts in gas leaving

100

(mol % A + mol % B)

100

(2.5 + 1.5)

96 kmol

96

85
100
n

88.54 kmol per unit time

Thus,

M.B. of Solute A :
A in inlet gas
0.15 100

A in outlet gas + A absorbed in solvent

0.025 88.54

A absorbed =
% recovery of A

Solvent B in gas leaving

35

15

+ A absorbed
2.21

'A' absorbed
100
'A' in inlet gas

12.79
100
15

0.015

12.79 kmol / time

85.27 %

88.54 =

1.33 kmol

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tower per unit time

Fraction of solvent fed to column lost in gas leaving the tower

=

'B' in gas leaving

'B' entering the tower

1.33
200

0.0066

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