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PROCESS CALCULATIONS
PROCESS CALCULATIONS
SECOND EDITION
V. VENKATARAMANI Formerly Professor
Department of Chemical Engineering National Institute of Technology Tiruchirappalli
N. ANANTHARAMAN Professor
Department of Chemical Engineering National Institute of Technology Tiruchirappalli
K.M. MEERA SHERIFFA BEGUM Associate Professor
Department of Chemical Engineering National Institute of Technology Tiruchirappalli
New Delhi-110001 2011

PROCESS CALCULATIONS, Second Edition
V. Venkataramani, N. Anantharaman and K.M. Meera Sheriffa Begum
2011 by PHI Learning Private Limited, New Delhi. All rights reserved. No part of this book may be reproduced in any form, by
mimeograph or any other means, without permission in writing from the publisher.
ISBN-978-81-203-4199-9
The export rights of this book are vested solely with the publisher.
Second Printing (Second Edition) February, 2011
Published by Asoke K. Ghosh, PHI Learning Private Limited, M-97, Connaught Circus, New Delhi-110001 and Printed by Meenakshi
Art Printers, Delhi-110006.

To My Parents
V. Venkataramani
K.M. Meera Sheriffa Begum
To My Mother
N. Anantharaman
Contents
Preface .............................................................................................................. xi Preface to the First
Edition ............................................................................ xiii Acknowledgements
........................................................................................... xv
1 UNITS AND DIMENSIONS 16
1.1 Introduction ..................................................................................... 1
1.2 Basic Units and Notations ............................................................... 1
1.3 Derived Units ................................................................................... 2
1.4 Definitions ....................................................................................... 3
Worked Examples ..................................................................................... 3
Exercises ................................................................................................... 6
2 MASS RELATIONS 734
2.1 Mass Relations in Chemical Reaction ............................................. 7
2.2 Conservation of Mass ...................................................................... 8
2.3 Avogadros Hypothesis .................................................................... 9
2.4 Limiting Reactant and Excess Reactant .......................................... 9
2.5 Conversion and Yield ....................................................................... 9
2.6 Composition of Mixtures and Solutions ........................................ 10
2.6.1 Weight Percent ................................................................... 10
2.6.2 Volume Percent .................................................................. 10
2.6.3 Mole Fraction and Mole Percent ....................................... 11
2.6.4 Atomic Fraction and Atomic Percent ................................ 11
2.6.5 Composition of Liquid Systems ........................................ 11
2.7 Density and Specific Gravity ......................................................... 12
2.7.1 Baume (Be) Gravity Scale ............................................. 12
2.7.2 API Scale (American Petroleum Institute) ........................ 12
2.7.3 Twaddell Scale ................................................................... 13
2.7.4 Brix Scale .......................................................................... 13
Worked Examples ................................................................................... 13
Exercises ................................................................................................. 32
vii
viii
CONTENTS
3 IDEAL GASES 3573
3.1 Relation between Mass and Volume for Gaseous Substances ....... 35
3.1.1 Standard Conditions .......................................................... 35
3.1.2 Ideal Gas Law .................................................................... 35
3.2 Gaseous Mixture ............................................................................ 36
3.2.1 Partial Pressure (PP) .......................................................... 36
3.2.2 Pure Component Volume (PCV) ....................................... 36
3.2.3 Daltons Law ..................................................................... 37
3.2.4 Amagats Law (or) Leducs Law ....................................... 37
3.3 Average Molecular weight ............................................................. 38
3.4 Density of Mixture ......................................................................... 38
Worked Examples ................................................................................... 38
Exercises ................................................................................................. 70
4 VAPOUR PRESSURE 7486
4.1 Effect of Temperature on Vapour Pressure .................................... 74
4.2 Hausbrand Chart ............................................................................ 75
Worked Examples ................................................................................... 75
Exercises ................................................................................................. 85
5 PSYCHROMETRY 87110
5.1 Humidity ........................................................................................ 87
5.2 Definitions ..................................................................................... 87
Worked Examples ................................................................................... 90
Exercises ............................................................................................... 106
6 CRYSTALLIZATION 111121 Worked Examples
................................................................................. 112 Exercises
............................................................................................... 120
7 MASS BALANCE 122179
Worked Examples ................................................................................. 122
Exercises ............................................................................................... 173
8 RECYCLE AND BYPASS 180195
8.1 Recycle ........................................................................................ 180
8.2 Bypass .......................................................................................... 180
8.3 Purge............................................................................................ 180
Worked Examples ................................................................................. 181
Exercises ............................................................................................... 195
CONTENTS ix
9 ENERGY BALANCE 196220
9.1 Definitions ................................................................................... 196
9.1.1 Standard State .................................................................. 196
9.1.2 Heat of Formation ............................................................ 196
9.1.3 Heat of Combustion ......................................................... 197
9.1.4 The Heat of Reaction ....................................................... 197
9.1.5 Heat of Mixing ................................................................ 197
9.2 Hesss Law ................................................................................... 197
9.3 Kopps Rule ................................................................................. 198
9.4 Adiabatic Reaction Temperature ................................................. 198
9.5 Theoretical Flame Temperature ................................................... 198
Worked Examples ................................................................................. 198
Exercises ............................................................................................... 217
10 PROBLEMS ON UNSTEADY STATE OPERATIONS 221228 Worked Examples
................................................................................. 221 Exercises
............................................................................................... 227
T ables .................................................................................................... 229234
I Important Conversion Factors .............................................................229
II Atomic Weights and Atomic Numbers of Elements ......................... 231
III(a) Empirical Constants for Molal Heat Capacities of Gases at Constant Pressure
................................................................................. 234
III(b)Molal Heat Capacities of Hydrocarbon Gases .................................. 234
Answers to Exercises........................................................................... 235245
Index...................................................................................................... 247248
Preface
The objective of this book is to enrich a budding chemical engineer the techniques involved in
analyzing a process plant by introducing the concepts on units and conversions, mass and energy
balances. This will enable him to achieve a proper design of process equipment. An attempt has been
made to explain the principles involved through numerical examples. The problems are not only
confined to SI system of units but also worked out in other systems like FPS, CGS and MKS systems.
We feel that our attempt will be more rewarding if students come across data presented in FPS, CGS
and MKS systems while designing equipment, since different reference books give standard values
and data in various units.
The book covers various interesting topics such as units and dimensions, mass relations, properties of
gases, vapour pressure, psychrometry, crystallization, mass balance including recycle and bypass,
energy balance and unsteady state operations. The second edition is now enriched with additional
worked examples and exercises to give additional exposure and practice to students.
The text is designed for a one semester programme as a four credit course and takes care of the
syllabus on Process Calculations of most of the universities in India.
V. Venkataramani N. Anantharaman K.M. Meera Sheriffa Begum
xi
Preface to the First Edition
Chemical engineers in process industries generally need to focus on design, operation, control and
management of a process plant. It is, therefore, absolutely essential for them to be conversant with the
mass and energy conservation techniques at every stage of the process to achieve economy in the
design of process equipment in various units of the plant. This book aims at imparting knowledge of
the basic chemical engineering principles and techniques used in analyzing a chemical process. By
applying the relevant techniques, a chemical engineer is able to evaluate material and energy balances
in different units and present the information in a proper form so that the data can be used by the
management in taking correct decisions. Keeping this in mind, an attempt has been made to give a
brief theory on the principle involved and more emphasis on numerical examples.
Since data are generally obtained in different units, the worked examples are not confined to SI units,
but to other systems as well, such as FPS, CGS and MKS systems of units. The examples
incorporated in the text are simple and concrete to make the book useful for self-instruction.
The text is organized into ten chapters and appends three important tables. The organization is such
that the topics are presented in order of easy comprehension rather than following a logical sequence,
e.g. the chapter on unsteady state operations has been included as the last chapter so that students can
absorb the problems easily. We strongly feel that once the student understands the topics presented in
this book, he will find other advanced courses in chemical engineering simple and easy to follow.
The topics covered in this book cater to the syllabi on Process Calculations of most universities
offering courses in chemical engineering and its allied branches at the undergraduate level.
V. Venkataramani N. Anantharaman xiii
Acknowledgements
At the outset, we wish to thank the almighty for his blessings.
V. Venkataramani wishes to acknowledge his wife, Prof. (Mrs.) Booma Venkataramani, sons Mr. V.
Ravi Chandar, Mr. V. Hari Sundar and his daughters-in-law Mrs. Vandana Ravi Chandar and Mrs.
Ramya Hari Sundar and granddaughters Miss Vaishnavi Ravi Chandar and Miss Sadhana Hari Sundar
for their support, cooperation and patience shown during the preparation of this book.
N. Anantharaman wishes to thank his mother, wife, Dr. Usha Anantharaman, sons Master A. Srinivas
and A. Varun for all their patience, cooperation and support shown during the preparation of this
book. The encouragement received from his brothers and sisters and their family members is
gratefully acknowledged. He also wishes to place on record the support received from his brothers-
in-law and sisters-in-law and their family members.
K.M. Meera Sheriffa Begum wishes to acknowledge her mother, husband Mr. S. Malik Raj and baby
M. Rakshana Roshan for all their encouragement, support and cooperation while preparing this book.
She also wishes to place on record the support received from her parents-in-law. The support
received from her brothers, sisters, in-laws and their families is gratefully acknowledged.
We also thank Director, NIT, Tiruchirappalli for extending all the facilities and his words of
appreciation.
We wish to acknowledge the support and encouragement received from the Head of Chemical
Engineering Department and all our colleagues during the course of preparation of this book.
We also wish to place on record the suggestions received from students, especially those at NIT,
Tiruchirappalli, and also the faculty from other institutions.
xv xvi
ACKNOWLEDGEMENTS
We gratefully acknowledge all the well-wishers.
Finally, we wish to thank the publishers, PHI Learning, New Delhi for encouraging us to bring out the
second edition of the book.
V. Venkataramani N. Anantharaman K.M. Meera Sheriffa Begum
Units and Dimensions 1
1.1 INTRODUCTION
Chemical engineers are concerned with the design and development of processes which involve
changes in the bulk properties of matter. To make a quantitative estimation of these processes,
chemical equations showing the quantities of reactants and products are used. Though internationally
we follow SI system of units, a chemical engineer is expected to be familiar and conversant with all
the systems so far adopted for measuring and expressing various quantities. A review of literature and
data over the years will be available in various units. These are used to express properties, process
variables and design parameters in FPS, CGS, MKS and SI systems of Units. Hence, one has to be
conversant with their use and applications. This chapter deals with the basic notations and conversion
of a given quantity from one system of units to another.
The quantities used in our analysis are classified as fundamental quantities and derived quantities.
The fundamental quantities comprise length, mass, time and temperature. The quantities such as force,
density, pressure, mass flow rate derived from the fundamental quantities are called derived
quantities. While handling these quantities, we come across different systems of units as mentioned
earlier. Now let us see in detail these systems of units and their conversion from one unit to another.
1.2 BASIC UNITS AND NOTATIONS
English Metric Engineering System Engineering,
CGS MKS
International, FPS SI
Mass ( m) lb g kg kg Length (L)ft cmm m Time (t)ssss Temperature (T)F C C K
1
Mass (m)
1 kg = 2.205 lb
Length (L)
1 ft = 30.48 cm
= 0.3048 m
Time (t)
1 h = 3600 s
Temperature (T )
C=
F 32
(Celsius and Centigrade are same)
1.8
1.3 DERIVED UNITS
Area: = length breadth (L
2
):
1 ft
2
= 0.0929 m
2
10.76 ft
2
= 1 m
2
Force: = mass acceleration (mL/t
2
):
1 dyne = 1 g cm/s
2
(Force applied on a mass of 1 g, which gives an acceleration of 1 cm/s
2
)
1 Newton (N) = 1 kg m/s
2
= (1000 g) (100 cm)/s
2
1 N = 10
5
g cm / s
2
= 10
5
dynes
Work/energy: = 1 kg m/s
2
1 erg is the amount of work done on a mass of 1 g when it is displaced by 1 cm by applying a force of
1 dyne.
1 erg = [1 dyne] [1 cm]
= [1 g cm/s
2
] [1 cm]
= 1 g cm
2
/s
2
1 Joule = (1 N) (1 m)
= 10
5
g cm/s
2
100 cm
= 10
7
g cm
2
/s
2
1 Joule = 10
7
erg
Heat Unit:
1 Btu = 0.252 kcal = 252 cal
1 cal = 4.18 J
1 J/s = 1 W
1.4 DEFINITIONS
System. This refers to a substance or group of substances under consideration, e.g. storage tank,
water in a tank, hydrogen stored in cylinder, etc.
Process. Changes taking place within the system is called process, e.g. burning of fuel, or reaction
between two substances like hydrogen and oxygen to form water.
Isolated system. Boundaries of the system are limited by a mass of material, and its energy content is
completely detached from all other matter and energy. In an isolated system, the mass of the system
remains constant, regardless of the changes taking place within the system.
Extensive property. It is a state of system, which depends on the mass under consideration, e.g.
volume.
Intensive property. This state of a system is independent of mass. An example of this property is
temperature.
WORKED EXAMPLES
1.1 The superficial mass velocity is found to be 200 lb/h.ft
2
. Find its equivalent in kg/s.m
2
G (Mass velocity) = (200) lb/h.ft
2
=
(200)

11 1
m
2
(3600 s) (0.0929)

= 0.2712 kg/s.m
2
1.2 Convert the heat transfer coefficient of value 100 Btu/h.ft
2
.F into W/m
2
C
h (Heat transfer coefficient) = (100)
(0.0929 m
2
)
(1.8 C) [1 degree variation in Farh. scale is equivalent to 1.8 times the variation in celsius scale]
= 4.186 10
2
kcal/s.m
2
C = 4.186 10
2
10
3
4.18 W/m
2
C = 174.98 W/m
2
C
1.3 The rate of heat loss per unit area is given by (0.5) [(DT)
1.25
/(D)
0.25
] Btu/h ft
2
for a process,
where, DT is in F and D is in ft. Convert this relation to estimate the heat flux in terms of kcal/h. m
2
using DT in C and D in m.
We know that,
9
C
1
+ 32 = F
15

9
C
2
+ 32 = F
25
Therefore,
1.8 [DC] = (DF)

qT
()1.25

0.5()
0.25
A
q
, Btu/h ft
2
= 0.5
'(F)1.25
A (ft)
0.25
We know that,
1 Btu = 0.252 kcal
1 ft
2
= 0.0929 m
2
1 ft = 0.3048 m
For DT F = 1.8 DT C

1.25
Btu/h ft
2 = 0.5 '
(ft)
0.25 (a)


(1.8
'
T
C)

1.25

= (0.5)
(Dm/0.3048)
0.25(b)
= (0.7746)

'(C)
1.25
0.25
(m)
Btu/h ft
2
= (0.252 kcal)/h (0.0929 m
2
)
= 2.713 kcal/h m
2
(c)
From (b) and (c) we get the expression for heat flux in units of kcal/h m
2
with temperature difference
in Celsius and diameter in metre as:
Heat flux, kcal/h m
2
=
(m)0.25

T C)
1.25
'

2.713

(2.101)(
'
T
C)

1.25

=
(m)
0.25 (d)

Now let us check the conversion with the following data: D = 0.2 ft, i.e. D = 0.06096 m
DT = 18 F, i.e. DT = 10 C
From Eq. (a), heat flux is = 0.5
(18)
1.25

0.25
= 27.72 Btu/h ft
2
= 75.2 kcal/h m
2
(0.2)
Also, from Eq. (d), heat flux = 2.101

(10)
1.25
(0.06096)
0.25
= 75.2 kcal/h m
2
Both the values agree.
1.4 If C
p
of SO
2
is 10 cal/g mole K, what is the value in FPS units? The C
p
value is the same in all
units, i.e. 10 Btu/lb mole R.
1.5 Iron metal weighs 500 lb and occupies a volume of 29.25 litres. Find the density in kg/m
3
.
Basis: 500 lb of Iron = 500/2.2 = 227.27 kg
29.25 lit = 29.25 10
3
m
3
227.27
10
3
= 7770 kg/m
3
Density =
29.25
1.6 Etching operation follows the relation d = 16.2 16.2e
0.021t
, where t is in s. and d is in microns.
Convert this equation to evaluate d in mm with t in min.
d = 16.2 [1 e
0.021t
]
Let d be in mm and t be in min. (d = d 10
3
and t = t 60) Then, d = d 10
3
= 16.2 [1 e
0.021t
60
]
d = 0.0162 [1 e
1.26t
]
1.7 The density of fluid is given by r = 70.5 exp (8.27 10
7
). Convert this equation to calculate the
density in kg/m
3
with pressure in N/m
2
.
1000 kg/m
3
= 62.43 lb/ft
3
14.7 psi = 1.0133 10
5
N/m
2
1 kg/m
3
= 62.43 10
3
lb/ft
3
Let, r be in kg/m
3
and p be in N/m
2
.
Then, (r 62.43 10
3
) = 70.5 exp (8.27 10
7
p 14.7/1.0133 10
5
) r (kg/m
3
) = 1.129
10
3
exp [119.97 10
12
p (N/m
2
)]
1.8 Vapour pressure of benzene in the range of 7.5 C to 104 C is given by log
10
(p) = 6.9057
1211/(T + 220.8), where T is in C and p is in torr 1 torr = 133.3 N/m
2
. Convert it to SI units.
Let p be in N/m
2
and T be in K.
Then, log

p
= 6.9057
1211

(T
273)
220.8

1211
log p log 133.3 = 6.90305
T 52.2

log (p
1211
.) = 9.0305
T52.2
EXERCISES
1.1 Convert the following quantities:
(a) 42 ft
2
/h to cm
2
/s
(b) 25 psig to psia
(c) 100 Btu to hp-h
(d) 30 N/m
2
to lbf/ft
2
(e) 100 Btu/h ft
2
F to cal/s cm
2
C
(f) 1000 kcal/h mC to W/m K
1.2 The heat transfer coefficient for a stream to another is given by h = 16.6 C
p
G
0.8
/D
0.2
where h = Heat transfer coefficient in Btu/(h)(ft)
2
(F) D = Flow diameter, inches
G = Mass velocity, lb/(s)(ft)
2
C
p
= Specific heat, Btu/(lb) (F)
Convert this equation to express the heat transfer coefficient in kcal/ (h)(m)
2
(C)
With D = Flow diameter in m, G = Mass velocity in kg/(s)(m)
2
and C
p
= Specific heat, kcal/(kg) (C)
1.3 Mass flow through a nozzle as a function of gas pressure and temperature is given by m = 0.0549
p/(T)
0.5
where m is in lb/min, p is in psia and T is in R, where T(R) = T F + 460. Obtain an
expression for the mass flow rate in kg/s with p in atmospheres (atm) and T in K.
1.4 The flow past a triangular notch weir can be calculated by using the following empirical formula:
q = [0.31 h
2.5
/g
0.5
] tan F
where q = Volumetric flow rate, ft
3
/s
h = Weir head, ft
g = Local acceleration due to gravity, ft/s
2
F = Angle of V-notch with horizontal plane
1.5 In the case of liquids, the local heat transfer coefficient, for long tubes and using bulk-temperature
properties, is expressed by the empirical equation,
h
= 0.023
G
0.8
k
0.67
C
0.5
/(D
0.2
m
0.47
p )
where G = Mass velocity of liquids, lb/ft
2
.s
k = Thermal conductivity, Btu/ft.h.F
C
p
= Specific heat, Btu/lb F
D = Diameter of tube, ft
m = Viscosity of liquid, lb/ft.s
Convert the empirical equation to SI units.
Mass Relations 2
2.1 MASS RELATIONS IN CHEMICAL REACTION
In stoichiometric calculations, the mass relations between reactants and products of a chemical
reaction are considered and are based on the atomic weight of each element involved in the reaction.
For the following reactions the material balance is established as indicated below:
(i) CaCO
3
CaO + CO
2
(2.1) [40 + 12 + 3 16] [40 + 16] + [12 + 32] 100 56 + 44
(ii) 3Fe + 4H
2
O Fe
3
O
4
+ 4H
2
(2.2) (3 55.84) + 4(2 1 + 16) (55.84 3 + 4 16) + 4(2 1)
167.52 + 72 231.52 + 8 239.52 239.52
Based on the reactions given by Eqs. (2.1) and (2.2) we conclude that when 100 parts by weight of
CaCO
3
reacts, 56 parts by weight of CaO and 44 parts by weight of CO
2
are formed. Similarly, when
167.52 parts by weight of iron reacts with 72 parts by weight of steam (water), we get 231.52 parts
by weight of magnetite and 8 parts by weight of hydrogen. Thus the total weight of reactants is always
equal to the total weight of products.
Such computations will help one to estimate the quantity of reactants needed to obtain a specified
amount of product.
gram atom (or g atom) = Mass in grams/Atomic weight katom (or kg atom) = Mass in kg/Atomic
weight
gram mole (or g mole) = Mass in grams/Molecular weight kmole (or kg mole) = Mass in
kg/Molecular weight
7
The conclusions based on reactions (2.1) and (2.2) on material balance can be expressed in other
forms too, as per the definitions given above:
1 kmole of CaCO
3
gives 1 kmole of CaO and 1 kmole of CO
2
Similarly, 3 kmoles of iron reacts with 4 kmoles of steam (water) to yield 1 kmole of oxide and 4
kmoles of hydrogen. When such balances (on molar basis) are made, the number of moles on the
reactants side need not be equal to the total numbers of moles on the product side.
One atom of oxygen weighs = 16 grams O
One atom of hydrogen weighs = 1 gram H
One molecule of oxygen weighs = 32 grams O
One molecule of hydrogen weighs = 2 grams H
In other words,
16 grams of oxygen
32 pounds of oxygen
2 g atoms of oxygen
1 gram of hydrogen
2 kg of hydrogen
2 kg atoms of hydrogen = 1 kmole of hydrogen
\ g atom or lb atom = Mass in grams or pounds/Atomic weight \ g mole or lb mole = Mass in grams or
pounds/Molecular weight = 1 g atom of oxygen = 1 lb mole of oxygen = 1 g mole of oxygen = 1 g
atom of hydrogen = 1 kmole of hydrogen
2.2 CONSERVATION OF MASS
The law of conservation of mass states that mass can neither be created nor be destroyed. It is the
basic principle adopted in solving the material balance problems in chemical process calculations,
whether a chemical reaction is involved or not. However, while applying the law of conservation of
mass, one should not apply it for the conservation of molecules. We frequently come across chemical
reactions in which the total number of moles on the reactant side is not equal to the total number of
moles on the product side. For example:
Na
2
CO
3
+ Ca(OH)
2
CaCO
3
+ 2NaOH
The total number of moles on the reactant side is 2 and on the product side 3. Here the mass balance
is ensured but not the mole balance. Now consider the reaction:
2Cr
2
O
3
+ 3CS
2
2Cr
2
S
3
+ 3CO
2
Here the total number of moles both on the reactant side and the product side is 5. Hence both the
conservation of mass and the conservation of moles are observed.
2.3 AVOGADROS HYPOTHESIS
1 g mole of any gaseous substance at NTP occupies 22,414 cc or
22.414 litres and 1 lb mole of the same substance occupies 359 ft
3
at NTP.
1 kmole of any gaseous substance occupies 22.414 m
3
at NTP.
Note: NTP = Normal temperature (273 K) and pressure (1 atmosphere) are also referred to at times
as standard conditions (SC).
2.4 LIMITING REACTANT AND EXCESS REACTANT
For most of the chemical reactions the reactants will not be used in stoichiometric proportion or
quantities. One of the reactants will be present in excess and remain unreacted even when the other
reactant has completely reacted. The reactant thus present in excess is termed excess reactant and the
other reactant which is present in a lesser quantity and cannot react with whole of the other reactant
(excess reactant) is called limiting reactant. All calculations involved in estimating the quantity of
product and conversion are always based on the limiting reactant. The amount by which any reactant
is present in excess to that required to combine with the limiting reactant is usually expressed as
percentage excess. The percentage excess of any reactant is defined as the percentage ratio of the
excess to that theoretically required by the stoichiometric equation for combining with the limiting
reactant. A limiting reactant is the one, which will not be present in the product, whereas the excess
reactant is the one, which will always be present in the product.
Let us consider that 18 kg of carbon is burnt with 32 kg of oxygen. As per stoichiometry
C + O
2
CO
2
i.e. 12 kg of carbon will burn with 32 kg of oxygen to form 44 kg of CO
2
.
Hence, for 18 kg of carbon to react fully we should have 48 kg of oxygen. Since 32 kg of oxygen
alone is available, it is called the limiting reactant and carbon is called the excess reactant. For 32 kg
of oxygen to react fully, it is sufficient to have 12 kg of carbon. However 6 kg of carbon is present in
excess.
Hence % excess of carbon is =
6
100 = 50%.
12
2.5 CONVERSION AND YIELD These terms are used for a chemical reaction where the reactants
give out new compounds or products.
Conversion is the ratio of the amount of material actually converted to that present initially, whereas
the yield is the amount of desired product actually formed compared to that which can be formed
theoretically.
Conversion for a reaction is based on the limiting reactant whereas the yield is based on the product
formed.
2.6 COMPOSITION OF MIXTURES AND
SOLUTIONS
Different methods are available for expressing composition of mixtures of gases, liquids and solids.
Conventionally the composition of solids is either expressed on weight basis or mole basis. Let us
consider a binary system comprising components A and B.
W = Total weight of the system.
W
A
, W
B
= Weight of components A and B respectively. M
A
, M
B
= Molecular weight of components A
and B respectively,
if they are compounds.
A
A,
A
B
= Atomic weight of components A and B respectively, if they are elements.
V = Volume of the system.
V
A
and V
B
= Pure component volume of components A and B respectively.
2.6.1 Weight Percent
This is defined as the ratio of weight of a particular component to the total weight of the system in
every 100 part, i.e.
Weight % of A =
WA
100
W
This method of expressing composition is generally employed in solid and liquid systems and not
used in gaseous system. One major advantage of weight percent is, its independence to changes in
temperature and pressure.
The composition of a solid mixture is to be always taken as weight % when nothing is mentioned
above its units.
2.6.2 Volume Percent
The ratio of the volume of each component and the total volume of the system, for each 100 part of the
total volume is called volume percent Volume % of A =
VA
100
V
This method of expressing composition is employed always for gases, rarely for liquids and seldom
for solids. The composition of a gas mixture is to be taken as volume % when nothing is mentioning
about its units.
The volume % is also equal to mole % for ideal gases but not for liquids and solids. This is based on
Avogadros law.
2.6.3 Mole Fraction and Mole Percent
These concepts are generally adopted in the case of a mixture containing molecules of different
species.

W
A
MA
Mole fraction of A =
WA WB
M
A
M
B
Mole % of A = Mole fraction of A 100
2.6.4 Atomic Fraction and Atomic Percent This is adopted when a mixture contains two or more
atoms. W
A
Atomic fraction of
A
=
A
A
W
A
W
B
A
A
A
B
Atomic % of A = Atomic fraction of A 100
2.6.5 Composition of Liquid Systems
In the case of liquids we come across more number of methods of expressing compositions of the
liquid constituents.
(i) Weight ratio (ii) Mole ratio (iii) Molality
(iv) Molarity
= Weight of solute/weight of solvent
= g moles of solute/g moles of solvent
= g moles of solute/1 kg of solvent
= Number of g moles of solute/1 litre of solution
(v) Normality (N) = Number of gram equivalents of solute/1 litre of solution
Hence, concentration in grams per litre = Normality ( N) Equivalent weight of solute
For very dilute aqueous solutions, molality = molarity
2.7 DENSITY AND SPECIFIC GRAVITY
Density is defined as mass per unit volume and it varies with temperature. Specific gravity is the ratio
of density of a liquid to that of water. However, in the case of gases, it is defined as the ratio of its
density to that of air at same conditions of temperature and pressure.
Over a narrow range of temperature, the variation in density of solids is not high. However, in the
case of liquids and gases the variation in density is significant. Similarly, the densities vary
significantly with concentration also. This property of density and specific gravity varying with
concentration is very widely used both in industries and markets as an index for finding the
composition of a system comprising a specific solute and a specific solvent.
Several scales are in use in which specific gravities are expressed in terms of a degree, which are
related to specific gravities and densities by arbitrary mathematical definitions.
2.7.1 Baume (

Be) Gravity Scale

For liquids lighter than water
Degrees Baume =
140
130
G
G
is the specific gravity at
60
F
15
60
15


Thus, water will have a gravity of 10 Be and this degree decreases with increase in specific
gravity.
For liquids heavier than water

145
Degrees Baume = 145
G
In this scale the degree increases with increase in specific gravity.
2.7.2 API Scale (American Petroleum Institute) This scale is used for expressing gravities of
petroleum products. This is similar to Baume scale for liquids lighter than water.
Degrees API =
141.5
131.5
G
2.7.3 Twaddell Scale
This scale is used for liquids heavier than water. Degrees Twaddell (Tw) = 200 (G 1.0)
2.7.4 Brix Scale
This scale is used in sugar industry and 1 degree Brix is equal to 1% sugar in solution.
Degree Brix =
400
400
G
WORKED EXAMPLES 2.1 Convert 5000 ppm into weight %.
5000 100
= 0.5%106
2.2 The strength of H
3
PO
4
was found to be 35% P
2
O
5
. Find the weight % of the acid.
The acid can be split into
2H PO

P O + 3H O

34 25 2
(2 98)
142
(3 18)

196 units of the acid contains 142 units of the pentaoxide. The weight % of pentaoxide is (142/196)
which is 72.5% for pure acid. When the strength of pentoxide is 35%, the weight % of acid is
=
48.3%
2.3 What is the volume of 25 kg of chlorine at standard condition?
25 kg Cl
2
=
25
kmoles of Cl
22 35.46

25 22.414
= 7.9 m
3
Volume =
2 35.46
2.4 How many grams of liquid propane will be formed by the liquefaction of 500 litres. of the gas at
NTP? Molecular weight of propane (C
3
H
8
) is 44
1 g mole of any gas occupies 22.414 litres at NTP
500 litres of propane at NTP =
500
= 22.31 g moles
22.414
22.31 g moles of propane weighs = 22.31 44 = 981.52 g. 2.5 Find the volume of (a) 100 kg of
hydrogen and (b) 100 lb of hydrogen at standard conditions?
(a) 100 kg of H
2
= 50 kmoles of hydrogen
volume occupied by 50 kmoles of hydrogen 50 22.414
= 1120.7 m
3
(b) 100 lb of H
2
50 lb moles of hydrogen
Volume occupied by 50 lb moles of hydrogen 50 359 = 17950 ft
3
2.6 A solution of naphthalene in benzene contains 25 mole % Naphthalene. Express the composition
in weight %. Basis: 100 g moles of solution
Component Molecular weight Weight, Actual g mole weight, g
Composition in weight percent
Naphthalene C
10
H
8
128 Benzene C
6
H
6
78 25 25 128 = 3200 75 75 78 = 5850 3200 100/9050 = 35.35 5850 100/9050 = 64.65
Total 9050 100.00
2.7 What is the weight of one litre of methane CH
4
at standard conditions? 22.414 litres of any gas at
NTP is equivalent to 1 g mole of that gas

1
= 0.0446 g mole\ 1 litre of methane 1
22.414
\ Weight of one litre methane = 0.0446 16 = 0.714 g
2.8 A compound whose molecular weight is 103 analyses C : 81.5, H : 4.9 and N : 13.6 by weight.
What is the formula?
Basis: 100 g of substance
Element Atomic weight
Carbon 12
Hydrogen 1
Nitrogen 14
Weight, g Weight, Rounding of Weight of g atom atoms each element
81.5 81.5/12 = 6.8 7 84
4.9 4.9/1 = 4.9 5 5
13.6 13.6/14 = 0.9 1 14
Total 103
Hence the formula obtained after rounding is correct. So the molecular formula is C
7
H
5
N
2.9 An analysis of a glass sample yields the following data. Find the mole %.
Na
2
O : 7.8%, MgO : 7.0%, ZnO : 9.7%, Al
2
O
3
: 2.0%, B
2
O
3
: 8.5% and rest SiO
2
.
Basis: 100 g of glass sample
Component Weight, g Molecular weight g mole mole %
Na
2
O 7.8 62.0 0.1258 7.665
MgO 7.0 40.3 0.1737 10.583
ZnO 9.7 81.4 0.1192 7.262
Al
2
O
3
2.0 102.0 0.0196 1.194
B
2
O
3
8.5 69.6 0.1221 7.439
SiO
2
65.0 60.1 1.0815 65.857
Total 100.0 1.6419 100.0
2.10 A gaseous mixture analyzing CH
4
: 10%, C
2
H
6
: 30% and rest H
2
at 15 C and 1.5 atm is flowing
through an equipment at the rate of 2.5 m
3
/min. Find (a) the average molecular weight of the gas
mixture, (b) weight % and (c) the mass flow rate.
Basis: 100 g moles of the gaseous mixture.
Component Weight, Molecular Weight, Weight % g mole weight g
CH
4
10 16 160 13.56
C
2
H
6
30 30 900 76.27
H
2
60 2 120 10.17
Total 100 1180 100
The average molecular weight =
1180
= 11.8
100

Volumetric flow rate at standard conditions = 2.5 (273/288) = 3.555 m
3
/min
Moles of the gas =
3.555
= 0.156 kmole
22.414
Mass flow rate = moles average molecular weight = 0.156 11.8 = 1.84 kg/min 2.11 In an
evaporator a dilute solution of 4% NaOH is concentrated to 25% NaOH. Calculate the evaporation of
water per kg of feed. Basis: 1 kg of feed.
NaOH present is 0.04 kg, which appears as 25% in the thick liquor formed
Weight of thick liquor formed =
0.04
= 0.16 kg
0.25
Weight of water evaporated = (1 0.16) = 0.84 kg
Water evaporated per kg of feed = 0.84 kg
2.12 The average molecular weight of a flue gas sample is calculated by two different engineers. One
engineer used the correct molecular weight of N
2
as 28, while the other used an incorrect value of 14.
They got the average molecular weight as 30.08 and the incorrect one as 18.74. Calculate the %
volume of N
2
in the flue gases. If the remaining gases are CO
2
and O
2
calculate their composition
also.
Basis: 100 g moles of flue gas
Component g mole I Engineer II Engineer
N
2
x 28x 14x CO
2
y 44y 44y O
2
z 32z 32z
Total 100 3008 1874
x + y + z = 100 (i)
28x + 44y + 32z = 3008 (ii)
14x + 44y + 32z = 1874 (iii) Solving Eqs. (i), (ii) and (iii), we get
x = Moles of nitrogen = 81%
y = Moles of carbon dioxide = 11%
z = Moles of oxygen = 8%
2.13 An aqueous solution contains 40% of Na
2
CO
3
by weight. Express the composition in mole
percent.
Basis: 100 g of solution
Component grams Molecular g mole Composition in weight mole % Na
2
CO
3
40 106 40/106 = 0.377
0.377 100/3.71 = 10.16 Water 60 18 60/18 = 3.333 3.333 100/3.71 = 89.84 Total 3.710 100.00
2.14 What is the weight of iron and water required for the production of 100 kg of hydrogen?

3Fe
4H O
+
Fe O + 4H
234 2
(355.84) (4 18) (3
55.84) (4 16)
(4 2 1)+
167.52 72 231.52 8

239.52 239.52
Method 1 (Based on absolute mass)
167.52 kg of Fe is required for producing 8 kg of H
2
\ For producing 100 kg of H
2
(by stoichiometry)
100 t167.52
Iron (Fe) required =
8
= 2094 kg
Similarly, for getting 100 kg of H
2
the amount of steam (H
2
O) required is
=
100 t 72
= 900 kg
8
The total weight of reactants is
2094 kg Fe and 900 kg H
2
O = 2994 kg
The weight of Fe
231.52
2094 = 2894 kg
3
O
4
formed is =
167.52
\ The total weight of products is (100 kg H
2
+ 2894 kg Fe
3
O
4
) = 2994 kg
The total weight of reactants is (2094 kg Fe + 900 kg H
2
O) = 2994 kg
Method 2 (Based on moles)
100 kg of H
2
4 kmoles H
2
comes from
50 kmoles of H
2
comes from Weight of 37.5 katoms Fe
50 kmoles H
2
from
Weight of 50 kmoles H
2
O Moles of Fe
3
O
4
formed is
Weight of Fe
3
O
4
formed is
Total weight of reactants Total weight of products = 50 kmoles
= 3 katoms of Fe (by stoichiometry)
=

50
t
= 37.5 katoms Fe
4
= (37.5 55.84) = 2094 kg of iron
=

50
kmoles of water
4t

= (50 18) = 900 kg H
2
O
=
37.5
kmoles
3
37.5
=

231.52 = 2894 kg

= 2994 kg
= 2994 kg
2.15 How much super phosphate fertilizer can be made from one ton of calcium phosphate 93.5%
pure?
Atomic weights are: Ca : 40, P : 31, O : 16, S : 32
Ca
3
(PO
4
)
2
+ 2H
2
SO
4
CaH
4
(PO
4
)
2
+ 2CaSO
4
310 (2 98) 234 (2 136) 506 506
One ton of raw calcium phosphate contains 0.935 tons of pure calcium phosphate
Weight of super phosphate formed is = 234
0.935
= 0.70577 tonne\
310
2.16 SO
2
is produced by the reaction between copper and sulphuric acid. How much Cu must be used
to get 10 kg of SO
2
?
Cu +2H SO

24

CuSO +SO +2H O

4 2 2
63.54 64
64 kg of sulphur dioxide is obtained from 63.54 kg of copper. 10 kg of sulphur dioxide will be
obtained from 9.93 kg of copper. 2.17 How much potassium chlorate must be taken to produce the
same amount of oxygen that will be produced by 2.3 g of mercuric oxide? 2KClO
3
2KCl + 3O
2
(2 122.46) (2 74.46) (6 16) 244.92 148.92 96
2HgO 2Hg + O
2
(2 216.6) (2 200.6) (2 16)
433.2 g HgO gives 32 g of oxygen
2.3 g of HgO will give (32 2.3/433.2) = 0.1698 g of O
2
0.1698 g O
2
is obtained from (244.92 0.1698)/96 = 0.4332 g of KClO
3
.
2.18 Ammonium phosphomolybdate is made up of the radicals NH
3
, H
2
O, P
2
O
5
and MoO
3
. What is %
composition of the molecule with respect to these radicals?
The formula of ammonium phosphomolybdate is
(NH
4
)
3
PO
4
12MoO
3
3H
2
O
First let us form the final product from the radicals:
3NH
3
+ 4.5H
2
O + 12MoO
3
+ P
2
O
5
(NH
4
)
3
PO
4
12MoO
3
3H
2
O
(317 = 51) (4.518 = 81) (12144 = 1728) (142 = 71) 1931
% of NH
3
=51
100
= 2.64
1931

% of H
2
O= 81
100
= 4.19
1931

% of MoO
3
= 1728
100
= 89.49
1931

% of P
2
O
5
=71
100
= 3.68
1931
Total = 100.00
2.19 How many grams of salt are required to make 2500 g of salt cake? How much Glaubers salt can
be obtained from this?
The molecular formula of Glaubers salt is Na
2
SO
4
10H
2
O
(142 + 180 = 322)

2NaCl
H SO Na SO
+ 2HCl

(2

58.46 =116.92)
+
24 24

98 142 (236.46)
Thus, 142 g of Na
2
SO
4
is obtained from 116.92 g NaCl. 2500 g of salt cake is obtained from 116.92
2500/142 = 2058.45 g NaCl
Hence, salt needed is 2058.45 g
Glaubers salt (Na
2
SO
4
10H
2
O) obtained is 2500 322/142 = 5669 g
2.20 (a) How many grams of K
2
Cr
2
O
7
are equivalent to 5 g KMnO
4
? (b) How many grams of KMnO
4
are equivalent to 5 g K
2
Cr
2
O
7
? 2KMnO
4
+ 8H
2
SO
4
+ 10FeSO
4
5Fe
2
(SO
4
)
3
+ K
2
SO
4
+ 2MnSO
4
+ 8H
2
O
K
2
Cr
2
O
7
+ 7H
2
SO
4
+ 6FeSO
4
3Fe
2
(SO
4
)
3
+ K
2
SO
4
+ (Cr
2
SO
4
)
3
+ 7H
2
O
2KMnO
4
gives 5Fe
2
(SO
4
)
3
(2 158 = 316) (5 400 = 2000)
K
2
Cr
2
O
7
gives 3Fe
2
(SO
4
)
3
(294) (3 400 = 1200)

1200 t 316
= 189.6 g KMnO
4
\ 294 g K
2
Cr
2
O
7
is equivalent to
2000

3 t189.6
= 1.935 g KMnO
4
\ 3 g K
2
Cr
2
O
7

294
Similarly, 5 g KMnO
4

5 t 294
= 7.75 g K
2
Cr
2
O
7

189.6

Alternatively,
53t
= 7.75 g K
2
Cr
2
O
71.935
2.21 If 45 g of iron react with H
2
SO
4
, how many litres of hydrogen are liberated at standard
condition?
There are two possible reactions in this case: (a) Case I
Fe H SO FeSO + H

(55.85)
+

24
4 2 (i)
(2)

The weight of hydrogen formed by reaction (i) is = 45
2
= 1.611 g,
55.85

i.e.
1.611
= 0.806 g mole
2
0.806 g mole 0.806 22.414 = 18.06 litres
(b) Case II

2Fe
3H SO
Fe (SO ) + 3H

(111.7)
+24 2 43 2 (ii)
(6)

The moles of hydrogen formed by reaction (ii) is 45
6
= 2.418 g
111.7
2.418 g H
2
= 1.209 g moles of hydrogen 1.209 22.414 27.1 litres
2.22 A natural gas has the following composition by volume CH
4
: 83.5%, C
2
H
6
: 12.5%, and N
2
: 4%.
Calculate the following:
(a) composition in mole % (b) composition in weight % (c) average molecular weight (AVMWT) (d)
density at standard condition (kg/m
3
) Basis: 100 kmoles of gas mixture
Component Molecular mole % Weight, kg Weight % weight
CH
4
16 83.5 83.5 16 = 1336 1336 100/1823 = 73.29
C
2
H
6
30 12.5 12.530 = 375 375 100/1823 = 20.57
N
2
28 4.0 4.028 = 112 112100/1823 = 6.14
Total 1823 100.0
(c) Average molecular weight =
1823
= 18.23
100

Volume at standard condition = 00 22.414 = 2241.4 m
3
(d) Density of gas at standard condition =

1823
= 0.813 kg/m
3
2241.4
2.23 Convert 54.75 g/litre of HCl into molarity.
Molarity = g moles/litre of solution
=
54.75
= 1.5
36.45
2.24 A solution of NaCl in water contains 230 g of NaCl per litre at 20 C. The density of the
solution at this temperature is 1.148 g/cc. Find the composition in (a) weight % (b) volume % of
water (c) mole % (d) atomic % (e) molality and (f) g NaCl/g water.
Basis: (a) 1 litre of solution has a weight of 1148 g
Component Molecular Weight, g Weight, %g mole mole % weight
NaCl 58.5 230 20.03 230/58.5 = 3.93 3.93/54.93 = 7.15 Water 18 918 79.97 918/18 = 51.00 51/54.93 = 92.85 Total 1148 100.00 54.93
100.00
(b) Volume % of water: 918 g is present in 1 litre of solution, i.e.
918 cc water is present in 1000 cc. of solution (density of water is
1 g/cc)
Volume % = 91.8%
(d)
Element g atoms Atomic %
Na 3.93 2.443
Cl 3.93 2.443
H 102.00 63.409
O 51.00 31.705
Total 160.86 100.000
(All are based on the molecular formula)
(e) Molality = g moles of solute in 1 kg of solvent (3.93 1000/918) or, 3.93 g moles of NaCl is
present in 918 g of water (i.e.) 4.28 g moles/1000 g of solvent
Molality = 4.28
Molarity = Moles of solute per litre of the solution = 3.93
(f) g NaCl/g water =
230
= 0.252
918
2.25 A benzene solution of anthracene contains 10% by weight of the solute. Find the composition in
terms of (a) molality (b) mole fraction. Basis: 100 g of solution
Component Molecular Weight, g Weight, mole weight g mole fraction Anthracene 178 10 (10/178)
0.046 0.0562 Benzene 78 90 (90/78) 0.954 1.1538 Total 1.2100 1.00
Molality = g moles of anthracene in 1000 g benzene
=
0.0562
1000 = 0.624
90

2.26 Calculate the weight of NaCl that should be placed in a 1 litre volumetric flask to prepare a
solution of 1.8 molality. Density of this solution is 1.06 g/cc
Molality = g moles of NaCl/1000 g of water
= 1.8
or, 1.8 g moles NaCl = (1.8 58.46) = 105.228 g
Component Weight, g Weight % NaCl 105.228 9.52
H
2
O 1000.000 90.48
1105.228 100.00
Density of this solution = 1.06 g/cc
Volume of this solution, i.e. mass/density =
1105.228
= 1042.67 cc
1.06
or 1042.67 cc of this solution contains 105.228 g of NaCl
1000 cc of this solution will have = 1000
105.228
\
1042.67
= 100.92 g of NaCl. NaCl needed = 100.92 g
2.27 For the operation of a refrigeration plant it is desired to prepare a solution of 20% by weight of
NaCl solution.
(a) Find the weight of salt that should be added to one gallon of
water at 30C?
(b) What is the volume of this solution?
Basis: 100 lb of solution
It will have 20 lb NaCl and 80 lb water
80 lb water = 1.28 ft
3
(since the density of water is 62.47 lb/ft
3
) We know that 1 ft
3
= 7.48 gallons
Therefore, 1.28 ft
3
= 9.57 gallons.
20
(a) Weight of salt per gallon of water =

= 2.09 lb.

(b) Specific gravity of NaCl solution at 30 C = 1.14

\ Density of solution = 1.14 62.4 = 71.14 lb/ft
3
Weight of 1 gallon of water =
62.47
= 8.35 lb.
7.48
Total weight of solution = weight of water + weight of salt = 8.35 + 2.09 = 10.44 lb.
Hence, volume of the above solution =

10.44
= 0.147 ft
3
71.14
= 1.1 gallons.
2.28 (a) A solution has 100 Tw gravity. What is its specific gravity and Be?
(b) An oil has a specific gravity of 0.79. Find API and Be (a) 100 = 200 (G 1) \ G = 1.5
Be = 145
145
145
= 145

= 48.3 Be
G

141.5

141.5
131.5 = 47.6

131.5 = (b) API =

140
Be
=

130 = 47.2

2.29 An aqueous solution contains 15% ethyl alcohol by volume. Express the composition in weight
% and mole %. Density of ethyl alcohol and water are 790 kg/m
3
and 1000 kg/m
3
respectively. Basis:
1 m
3
of solution.
Compound Molecular Volume, Density, Weight, Number Weight mole weight m
3
kg/m
3
kg of moles %%
Ethanol 46 0.15 790 118.5 2.576 12.235 5.173 Water 18 0.85 1000 850 47.222 87.765 94.827 Total 1.00 968.5 49.798 100 100
2.30 The quality of urea is expressed in terms of nitrogen content. If the nitrogen content in the sample
is only 40%, estimate the purity of sample in terms of urea content.
The molecular weight of urea (NH
2
CONH
2
) is 60 and that of N
2
is 28. Basis: 100 kg of sample
60 kg of urea has 28 kg of N
2
100 kg of urea will have = 28
100
= 46.67 kg of N
260
(Theoretically)
The given sample has 40% N
2
Hence, the % purity is = 40
100
= 85.71%
46.67
2.31 If the nitrogen content in ammonium nitrate sample is 28%, estimate the purity of ammonium
nitrate.
Molecular weight of ammonium nitrate, NH
4
NO
3
= 80
% Nitrogen in pure ammonium nitrate = 28
100
= 35%
80
The % of nitrogen in the sample is 28
28
Hence, the purity of ammonium nitrate is

100 = 80%

2.32 Nitrobenzene is produced by reacting nitrating mixture with benzene. The nitrating mixture
contains 31.5% HNO
3
, 60% H
2
SO
4
and 8.5% H
2
O. A charge contains 663 kg of benzene and 1700 kg
of nitrating mixture which sent into the reactor. If the reaction is 95%, then calculate the amount of
nitrobenzene and spent acid produced. The reaction is
C
6
H
6
+ HNO
3
C
6
H
5
NO
2
+ H
2
O
Feed, C
6
H
6
: 663/78 = 8.5 kmole
HNO
3
: 31.5% of 1700 kg = 535.5 kg = 8.5 kmoles H
2
SO
4
: 60 % of 1700 kg = 1020 kg = 10.408
kmoles H
2
O : 8.5 % of 1700 kg = 144.5 kg = 8.028 kmoles Reaction is 95% complete
Hence, HNO
3
unreacted : 0.05 8.5 = 0.425 kmole C
6
H
6
unreacted : 0.05 8.5 = 0.425 kmole
H
2
SO
4
unreacted : 10.408 kmoles
H
2
O unreacted : 8.028 kmoles
H
2
O formed : 8.5 0.95 = 8.075 kmoles Nitrobenzene formed : 8.5 0.95 = 8.075 kmoles
Component Weight, Molecular Weight, Weight, kmole weight kg %
HNO
3
0.425 63 26.775 1.133
H
2
SO
4
10.408 98 1020.000 43.165
H
2
O (8.075 + 8.028) = 16.103 18 289.850 12.266
Nitrobenzene 8.075 123 993.225 42.032
C
6
H
6
0.425 78 33.150 1.403
Total 2363.00 100%
Nitrobenzene produced = 993.225 kg
Spent acid = 26.775 + 1020.000 + 289.85 = 1336.63 kg 2.33 A sample of caustic soda flake contains
74.6% Na
2
O by weight. Estimate the purity of flakes.
Reaction is as follows:
2NaOH Na
2
O + H
2
O
Amount of Na
2
O in pure flakes = 62 100/80 = 77.5% % Purity = 0.746/0.775 100 = 96.26%
2.34 Two kg of CaCO
3
and MgCO
3
was heated to a constant weight of 1.1 kg. Calculate the %
amount of CaCO
3
and MgCO
3
in reacting mixture.
Reaction is as follows:
CaCO
3
CaO + CO
2
(100) (56) (44)
MgCO
3
MgO + CO
2
(84) (40) (44)
Let, x be the amount of CaCO
3
.
Therefore, (2 x) be the weight of MgCO
3
100 kg of CaCO
3
gives 56 kg of CaO
Therefore, x kg of CaCO
3
gives
56x
= 0.56x kg of CaO.
100
Similarly, 84 kg of MgCO
3
gives 40 kg of MgO
40
Therefore, (2
x
) kg of MgCO
3
gives

(2 x) kg of MgO

The weight of product left behind is 1.1 kg, i.e. weight of MgO + CaO left behind
0.56x + (0.4672)(2 x) = 1.1
0.0838x = 1.1 0.96524
Therefore, x = 1.761 kg
Component Weight, kg Weight, %
CaCO
3
1.761 88.05
MgCO
3
0.239 11.95
Total 2.000 100.00
2.35 The composition of NPK fertilizer is expressed in terms of N
2
, P
2
O
5
and K
2
O each of about 15
weight %. Anhydrous ammonia, 100% phosphoric acid and 100% KCl are mixed to get 1 ton of
fertilizer. Estimate the amount of filler in the NPK fertilizer.
Basis: 1000 kg of fertilizer
Reactions are:
2NH
3
N
2
+3H
2
(34) (28) (6)
2H
3
PO
4
P
2
O
5
+3H
2
O
(196) (142) (54)
2KCl + H
2
O K
2
O + 2HCl
(149) (18) (94) (73)
N
2
, K
2
O and P
2
O
5
are each equivalent to 15 weight % = 150 kg each Ammonia reacted = 34
150
= 182.14 kg
28

H
150
= 207.04 kg
3
PO
4
needed = 196
142

KCl needed = 149
150
= 237.77 kg
94
The amount of inert material/filler = 1000 626.95 = 373.05 kg
2.36 A solution whose specific gravity is 1 contains 35% A by weight and the rest is B. If the specific
gravity of A is 0.7, find the specific gravity of B.
Basis: 1000 kg of solution
Weight of A: 350 kg
Weight of B: 650 kg
Volume of solution = 1 m
3
(since density is 1000 kg/m
3
due to specific gravity being unity)
Mass/volume = density
Assuming ideal behaviour

350 650
= 1700 SB

r
B
= 1300 kg/m
3
Therefore, specific gravity of B = 1.3
2.37 An aqueous solution contains 47% of A on volume basis. If the density of A is 1250 kg/m
3
,
express the composition of A in weight %.
Basis: 1 m
3
of solution
Volume of A in solution = 1 0.47 = 0.47 m
3
Weight of A = 0.47 1250 = 587.5 kg
Volume of water = (1 0.47) = 0.53 m
3
Therefore, the weight of water = 0.53 m
3
1000 = 530 kg
Hence, weight % of A =
587.5
= 52.57%
530 587.5
2.38 An aqueous solution contains 43 g of K
2
CO
3
in 100 g of water. The density of solution is 1.3
g/cc. Find the composition in molarity and molality.
Basis: 100 g of solvent
Weight of K
2
CO
3
= 43 g
Weight of solution = 143 g
Density of solution = 1.3 g/cc
Volume of solution =
143
= 110 cc
1.3

Moles of solute = Weight/Molecular weight =
43
= 312 g moles
138

Molarity = g mole/volume of solution in lit =
0.312
= 2.833M
0.11
Molality = g mole/kg of solvent =
0.312
= 3.12 g moles/kg solvent.
0.1
2.39 A gaseous mixture contains ethylene: 30.6%, benzene: 24.5%, O
2
: 1.3%, ethane: 25%, N
2
: 3.1%
and methane: 15.5% in volume basis. Estimate the composition in mole %, weight %, average
molecular weight and density.
Basis: 100 kmoles of mixture
Compound mole % Molecular weight Weight, kg Weight %
C
2
H
4
30.6 28 856.8 22.00
C
6
H
6
24.5 78 1911.0 49.07
O
2
1.3 32 41.6 1.07
CH
4
15.5 16 248.0 6.37
C
2
H
6
25 30 750.0 19.26
N
2
3.1 28 86.8 2.23
Total 3894.2 100.00
Density = Weight/Volume =
3894.2
22.414 = 1.737 kg/m
3
= 1.737 g/l.
100
2.40 A compound has a composition of 9.76% Mg, 13.01% S, 26.01% O
2
and 57.22% H
2
O by
weight. Find the molecular formula of this compound.
Basis: 100 g of compound
Compound Weight, Atomic weight Number g or Molecular of moles weight
Mg 9.76 24 0.410
S 13.01 32 0.410
O 26.01 16 1.615
H
2
O 57.22 18 2.8738
Converting to whole numbers dividing by 0.41
1
1
3.94
6.92
Therefore, molecular formula of the compound = MgSO
4
.7H
2
O 2.41 A substance on analysis gave
1.978 g of Ag, 0.293 g of S and 0.587 g of O
2.
Find the molecular formula of the compound.
Compound Weight, Atomic weight g or Molecular weight Number Converting to of moles whole
numbers dividing by 9.156 10
3
Ag 1.978 108
S 0.293 32
O
2
0.587 16
Molecular formula = Ag
2
SO
4
0.0183 2
9.156 10
3
1
0.0367 4.04
2.42 Two engineers are estimating the average molecular weight of gas containing oxygen and another
gas. One uses the molecular weight as 32 and finds the average molecular weight as 39.8 and the
other uses the atomic weight of oxygen as 16 and finds the average molecular weight as 33.4.
Estimate the composition of the gas mixture.
By using the atomic weight of oxygen as 16, the value is 33.4 and by using the molecular weight of
oxygen, the value is 39.8. Let x be the mole fraction of oxygen in the mixture and the molecular weight
of the other gas be M
39.8 = (x) (32) + (1 x) (M)
33.4 = (x) (16) + (1 x) (M)
Solving, we get x = 0.4
i.e the fraction of oxygen in the mixture is 0.4
2.43 A mixture of methane and ethane has an average molecular weight of 21.6. Find the composition.
Let the mole fraction of methane be X
21.6 = (Molecular weight of CH
4
)(X) + (Molecular weight of C
2
H
6
) (1 X)
21.6 = 16 X + 30 (1 X)
Solving, we get X = 0.6
2.44 A mixture of FeO and Fe
3
O
4
was heated in air and is found to gain 5% in mass. Find the
composition of initial mixture.
Reactions involved are:
2FeO + 0.5 O
2
Fe
2
O
3
2Fe
3
O
4
+ 0.5 O
2
3 Fe
2
O
3
Basis: 100 kg of feed mixture
Let X be the weight of FeO in the mixture
From 144 kg of FeO, Fe
2
O
3
formed is 160 kg
Therefore, from
X
kg of FeO, Fe
2
O
3
formed is 160

X 144 From 232 kg of Fe
3
O
4,
Fe
2
O
3
formed is 480 kg
Therefore, from (100
X
) of Fe
3
O
4
,Fe
2
O
3
formed is (100 X )
(480) 464 Since 5% gain in mass is observed, the weight of final product is 105 kg, i.e.

160X
tt
(480)
105
144 464
Solving, X, the weight of FeO = 20.25 kg
Fe
3
O
4
= (100 83.45) = 79.75 kg
2.45 A sample of lime stone has 54.5% CaO. Find the weight % of lime stone.
Basis: 100 kg of lime stone
100 kg of CaCO
3
will have 56% CaO
If the CaO is 54.5%, then % of CaCO
3
in the sample is
54.5 100/50 = 97.32%
2.46 Express the composition of magnesite in mole %.
Compound Weight %
MgCO
3
81
SiO
2
14
H
2
O5
Compound Weight % Molecular weight moles mole % MgCO
3
81 84 0.964 65.34
SiO
2
14 60 0.233 15.82
H
2
O 5 18 0.278 18.83
2.47 The concentration of H
3
PO
4
is expressed in terms of P
2
O
5
content. If 35% P
2
O
5
is reported, find
the composition of H
3
PO
4
by weight. P
2
O
5
+ 3H
2
O 2H
3
PO
4
(142) (54) (98)
i.e. 142 kg of P
2
O
5
196 kg of H
3
PO
4
Therefore, 35 kg of P
2
O
5
35
196
= 48.3 H
3
PO
4142
i.e. H
3
PO
4
is 48.3%
2.48 Ten kg of PbS and 3 kg of oxygen react to yield 6 kg of Pb and 1 kg of PbO
2
according to the
reaction shown below:
PbS + O
2
Pb + SO
2
(1) PbS + 2O
2
PbO
2
+ SO
2
(2) Estimate (i) unreacted PbS, (ii) % excess
oxygen supplied, (iii) total SO
2
formed, and (iv) the % conversion of PbS to Pb.
PbS + O
2
Pb + SO
2
(1)
(239.2) (32) (207.2) (64)
PbS + 2O
2
PbO
2
+ SO
2
(2)
(239.2) (64) (239.2) (64)
207.2 kg of Pb comes from 239.2 kg of PbS [from stoichiometry Eq. (1)] Therefore, 6 kg of Pb comes
from 239.2
6
= 6.927 kg of PbS
207.2
239.2 kg of PbO
2
comes from 239.2 kg of PbS
Therefore, 1 kg of PbO
2
comes from 1 kg of PbS
Therefore, total PbS reacted [from Eqs. (1) and (2)]
= 6.927 + 1 = 7.927 kg
Unreacted PbS = 10 7.927 = 2.073 kg
O
2
required for this process
From Reaction 1:
32 kg of oxygen is needed to produce 207.2 kg of Pb
Therefore, to produce 6 kg of PbO
2
, oxygen needed = 6
32
= 0.927 kg
207.2
From Reaction 2:
239.2 kg of PbO
2
requires 64 kg of oxygen
Therefore, to produce 1 kg of PbO
2
, oxygen required is 268 kg Therefore, total oxygen used = 0.927 +
0.268 = 1.195 kg
(3
1.195)
Percentage excess O
2
supplied =

100 = 151%

Amount of SO
2
formed
If 207.2 kg of Pb is formed, SO
2
formed is 64 kg
If 6 kg of Pb is formed, SO
6
= 1.853 kg
2
formed is 64
207.2
If 239.2 kg of PbO
2
is formed, SO
2
formed is 64 kg
If 1 kg of PbO
64
= 0.268 kg
2
is formed, SO
2
formed is
239.2
Total SO
2
formed = 1.853 + 0.268 = 2.121 kg
% conversion of PbS fed to Pb = Mass of PbS converted to Pb/Total mass of PbS
= 6.927
100
= 69.27%
10
2.49 The composition of a liquid mixture containing A, B and C is peculiarly given as 11 kg of A, 0.5
kmole of B and 10 wt of % C. The molecular weights of A, B and C are 40, 50 and 60 respectively
and their densities are 0.75 g/cc, 0.8 g/cc and 0.9 g/cc respectively. Express the composition in
weight %, mole %. Also give its average molecular weight and density assuming ideal behaviours.
Let the weight of mixture be W kg
Weight of A = 11 kg
Weight of C (10%) = 0.1W kg
Weight of B = W 11 0.1W = 0.5 kmole
= 0.5 50 = 25 kg
i.e. weight of B = W 11 0.1W = 25 kg
0.9W = 36 kg
W = 40 kg
i.e. total weight of mixture is 40 kg.
Component Weight, Weight, Molecular moles, mole Density, Volume, kg % weight kmole % kg/m
3
m
3
A 11 27.5 40 0.275 32.66 750 0.0147
B 25 62.5 50 0.500 59.38 800 0.0313
C 4 10.0 60 0.067 7.96 900 0.0044
Total 40 100.00 0.842 100.00 0.0504
40
= 793.65 kg/m
3
Average density = Mass/Volume =
0.0504

Average molecular weight = Weight/Total moles =
40
= 47.5
0.842
(Check: Average molecular weight
= 40 0.3266 + 50 0.5938 + 60 0.0796 = 47.5)
EXERCISES
2.1 How many g moles are equivalent to 1.0 kg of hydrogen? 2.2 How many kilograms of charcoal is
required to reduce 3 kg of arsenic trioxide?
As
2
O
3
+ 3C 3CO + 2As
2.3 Oxygen is prepared according to the following equation: 2KClO
3
2KCl + 3O
2
. What is the
yield of oxygen when 9.12 g
of potassium chlorate is decomposed? How many grams of potassium chlorate must be decomposed
to get 5 g of oxygen?
2.4 An aqueous solution of sodium chloride contains 28 g of NaCl per 100 cc of solution at 293 K.
Express the composition in (a) percentage NaCl by weight (b) mole fraction of NaCl and (c) molality.
Density of solution is 1.17 g/cc.
2.5 An aqueous solution has 20% sodium carbonate by weight. Express the composition by mole ratio
and mole percent.
2.6 A solution of caustic soda in water contains 20% NaOH by weight. The density of the solution is
1196 kg/m
3
. Find the molarity, normality and molality of the solution.
2.7 A saturated solution of salicylic acid in methanol contains 64 kg salicylic acid per 100 kg
methanol at 298 K. Find the composition by weight % and volume %.
2.8 A solution of sodium chloride in water contains 270 g per litre at 323 K. The density of this
solution is 1.16 g/cc. Estimate the composition by weight %, volume %, mole %, atomic %, molality
and kg of salt per kg of water.
2.9 A mixture of gases has the following composition by weight at 298 K and 740 mm Hg.
Chlorine: 60%, Bromine: 25% and Nitrogen: 15%.
Express the composition by mole % and determine the average molecular weight.
2.10 Wine making involves a series of very complex reactions most of which are performed by
microorganisms. The initial concentration of sugar determines the final alcohol content and sweetness
of the wine. The general convention is to adjust the specific gravity of the starting stock to achieve a
desired quality of wine. The starting solution has a specific gravity of 1.075 and contains 12.7 weight
% of sugar. If all the sugar is assumed to be C
12
H
22
O
11
, determine
(a) kg sugar/kg H
2
O
(b) kg solution/m
3
solution
(c) g sugar/litre solution
2.11 The synthesis of ammonia proceeds according to the following reaction
N
2
+ 3H
2
2NH
3
In a given plant, 4202 lb of nitrogen and 1046 lb of hydrogen are fed to the synthesis reactor per hour.
Production of pure ammonia from this reactor is 3060 lb/h.
(a) What is the limiting reactant?
(b) What is the percent excess reactant?
(c) What is the percent conversion obtained (based on the limiting reactant)?
2.12 How many grams of chromic sulphide will be formed from 0.718 g of chromic oxide according
to the following equation?
2Cr
2
O
3
+ 3CS
2
2Cr
2
S
3
+ 3CO
2
2.13 How many kilograms of silver nitrate are there in 55.0 g mole silver nitrate?
2.14 Phosphoric acid is used in the manufacture of fertilizers and as a flavouring agent in drinks. For
a given 10 weight % phosphoric acid solution of specific gravity 1.10, determine:
(a) the mole fraction composition of this mixture.
(b) the volume of this solution, which would contain 1 g mole H
3
PO
4
. 2.15 Hydrogen gas in the
laboratory can be prepared by the reaction of sulphuric acid with zinc metal
H
2
SO
4
(l) + Zn(s) ZnSO
4
(s) + H
2
(g)
How many grams of sulphuric acid solution (97%) must act on an excess of zinc to produce 12.0 m
3
/h
of hydrogen at standard conditions. Assume all the acid used reacts completely.
2.16 Sulphur dioxide may be produced by the reaction
Cu + 2 H
2
SO
4
CuSO
4
+ 2H
2
O + SO
2.
Find how much copper and how much 94% sulphuric acid must be used to obtain 32 kg of SO
2
.
2.17 Aluminium sulphate is produced by reacting crushed bauxite ore with sulphuric acid as shown
below:
Al
2
O
3
+ 3 H
2
SO
4
Al
2
(SO
4
)
3
+ 3 H
2
O
Bauxite ore contains 55.4% by weight Al
2
O
3
, the reminder being impurities. The sulphuric acid
contains 77.7% H
2
SO
4
, the rest being water. To produce crude aluminium sulphate containing 1798
kg of pure Al
2
(SO
4
)
3
, 1080 kg of bauxite ore and 2510 kg of sulphuric acid solution are used. Find (a)
the excess reactant, (b) % of excess reactant consumed, and (c) degree of completion of the reaction.
2.18 600 kg of sodium chloride is mixed with 200 kg of KCl. Find the composition in weight % and
mole %.
2.19 What is the weight of iron and water required to produce 100 kg of hydrogen.
2.20 Cracked gas from petroleum refinery has the following composition by volume:
Methane: 42%, ethane: 13%, ethylene: 25%, propane: 6%, propylene: 9%, and rest n-butane. Find:
(a) average molecular weight of mixture, (b) Composition by weight, and (c) specific gravity of the
gas mixture.
2.21 A gas contains methane: 45% and carbon dioxide: 45% and rest nitrogen. Express (i) the weight
%, (ii) average molecular weight, and (iii) density of the gas at NTP.
Ideal Gases 3
3.1 RELATION BETWEEN MASS AND VOLUME FOR GASEOUS SUBSTANCES
3.1.1 Standard Conditions
1 atm. pressure or 760 mm Hg or 29.92 inches of Hg and 0 C or 32 F By Avogadros Hypothesis,
1 g mole of any gas under standard conditions will occupy 22.414 litres 1 lb mole of any gas under
standard conditions will occupy 359 cu.ft.
T(K) = T C + 273.16
T(R) = T F + 459.69
3.1.2 Ideal Gas Law
The ideal gas law states that,
PV = nRT
P = Pressure of gas
V = Volume of n moles of gas
n = Number of moles of gas
R = Gas constant
T = Absolute temperature
Using the ideal gas law (PV = nRT) and the above information one can always determine the weight
of a gas if the volume is known and vice-versa.
Parameters
Pressure
Molar volume Absolute
temperature Gas constant
Normal Temperature and Pressure/Standard Conditions English Metric SI 1.033 kgf/cm
2
1.01325 bar 359 ft
1 atm3
/lb mole 22.414 m
3
/kmole 22.414 m
3
/kmole
491.69 273.16 K 273.16 K 0.73 atm ft
oR 3
/lb mole
o
R 0.085 kgf m
3
/kmole K 0.083 Bar m
3
/kmole K
35
Pressure 1 atm = 1.033 kgf/cm
2
= 1.01325 bar
1 atm = 14.67 psia = 10
5
N/m
2
= 760 mm Hg
1 atm = 760 Torr = 29.92 inches of Hg = 76 cm Hg
R =
PV
= 82.06 atm.cc/g mole K = 0.73 atm ft
3
/lb mole R
nT

R = 10.73 lb
f
ft
3
/in
2
lb mole R
Avogadros Number: 6.023 10
23
molecules per g mole
2.73 10
26
molecules per lb mole
6.023 10
26
molecules per kg mole
Different units are used to express pressure like atmosphere, mm of Hg, psia, kg/cm
2
, bar, N/m
2
, and
Pa. Similarly, volume is expressed in cm
3
, m
3
, litre, ft
3
and gallon. The temperature is expressed in
C, F, K and R. However, the temperature used in the application of Ideal gas law is in terms of K
or R.
Thus, the gas constant is a dimensional quantity. The following table gives the gas constant in
different units.
Temperature Pressure Volume Gas constant R
g

R psia in
3
18.51
R psia ft
3
10.73
R atmospheres ft
3
0.73
KPa m
3
8314
K atmospheres m
3
0.08206
K atmospheres cm
3
82.06
K cm Hg cm
3
6239.79
Units of gas
constant
in
3
psia/lb mole R ft
3
psia/lb mole R
ft
3
atm/lb mole R
m
3
Pa/kmole K
m
3
atm/kmole K
cm
3
atm/g mole K (cm
3
cm Hg)g mole K
R
g
= 8.314 J/(g mole) (K) = 1545 ft lb/lb mole R
3.2 GASEOUS MIXTURE
3.2.1 Partial Pressure (PP)
The partial pressure of a component gas that is present in a mixture of gases is the pressure that would
be exerted by that component gas if it alone were present in the same volume and at the same
temperature as the mixture.
3.2.2 Pure Component Volume (PCV)
The PCV of a component gas that is present in a mixture of gases is the volume that would be
occupied by that component gas if it alone were present at the same pressure and temperature as the
mixture.
Components A B C Sum of the quantities
Partial pressure p
A
p
B
p
C
P Number of moles n
A
n
B
n
C
n Pure component volume V
A
V
B
V
C
V
3.2.3 Daltons Law
The total pressure (P) exerted by a gaseous mixture in a definite volume is equal to the sum of partial
pressures.
p
A
+ p
B
+ p
C
= P
where p
A
, p
B
, p
C,
represent partial pressure of components A, B, C, .
3.2.4 Amagats Law (or) Leducs Law
The total volume (V ) occupied by a gaseous mixture is equal to the sum of the pure component
volumes
V
A
+ V
B
+ V
C
= V
V
A
, V
B
, V
C
, stand for pure component volume of components A, B, C,
Where ideal gas law is applicable;
n RT
; p
B
=
Bn RT
; p
C
=
Cn RT
(a) p
A
=
A
V V V
Adding all the partial pressures of A, B and C, we have,
RT
P
=
p
A
+
p
B
+
p
C
=

(n
A
+ n
B
+ n
C
)

Dividing, p
RT V nA
;
A
/P =
V ()RT n ++n
A BC
pressure fraction = mole fraction.
(b) PV
A
= n
A
RT; PV
B
= n
B
RT; PV
C
= n
C
RT
Adding P(V
A
+ V
B
+ V
C
) = RT (n
A
+ n
B
+ n
C
) = nRT = PV
nRTP
= N
AV
=
A
Dividing,
VA
()
AB C
n RT
++
or, V
A
= N
A
V
3.3 AVERAGE MOLECULAR WEIGHT
The weight of unit mole of the mixture is called average molecular weight, which is also equal to
total weight of the gas mixture divided by the total number of moles in the mixture. This is applicable
only for gaseous mixtures and not for solid or liquid mixtures. For example, air contains 79%
nitrogen and 21% oxygen by volume.
Basis: 100 kmole
Number of moles of nitrogen = 79
and those of oxygen = 21
Weight of a component = Number of moles respective molecular weight
\ Weight of nitrogen = 79 28 = 2212 kg
Weight of oxygen = 21 32 = 672 kg
2884 kg
\ The weight of 1 kmole = 2884/100 = 28.84 kg
Hence, the average molecular weight of air = 28.84
3.4 DENSITY OF MIXTURE
Density is defined as the weight of a mixture per unit volume and is independent of temperature. As
the volume of liquids and gases is a strong function of temperature, density also varies significantly
with temperature for a specified composition. However, in the case of solids the variation of density
with temperature is not very significant.
WORKED EXAMPLES
3.1 Calculate the volume of 15 kg of Chlorine at a pressure of 0.9 bar and 293 K.
Basis: 15 kg Cl
2
= 15/71.0 = 0.2113 kmole
1.0

293
= 5.643 m
3
Its volume is 0.2113 22.414
0.9 273
3.2 Calculate the volume occupied by 6 lb of chlorine at 743 mm Hg and 70 F Basis: 6 lb of Cl
2

6/71 = 0.0845 lb mole of chlorine Volume at standard condition = (0.0845 359) = 30.34 ft
3
PV1
Volume at given condition =
00
01

760
530
=

= 33.4 ft
3
3.3 Calculate the weight of 200 cu.ft. of water vapour at 15.5 mm Hg and 23 C
Basis: 200 ft
3
of gas at given condition

PV T0
Volume at standard condition =
11

15.5 273
= 3.76 ft3=

296
3.76
Moles of water
=

= 0.01047 lb mole

Weight of water = (0.01047 18) = 0.18846 lb 3.4 It is desired to compress 30 lb of CO

2
to a volume
of 20 ft
3
at 30
o
C.
Find the pressure of the gas stored (required)?
30 0.6818
Basis: 30 lb CO
2
=

= 0.6818 lb mole =
2.2046
= 0.3102 kmole Volume at standard condition = 0.3102 22.414 = 6.9528 m
3
Volume at given
condition = 20 0.02832 = 0.5664 m
3
PV T1
Pressure at the given condition P
1
=
00



6.9528
303
= 1

273
= 13.62 atm
3.5 Calculate the maximum temperature to which 10 lb of nitrogen enclosed in a 30 ft
3
chamber may
be heated without exceeding 100 psi pressure. Basis: 10 lb of N
2
= 10/28 = 0.357 lb mole
Volume at standard condition = 0.357 359 = 128.21 ft
3
TV P1
\ Temperature T
1
=
01
V
=

273
30100

= 435.4 K = 162.4 C
3.6 When heated to 100 C and 720 mm Hg, 17.2 g of N
2
O
4
gas occupies a volume of 11,450 cc.
Assuming that the ideal gas law applies, calculate the percentage dissociation of N
2
O
4
to NO
2
?
NO

24
2NO
2

(92) (2 46)
N
2
O
4
present initially = 17.2/92 = 0.187 g mole;
Let x g mole of N
2
O
4
dissociate,
then, 2x g moles of NO
2
is formed.
Total moles after dissociation = (0.187 x + 2x) = 0.187 + x
Parameter Given condition (1) Standard condition (0)
Pressure
Temperature Volume
720 mm Hg 760 mm Hg 373 K 273 K 11,450 cc ?
PV 0
Volume at standard condition =
11
01

720
273
= 11450

373
= 7939.2 cc
Therefore, no. of g moles remaining =
7939.2
= 0.354
22,414
\ (0.187 + x) = 0.354
\ x = 0.167
0.167
Percentage dissociation =

100 = 89.42%

3.7 Calculate the average molecular weight of a gas having the following composition by volume.
CO
2
: 13.1%, O
2
: 7.7% and N
2
: 79.2% Basis: 1 g mole of the gas
Component Volume % = Molecular g mole Weight, g mole % weight
CO
2
13.1 44 0.131 0.131 44 = 5.764
O
2
7.7 32 0.077 0.077 32 = 2.464
N
2
79.2 28 0.792 0.792 28 = 22.176
Total 100.0 1.000 30.404 Average molecular weight is 30.404.
3.8 Calculate the density in lb/ft
3
at 29.0 inches of Hg and 30 C for a mixture of hydrogen and oxygen
that contains 11.1% of hydrogen by weight.
Basis: 1 lb of gas mixture
Component Hydrogen Oxygen
Weight % Molecular weight lb mole 0.111 2 0.111/2 = 0.0555 0.889 32 0.889/32 = 0.0278 Total
0.0833 lb moles Temperature = 30 C = 86 F = 546 R
Volume of the gas at the given condition = 0.0833 359 (29.92/29)
3

(546/492) = 34.24 ft
3
Density = (1/34.24) = 0.0292 lb/ft
3.9 Calculate the density in g/litre at 70 F and 741 mm Hg of air
Basis: 1 g mole of air
Component Volume % = mole % Molecular weight Weight, g Oxygen 0.21 32 6.72 Nitrogen 0.79 28
22.12 Total 28.84 g
Volume of air = 1

22.414

530 760

= 24.8 litres

28.84
Density of air =

= 1.162 g/litre

3.10 In 1000 ft
3
of a mixture of hydrogen, nitrogen and carbon-dioxide at 250 F, the partial pressures
are 0.26, 0.32 and 1.31 atm. Assuming Ideal Gas behaviour, find the following:
(a) lb moles of H
2
; (b) mole fraction and mole % H
2
; (c) pressure fraction of H
2
(d) partial volume of
H
2
; (e) volume fraction and volume % of H
2
; (f) weight of H
2
; (g) weight fraction and weight % of
H
2
; (h) average molecular weight; (i) density of gas mixture; (j) density at standard condition
Also, show that volume % = pressure % = mole %
Basis: 1000 ft
3
of gas mixture
(a) Partial pressure of hydrogen = 0.26 atm V = 1000 ft
3
, T = 710 R Volume of H
2
at standard condition = 1000

0.26 492
1.00 710 = 180.169 ft
3
180.169

= 0.502 lb moles
2
=

lb moles of H

(b) Total pressure = (0.26 + 0.32 + 1.31) = 1.89 atm

Total moles =



1000 1.89 492 = 3.648 lb moles


mole fraction of hydrogen =
0.502
= 0.138
3.648
0.26

= 0.138(c) Pressure fraction of hydrogen =

(d) Partial volume of hydrogen is the volume occupied by 0.502 lb moles of it at 1.89 atm and 710 R
1710
Volume of H
2
= 0.502

359

= 138 ft
3 1.89

492


(e) Volume fraction of hydrogen =
138
= 0.138
1000
Thus volume % = pressure % = mole % (f) Weight of hydrogen = 0.502 2 = 1.004 lb (g) Basis 100
lb moles of gas mixture
Mole fraction of nitrogen =
0.32
= 0.169
189

Mole fraction of carbon dioxide =
1.31
= 0.693
1.89

Mole fraction of hydrogen =
0.26
= 0.138
1.89
Component Molecular mole % lb mole Weight, lb Weight % weight
Hydrogen 2 13.8 13.8 13.8 2 = 27.6 0.78
Nitrogen 28 16.9 16.9 16.9 28 = 473.2 13.33
Carbon dioxide 44 69.3 69.3 69.3 44 = 3049.2 85.89
Total 100.0 100.0 3550.0 100.00
(h) Average molecular weight =

3550

= 35.5

(i) 1000 ft
3
of gas at given condition

1000

492
1.89



= 1309.7 ft
3
at NTP condition
Number of moles =
1309.7
= 3.648 lb moles 3.648 35.5
359
= 129.55 lb.
129.55
\
Density at given condition =

= 0.12955 lb/ft
3


( j) Density at standard condition:
Volume at standard condition = 1000

1.89 492


= 1309.7 ft
3
129.55

= 0.09892 lb/ft
3
\ Density =

3.11 A certain gaseous hydrocarbon is known to contain less than 5 carbon atoms. This compound is
burnt with exactly the volume of oxygen required for complete combustion. The volume of reactants
(all gases) is 600 ml and the volume of products (all gases) under the same condition is 700 ml. What
is the compound?
Basis: 1 mole of hydrocarbon.
Let the hydrocarbon be C
x
H
y
y
y

O
2
xCO
2
+

H
2
O
4
C
x
H
y
+ x

y
x
y
Moles: 1 x
4 2

Total moles of reactants = 1
xy

4

y
Total moles of products =
x
Reactants (1
xy/4)
600 6 Products
++===
(xy/2) 700 7
7
y
7 + 7
x
+

= 6x + 3y

(7
x
6
x
) +
7y

= 7

x
5y
= 7
4
Since the hydrocarbon has carbon atoms less than 5, we have x < 5; solving above equation assuming
carbon atoms as 1, 2, up to 5 we get the values of y as indicated below:
5y
= 8; y =
32
x = 1;
4 5

5y
= 9; y =
36
x = 2;
4 5

x = 3;
5y
= 10; y =
40
= 8
4 5

5y
= 11 y =
44
x = 4
4 5
The value of y is to be an integer.
Hence, the hydrocarbon is C
3
H
8
: (Propane)
The combustion reaction is C
3
H
8
+ 5O
2
3CO
2
+ 4H
2
O
3.12 Combustion gases having the following molal composition are passed into an evaporator at 200
C and 743 mm Hg (N
2
: 79.2%, O
2
: 7.2%, CO
2
: 13.6 %) Water is added to the stream as vapour and
the gases leave at 85 C and 740 mm Hg with the following composition N
2
: 48.3%, O
2
: 4.4% and
H
2
O : 39%. Calculate (a) volume of gases leaving evaporator per 100 litres of gas entering and (b)
weight of water added per 100 litres of gas entering.
(N
2
, O
2
, CO
2
) Evaporator (N
2
, O
2
, CO
2
) + H
2
O
Water
Basis: 100 g moles gas entering
473 760
= 3972.31 litres 22.414

Volume = 100

This 100 g moles of entering gas 61% of gases leaving. \ g moles of gases leaving = 100/0.61 = 164
g moles. Water added = 164 100 = 64 g moles = 1152 g.
760 358
Volume of gas leaving = 164 22.414
740 273
(a)
Volume of gas leaving 4950.0t100
100 litres gas-entering 3972.31
= 124.6 litres
Volume of water added
1152.0

(b) 100 29 g.
100 litres gas-entering
t
3972.31

3.13 How many g moles of nitrogen will occupy 1000 m
3
at 112 10
3
N/m
2
and 400 K
PV = nRT, where R = 8.314 J/g mole K = 8.314 (Pa) (m
3
)/g mole K PV
=
112
103

n =
1000
= 33,678 g moles
RT 8.314 400
Alternatively ,
P
1
= 1.01325 10
5
N/m
2
T
1
= 273 K
since

11PVPV2 2 T
=
T12
V
1
(at NTP) =
112
10
3
tt1000
t
273
= 754.4 m
3
400 1.01325 t10
5

1000 g moles of gas occupies 22.414 m
3
at NTP,
Hence, 754.4 m
3
contains


1000
= 33,658 g moles of nitrogen

(Error is due to the fact that T

1
is taken as 273 K and not as 273.16 K on taking T
1
as 273.16 K the g
moles of nitrogen will be 33,677)
3.14 In the manufacture of hydrochloric acid, a gas is obtained that contains 25% HCl and 75% air by
volume. This gas is passed through an absorption system in which 98% of the HCl is removed. The
gas enters the system at 48.8 C and 743 mm Hg and leaves at 26.7 C and 738 mm Hg. Applying the
pure component volume method, calculate:
(a) The volume of gas leaving per 1000 litres entering the absorption column.
(b) The weight of HCl removed per 100 litres entering. Basis: In 100 litres of entering gas volume of
air = 75 litres Pure component volume of HCl = 25 litres
Pure component volume of HCl absorbed = (25 0.98) = 24.5 litres Pure component volume of HCl
remaining = 0.5 litres Volume of gas leaving = 75 + 0.5 = 75.5 litres
(a) Parameter Entering condition Leaving condition Pressure 743 mm Hg 738 mm Hg
Temperature 48.8 C 26.7 C Volume 75.5 litres ?
Volume of (entering) gas at leaving condition
= 75.5
743

299.7
= 70.8 lit.
738 321.8
Component Litre Volume % (or) mole % (b) Composition: HCl 0.5 0.66
Air 75.0 99.34
Total: 75.5 100.00
Volume of HCl absorbed at standard condition
= 24.5
743

492
= 20.3 litres
760 580

Weight of HCl absorbed =
20.3
36.5 = 33.057 g.
22.414
3.15 Absorbing chlorine in milk of lime produces calcium hypochlorite. A gas produced by the
Deacon process enters the absorption apparatus at 740 mm Hg and 75 F. The partial pressure of Cl
2
is 59 mm Hg and the remainder being inert gas. The gas leaves at 80 F and 743 mm Hg with Cl
2
having a partial pressure of 0.5 mm Hg. Calculate, by applying the partial pressure method:
(a) volume of gas leaving per 100 litres entering
(b) weight of Cl
2
absorbed.
Basis: 100 litres of gases entering
Partial pressure of inert gas entering = 740 59 = 681 mm Hg Partial pressure of inert gas leaving =
743 0.5 = 742.5 mm Hg Volume of inert gases entering = 100 litres (681 mm Hg)
681

299.7
Volume of inert gas leaving = 100
742.5 297
(a) Volume of gas leaving = 92.5 litres (743 mm Hg)
Volumes of Cl
2
entering and leaving are 100 litres and 92.5 litres Entering condition:
Parameter Given condition (1) Standard condition (0)
Pressure 59 mm Hg 760 mm Hg Temperature 297 K 273 K Volume 100 litres ?
Volume at standard condition of Cl
2
entering
= 100
59

273
= 7.14 litres
760 297
Volume at standard condition of Cl
2
leaving
= 92.5
0.5

273
= 0.055 litre
760 299.7
Volume at standard condition of Cl
2
absorbed
= 7.14 0.055 = 7.085 litres
(b) Weight of Cl
7.285
71 = 22.45 g.
2
absorbed =
22.414
3.16 Nitric acid is produced by the oxidation of ammonia with air. In the first step of the process,
ammonia and air are mixed together and passed over a catalyst at 700 C. The following reaction
takes place. 4NH
3
+ 5O
2
6H
2
O + 4NO. The gases from this process are passed into towers where
they are cooled and the oxidation is completed according to the reactions:
2NO + O
2
2NO
2
3NO
2
+ H
2
O 2HNO
3
+ NO
The NO liberated is re-oxidized in part and forms more nitric acid in successive repetitions of the
above reactions. The ammonia and the air enter the process at 20 C and 755 mm Hg. The air is
present in such proportion that the oxygen will be 20% in excess of that required for complete
oxidation of ammonia to nitric acid. The gases leave the catalyst at 700 C and 743 mm Hg. Given the
overall reaction: 2NO + 1.5O
2
+ H
2
O 2HNO
3
, calculate the following:
(a) The volume of air to be used per 100 litres of NH
3
entering the process (b) The composition of
gases entering the catalyzer
(c) The composition of gases leaving (assuming the reaction in catalyzer is 85%)
(d) The volume of gases leaving the catalyzer for 100 litres ammonia entering
(e) Weight of acid produced per 100 litres NH
3,
assuming 90% of the nitric oxide entering the tower
is oxidized to acid.
NH
3
Catalyzer
Air
Exit gas Absorber
HNO
3
Basis: 1 g mole of NH
3
overall reaction is NH
3
+ 2O
2
HNO
3
+ H
2
O O
2
required is 2 g moles
But O
2
supplied is 2 1.2 = 2.4 g moles
i.e. air supplied is
2.4
= 11.42 g moles
0.21
Thus, N
2
= 9.02 g moles.
(a) Volume of air = 11.42 22.414
293

760
= 276.4 litres
273 755

Volume of NH
3
= 1
293

760
= 24.2 litres 22.414
273 755

Volume of air/100 litres of NH
3
=
276.4 100
= 1142.2 litres
24.2
(b)
Component g mole mole % = volume % NH
3
1.00 8.0
O
2
2.40 19.3 N
2
9.02 72.7 Total 12.42 100.0
(c) Gases leaving catalyzer are nitrogen, oxygen, ammonia, nitric oxide and water:
N
2
(all that enters) = 9.02 g moles
NH
3
(85% conversion) = (1 0.85) = 0.15 g mole
O
5
= 1.06 g moles
2
consumed =
4
O
2
leaving = (2.4 1.06) = 1.34 g moles
NO formed = 0.85 g mole
H
6
= 1.275 g moles
2
O formed =
Component N
2
O
2
NH
3
NO H
2
O Total g moles 9.02 1.34 0.15 0.85 1.275 12.635
mole % = volume % 71.40 10.60 1.20 6.70 10.10 100.000
(d) Volume of gases leaving the catalyzer
= 12.635
973

760
= 1031.8 litres 22.414
273 243
This is the volume of gases leaving for 24.2 litres of ammonia entering
Therefore, for 100 litres of NH
3
entering
= (1031.8 100)/24.2 = 4264 litres of gas leaves
(e) NO entering the tower = 0.85 g mole
NO converted = 0.85 0.9 = 0.765 g mole
HNO
3
produced = 0.765 g mole = (0.765 63) = 48 g For 100 litres of NH
3
weight of HNO
3
produced
=
48 100
= 199 g
24.2
3.17 1000 kg/h of an organic ester C
19
H
36
O
2
is hydrogenated to C
19
H
38
O
2
in a process. The company purchases its H
2
in cylinders of 1 m
3
capacity. The pressure in cylinder is initially 10 kg/cm
2
(abs.) and drops to 2 kg/cm
2
(abs.) after use.
The company works 24 h/day, 7 days a week. How many cylinders are needed per week?
Basis: Ester being processed in one week = (1000 24 7) = 1,68,000 kg
C
19
H
36
O
2
+ H
2
C
19
H
38
O
2
296 2 298
296 kg of ester reacts with 2 kg of H
2
168000 kg of ester reacts with
2 168000
= 1135 kg of hydrogen
296

1 kmole of any gas occupies 22.414 m
3
at NTP
10
1

H
2
initially present in the cylinder (10 m
3
) = (1) = 0.45 kmole (by reducing to
NTP condition)
12
H
2
after use =

= 0.09 kmole

\ H
2
available from one cylinder = 0.36 kmole
1135
H
2
needed = 1135 kg =

= 567.5 kmoles

The number of cylinders required should be full number, rounded to next highest value
567.5

= 1577\ Cylinders required per week =

3.18 A mixture of toluene and air is passed through a cooler where some toluene is condensed. 1000
ft
3
of gases enter the cooler per hour at 100 C and 100 mm Hg (gauge). The partial pressure of
toluene is 300 mm Hg. 740 ft
3
of gases leave cooler per hour at 40 mm Hg and 50 C. Calculate the
weight of toluene condensed per hour. Vapour pressure of toluene at 50 C = 90 mm Hg.
Basis: One hour
100 mm Hg (gauge) = 860 mm Hg (abs.)

300
= 348.8 ft
3
Toluene entering =

Weight =
348.8
860



273 92 = 74 lb.

At exit, air is saturated with toluene.

90
Toluene leaving = 740

= 90 ft
3

Weight =
90
740



273 92 = 19 lb.

\ Weight of toluene condensed = 74 19 = 55 lb.
3.19 Air is dried from a partial pressure of 50 mm of water vapour to a partial pressure of 10 mm.
The temperature of entering air is 500 F and the pressure remains constant at 760 mm Hg. How much
water is removed per 1000 ft
3
of entering air?
Basis: 1000 ft
3
of entering air.
Moles of air entering =
1000 492
= 1.43 lb moles
359 960

Moles of water in it =
50
= 0.094 lb mole
760
Moles of dry air = (1.43 0.094) = 1.336 lb moles
Moles of water leaving =



10
= 0.0178 lb mole

Water condensed = (0.094 0.0178) = 0.0762 lb mole = 1.37 lb 3.20 Chimney gas has the following
composition:
CO
2
: 9.5%, CO : 0.2%, O
2
: 9.6% and N
2
: 80.7%. Using ideal gas law, calculate:
(a) its weight percentage
(b) volume occupied by 0.5 kg of gas at 30 C and 760 mm Hg. (c) density of the gas in kg/m
3
at
condition of (b)
(d) specific gravity of the gas mixture.
(Density of air may be taken as 1.3 g/cc)
Basis: 100 kmoles of chimney gas
(a)
Component Mol. weight Weight, kmole Weight, kg Weight %
CO
2
44 9.5 (9.5 44) = 418.0 13.978
CO 28 0.2 (0.2 28) = 5.6 0.187
O
2
32 9.6 (9.6 32) = 307.2 10.273
N
2
28 80.7 (80.7 28) = 2259.6 75.562
Total 100.0 2990.4 100.000
(b) 0.5 kg of gas =
0.5
= 0.01672 kmole
29.904
303

22.414

Volume at 30 C, 760 mm Hg = 0.01672

= 0.416 m
3
0.5

= 1.202 kg/m
3
(c) Density =

(d) Specific gravity = density of gas/density of air =
1.202
= 0.925
1.300
3.21 A producer gas has the
following composition CO
2
: 4.4%, CO : 23%, O
2
: 2.6% and N
2
: 70%. Calculate the following:
(a) volume of air at 25 C and 750 mm Hg required for the
combustion of 100 m
3
of gas at the same condition if 25% excess air is used
(b) the composition and volume of gases leaving the burner at 350 C and 750 mm Hg per 100 m
3
of
gas burnt.
Basis: 100 kmoles of producer gas.
CO = 23 kmoles
O
2
needed = 23/2 = 11.5 kmole; O
2
in feed = 2.6 kmoles O
2
actually needed = (11.5 2.6) = 8.9
kmoles
Air supplied =
8.9 1.25
= 52.98 kmoles
0.21
O
2
supplied = 52.98 0.21 = 11.125 kmoles
N
2
in air = 52.98 0.79 = 41.85 kmoles

298 760
Volume of feed = 100 22.414
273

750

= 2479.28 m
3
Volume of air = 52.98

22.414

298 760
= 1313.43 m
3


(a) Volume of air/100 m
3
of feed =
1313.43100
= 52.98 m
3
2479.28
(b) (assuming complete combustion)
CO
2
leaving the burner = (4.4 + 23) = 27.400 kmoles O
2
leaving = (8.9 0.25) = 2.225 kmoles N
2
leaving = (70 + 41.85) = 111.850 kmoles
141.475 kmoles
Composition of gases leaving (volume % = mole %): CO
2
: 19.37%, O
2
: 1.57% and N
2
: 79.06%
Volume of gases leaving = 141.475

22.414

623

760
273

750 = 7332.92 m
3
Volume of gases leaving/100 m
3
of feed =
7332.92 100
= 295.76 m
3
2479.28
3.22 Natural gas has the following composition: CH
4
: 94.1%, C
2
H
6
:3% and N
2
: 2.9%. This gas is
piped from the well at 80F and 80 psi. Calculate the following.
(a) Partial pressure of N
2
(b) Pure component volume of N
2
per 100 ft
3
of the gas (c) Density
Basis: 100 ft
3
of the natural gas
(a) Partial pressure of N
2
=
80 2.9
= 2.32 psia.
100

(b) Pure component volume of N
2
= 0.029 100 = 2.9 ft
3
(c) Volume of gas at NTP = 100

80 492
= 497 ft
3
14.67

540

No. of moles of gas =
497
= 1.38 lb moles.
359
Component mole % lb mole Weight, lb
CH
4
94.1 1.38 0.941 = 1.298 (1.298 16) = 20.777
C
2
H
6
3.0 1.38 0.03 = 0.042 (0.042 30) = 1.260
N
2
2.9 1.38 0.029 = 0.040 (0.040 28) = 1.120
Total 100.0 1.380 23.157

23.157

= 0.23157 lb/ft
3
Density of gas =

23.157

= 0.0466 lb/ft
3
Density at standard condition =

3.23 Compare pressures given by the ideal gas and van der Waals equation for 1 mole of CO
2
occupying a volume of (381 10
6
) m
3
at 40 C

RT
= 6.831 10
6
N/m
2
(a) Ideal gas law P =
nV

where, R = 8.314 N.m/g mole K (J/g mole K); T = 313 K; V = 381 10
6
m
3
(b) van der Waals equation
P
a
(V b) = nRT

a = 0.3646; b = 4.28 10
5
rest same as above
RTa
P
=

V

t
P = 65 62381

= 5.2 10
6
N/m
2
3.24 It is desired to market O
2
in small cylinders having volumes of 0.5 ft
3
and exactly containing 1 lb
of gas at 120 F. What is the pressure? Basis: 1 lb of O
2
= 1/32 = 0.031 lb mole; R = 0.73 ft
3
atm/lb
mole R
T = 120 + 460 = 580 R
P =
nRT
= 0.031 0.73
580
= 26.5 atm
V 0.5
3.25 A tire is inflated to 35 psig at 0 F. To what temperature it can be heated up to a pressure of 50
psig, volume remaining same? P
1
= 35 + 14.67 = 49.67 psia; P
2
= 50 + 14.67 = 64.67 psia. T
1
= 460
R; V
1
= V
2
; n
1
= n
2
; T
2
= ?
PV P V

11
2 2
T

()( ) ( )
460);600R
TT P2 49.6712 1
\ Temperature = 140 F
3.26 Calculate densities of C
2
H
6
and air at NTP.
At NTP 1 g mole occupies 22,414 cc.
Density of C
2
H
6
=
130
= 1.3 10
3
g/cc
22414

Density of air =
128.84
= 1.29 10
3
g/cc
22414
3.27 Acetylene gas is produced according to the reaction
CaC
2
+ 2H
2
O C
2
H
2
+ Ca(OH)
2
Calculate the number of hours of service that can be got from 1 lb of carbide in lamp burning 2 ft
3
of
gas/hour at 75 F and 743 mm Hg.
Basis: 1 lb of CaC
1
= 0.0156 lb mole.
2
=
64
CaC
2
+ 2H
2
O C
2
H
2
+ Ca(OH)
2
64 36 26 74
Volume of acetylene got = 0.0156

359

535 760
= 6.24 ft
3
492

743
6.24
Time of burning =

= 3.12 h.

A similar problem has been solved in MKS system also: Data: 1 kg CaC
2
; 25 C; 740 mm Hg; for a
lamp burning gas 40 litres h.
Basis: 1 kg CaC
2
=
1
= 0.0156 kmole.
64
Volume of C
2
H
2
= 0.0156

22414

298 760

= 392.6 litres.

392.6
Time of burning =

= 9.8 h.

3.28 By electrolyzing a mixed brine a mixture of gases is obtained at the cathode having the following
composition by weight: Cl
2
: 67%, Br
2
: 28%, O
2
: 5%. Calculate:
(a) composition by volume
(b) density at 25 C and 740 mm Hg
(c) specific gravity of the gas mixture.
Basis: 100 g of gas mixture
(a)
Component Molecular Weight, g Weight, Volume % weight g mole = mole %
Cl
2
71 67 (67/71) = 0.945 74.0
Br
2
160 28 (28/160) = 0.175 13.7
O
2
32 5 (5/32) = 0.156 12.3
Total 100 1.276 100
(b) Volume of gases = 1.276

22.414

298 760
= 32 litres

100
Density =

= 3.12 g/litre

(c) Density of air = 1.293 g/litre (at standard condition) Density of air at 25 C and 740 mm Hg

273 740
= 1.15 g/litre

= 1.293


Alternatively, volume of air at 25 C and 740 mm Hg
760 298
= 25.13 litres

= 22.414


Density of air =
28.84
= 1.15 g/litre
25.13

Specific gravity of gas mixture =
3.12
= 2.7
1.15
3.29 A mixture of NH
3
and air at 730 mm Hg and 30 C contains 5.1 NH
3
by volume. This gas is
passed at a rate of 100 ft
3
/min. through an absorption tower in which NH
3
is removed. The gases
leave the tower at 725 mm Hg and 20 C having 0.05% NH
3
by volume. Calculate:
(a) the rate of flow of gases leaving the tower and
(b) weight of NH
3
absorbed.
Basis: 100 ft
3
of entering gases.
Volume of NH
3
= 5.1 ft
3
and of air = 94.9 ft
3
(730 mm Hg, 30 C)
730 293
= 92.4 ft
3
Volume of air at exit condition = 94.9
725 303

92.4 ft
3
of air 99.95% of exit gas.
92.4
(a)
\
Volume of exit gas =

= 92.447 ft
3
/min.

Volume of NH
3
in exit = 0.047 ft
3
Volume of exit NH
3
at inlet condition = 0.047

725 303


= 0.0482 ft
3
(b) Volume of NH
3
absorbed = (5.1 0.0482) = 5.0518 ft
3
Volume of NH
3
absorbed at NTP = 5.0518

730 273


= 4.372 ft
3
Moles of NH
3
=
4.372
= 0.012 lb mole = 0.207020 lb
359
3.30 1000 ft
3
of moist air at 740 mm Hg and 30 C contains water vapour in such proportions that its
3.30 1000 ft
3
of moist air at 740 mm Hg and 30 C contains water vapour in such proportions that its
partial pressure is 22 mm Hg. Without the total pressure being changed, the temperature is reduced to
15 C and some water condenses. After that the partial pressure of water is 12.7 mm Hg. Using
partial pressure method, find the following: (a) Volume of gas after cooling and
(b) Weight of water condensed.
Basis: 1000 ft
3
of moist air at 740 mm Hg and 30 C
Partial pressure of water = 22 mm Hg
Partial pressure of air = (740 22) = 718 mm Hg
Partial pressure of air after cooling = (740 12.7) = 727.3 mm Hg
718288
= 938 ft
3
(a) Volume of air after cooling = 1000
After cooling volume of gases = Volume of water vapour + Dry air (740 mm, 15 C) (12.7
mm, 15 C)

12.7 303
Volume of air leaving at inlet condition = 938 = 570 ft
3
Volume of water vapour condensed = 1000 570 = 430 ft
3
43022273
(b) Water condensed =


18 = 0.562 lb
3.31 A producer gas has the following composition by volume CO : 23%, CO
2
: 4.4%, O
2
: 2.6% and
N
2
: 70%
(a) Calculate the ft
3
of gas at 70 F and 750 mm Hg per lb of carbon
present.
(b) Calculate the volume of air required for the combustion of 100 ft
3
of the gas if 20% excess air is
used.
(c) Calculate the volumetric composition of gases leaving assuming complete combustion.
(d) Calculate the volume of gases leaving at 600 F and 750 mm Hg per 100 ft
3
gas burnt.
Basis: 100 lb moles of gas
i.e. carbon in the feed = 23 + 4.4 = 27.4 atoms

530 760
= 39,200 ft
3
(a) Volume of gases = 100 359


Weight of carbon present = (27.4 12) = 328.8 lb.
39200
(Volume of gas/lb of carbon) =

= 119.2 ft
3
/lb.

23
(b) O
2
required for the combustion of CO =

= 11.5 lb moles

O
2
available in feed = 2.6 lb moles
Theoretical O
2
required = (11.5 2.6) = 8.9 lb moles
O
2
supplied = (8.9 1.2) = 10.68 lb moles
100

= 50.85 lb moles

Air supplied = 10.68

Volume of air = 50.85

359

530 760
= 19,930 ft
3



(70
o
F, 750 mm Hg)
Volume of feed = 100

359

530 760
= 39,200 ft
3


Volume of air/100 ft
3
of feed =
19930 100
39200
(c) CO
2
leaving = (23 + 4.4)
O
2
remaining = (10.68 8.9)
= 50.85 ft
3
= 27.40 lb moles = 1.78 lb moles N
2
leaving (from air) = (50.85 10.68) = 40.17 lb moles N
2
entering along with feed
N
2
Total
Total
Composition of CO
2
Volume % 19.66 = 70.00 lb moles = 110.17 lb moles = 139.35 lb moles
O
2
N
2
1.28 79.06
(d) Volume of gases leaving
= 139.35

359

760
1060


= 1,09,218 ft
3



1,09,218100
= 278.6 ft
3
Volume of gases/100 ft
3
of feed =
39,200
3.32 A furnace is to be designed to burn coke at the rate of 200 lb/h having a composition C : 89.1%
and ash : 10.9%. The grate efficiency of the furnace is such that 90% of the carbon present in the coke
charged is burnt. Air supplied is 30% in excess of that required for complete combustion. It may be
assumed that 97% of the carbon burnt is oxidized to carbon dioxide and the rest to carbon monoxide.
(a) Calculate the composition of the flue gases.
(b) If the flue gases leave the furnace at 550 F and 743 mm Hg, calculate the rate of flow of gases in
ft
3
/min.
Basis: 100 lb of coke.
C + O
2
CO
2
C : 89.1 lb. Ash : 10.9 lb.
Carbon burnt = 89.1 0.9 = 80.19 lb
Carbon burnt to CO
2
= 80.19 0.97 = 77.78 lb = 6.48 lb moles Carbon burnt to CO = 80.19 0.03 =
2.41 lb = 0.2 lb mole
32
308.88

O
2
supplied = 89.1

1.3 = 308.88 lb =

= 9.65 lb moles
100
Air supplied = 9.65

= 45.96 lb moles

N
2
in air = (45.96 9.65) = 36.31 lb moles
6.48
0.2
O
2
required =

= 6.58 lb moles

Excess O
2
leaving = (9.65 6.58) = 3.07 lb moles
(a)
Component lb mole mole % CO
2
6.48 14.07
CO 0.20 0.43
O
2
3.07 6.67
N
2
36.31 78.83
Total 46.06 100.00
(b) Volume of flue gases = 46.06

359

760
1010


= 34,722 ft
3


Hence, for 200 lb/h of coke charge, volume of flue gases is = (34,722 2) = 69,444 ft
3
/h
i.e. Volumetric flow rate of flue gases = 1157.4 ft
3
/min.
3.33 In the fixation of nitrogen by the arc process, air is passed through a magnetically flattened
electric arc. Some of the nitrogen is oxidized to NO, which on cooling, oxidizes to NO
2
. Of the NO
2
formed, 66% will be associated to N
2
O
4
at 26 C. The gases are then passed into water washed
absorption towers where nitric acid is formed.
3NO
2
+ H
2
O 2HNO
3
+ NO
NO liberated in this reaction will be reoxidized in cooler.
In the operation of such a plant it is possible to produce gases from the arc furnace in which the NO is
2% by volume while hot. The gases are cooled to 26 C at 750 mm Hg before entering the absorption
column.
(a) Calculate the composition of hot gases leaving the furnace
assuming air is at NTP.
(b) Calculate the partial pressure of NO
2
and N
2
O
4
in the gas entering
the absorption apparatus.
(c) Calculate the weight of acid formed per 1000 litres of gas entering the absorption system if the
combustion to HNO
3
of the combined nitrogen in the furnace gases is 85% complete.
H
2
O
Air
Arc
NO
Cooler
NO2
Chamber
N2O4 Abs.
N
2
,O
2
2% 26 C,
Col.
750 mm
HNO
3
Basis: 100 g moles of air contain N
2
: 79 g moles and O
2
: 21 g moles. (a) Reaction in arc furnace is
given as
N
2
+ O
2
2NO
which means x mole of N
2
react to give 2x mole of NO. Total moles of gas leaving = (79 x) + (21
x) + 2x = 100 (by stoichiometry) N
2
O
2
NO when x = 1, we have, N
2
O
2
NO

78 20 2

2x
% NO = 2 =
100
\ x = 1
(b) Reaction in cooler NO + O
2
NO
2
2 g moles of NO gives 2 g moles of NO
2
O
2
remaining = (20 1) = 19 g moles
Reaction in chamber is 2NO
2
N
2
O
4
66% of NO
2
remains as N
2
O
4
Moles of NO
2
associated to N
2
O
4
= (2 0.66) = 1.32 \ N
2
O
4
formed = 0.66 g mole
NO
2
remaining = 2 1.32 = 0.68 g mole
NO
2
N
2
O
4
O
2
N
2
Total
Total moles: 0.68 + 0.66 + 19 + 78 = 98.34
Partial pressure of NO
2
=
0.68 750
= 5.188 mm Hg.
98.34
Partial pressure of N
0.66 750
= 5.030 mm Hg.
2
O
4
=
98.34
(c) Combined N
2
: in NO
2
0.68 g mole
in N
2
O
4
(0.66 2) = 1.32 g moles/2 g moles
Thus, 3NO
2
+ H
2
O 2HNO
3
+ NO
Total moles of gas in 1000 litres of entering gas
PV
= RT
750
1000
=


760
= 40.25 g moles
Moles of NO
2
= (40.25)
(0.68)
= 0.278 g mole
98.34
3 moles of NO
2
yields 2 moles of HNO
3
.
2
\
0.278 kmole of NO
2
yields 0.278

0.85 = 0.158 kmole of HNO

3
(85% conversion)
\ Weight of HNO
3
formed = 0.158 63 = 9.95 g.
3.34 The gas leaving a gasoline stabilizer has the following analysis by volume C
3
H
8
: 8%, CH
4
:
78%, C
2
H
6
: 10% and C
4
H
10
:4%
This gas leaving at 90
o
F and 16 psia at the rate of 70,000 ft
3
/h is fed to gas reforming plant where the
following reaction takes place.
C
n
H
2n+2
+ nH
2
O nCO + (2n + 1)H
2
(1) CO + H
2
O CO
2
+ H
2
(2) Reaction (1) is 95% complete
and Reaction (2) is 90% complete. Find (a) Average molecular weight of the gas leaving stabilizer;
(b) weight of gas fed to reforming plant (lb/h) (c) weight of H
2
leaving (lb/h) and (d) composition of
gases leaving (weight %)
Basis: One hour = 70,000 ft
3
of gas.

492 16
= 68,295 ft
3
Volume of gas at NTP = 70,000
550

68,295
Moles of gas =

= 190.24 lb moles

Components C
3
H
8
CH
4
C
2
H
6
C
4
H
10
Total
Volume % 8 78 10 4 100 lb mole 15.22 148.39 19.02 7.61 190.24 Molecular weight 44 16 30 58
Weight, lb 669.68 2374.24 570.6 441.38 4055.9
(a) Average molecular weight of the gas leaving stabilizer
=
4055.9
= 21.32
190.24
(b)
C H

38
+ 3H O
2
3CO + 7H
2

44 54 84 14
CH
+ H O

42
CO + 3H
2
16 18
28
6

26 2
CH +2H O 2CO+5H
2
30 36
56
10
C H

410
+ 4H O
2
4CO + 9H
2

58 72 112 18
Weight of water produced from C
3
H
8
= (15.22 3 18) = 821.88 lb Weight of water produced from
CH
4
= (148.39 1 18) = 2,671.02 lb Weight of water produced from C
2
H
6
= (19.02 2 18) =
684.72 lb Weight of water produced from C
4
H
10
= (7.61 4 18) = 547.92 lb
Total = 4,725.54 lb CO + H
2
O CO
2
+ H
2
Total CO formed = (15.22 3) + 148.39 + (19.02 2) + (7.61 4) = 262.53 lb moles.
H
2
O needed for forming CO = (262.53 18) = 4725.54 lb. Weight of gas fed to reformer = [4055.9 +
(4725.54 2)] = 13,506.98 lb/h.
(c) Hydrogen formed:
From Reaction (1) (hydrocarbons undergo 95% conversion), we have
(15.22 0.95 7) + (148.39 0.95 3) + (19.02 0.95 5) + (7.61 0.95 9) = 679.535 lb moles
Total CO formed = (262.53 0.95) = 249.40 lb moles Hydrogen from CO (90% conversion) =
(249.40 0.90) = 224.46 lb moles \ Total hydrogen leaving reformer = (679.535 + 224.46) 2 = 1808
lb/h
(d) Gases leaving unreacted = HC, H
2
O, CO, CO
2
, H
2
H
2
= 1808.000 lb
C
3
H
8
15.22 0.05 44 = 33.484 lb
CH
4
148.39 0.05 16 = 118.712 lb
C
2
H
6
19.0 0.05 30 = 28.530 lb
C
4
H
10
7.61 0.05 58 = 22.069 lb
CO 249.4 0.1 28 = 698.320 lb
CO
2
249.4 0.9 44 = 9876.240 lb
H
2
O 262.53 0.05 18 = 236.277 lb
(from Reaction 1) H
2
O [4,725.54 (224.46 18)] = 685.260 lb
(from Reaction 2) 13,506.892 lb
Component C
3
H
8
CH
4
C
2
H
6
C
4
H
10
CO CO
2
H
2
OH
2
Total
Weight, lb 33.484 118.712 28.53 22.069 698.32 9,876.24 921.537 1808 13,506.892 Weight % 0.248 0.879 0.212 0.163 5.17 73.12 6.823
13.385 100.000
3.35 Analysis of a sewage gas sample from municipal sewage plant is given. CH
4
: 68%, CO
2
: 30%
and NH
3
: 2%. 600 m
3
/h of this gas at 30
o
C and 2 atmospheres is flowing through a pipe. Find (a) the
average molecular weight of the sewage gas and (b) the mass rate of flow of gas in kg/h and (c)
density of the gas.
Basis: 100 kmoles of the sewage gas.
(a) the average molecular weight can be calculated from the following table.
Gas Molecular weight Weight, kmole Weight, kg
CH
4
16 68 68 16 = 1,088
CO
2
44 30 30 44 = 1,320
NH
3
17 2 2 17 = 34
Total 100 2,442
Average molecular weight =
2, 442
= 24.42
100
(b) Volumetric flow rate at standard condition
= 600
2732
= 1081.2 m
3
/h
3031
1081.2
Molar flow rate of gases =

= 48.24 kmoles/h

We know that 100 kmoles of this gas weighs = 2,442 kg Therefore, the weight of 48.24 kmoles
2,44248.24
= 1,178 kg.= 100
Hence, the mass flow rate of gas in kg/h = 1,178 kg/h
(c) Density of the gas is
2442
= 2.26 kg/m
3
.
1081.2
3.36 In the process of manufacturing Cl
2
, HCl gas is oxidized with air as follows:
4HCl + O
2
2Cl
2
+ 2H
2
O
If the air used is 30% excess and oxidation is 80% complete, find the composition of dry gases
leaving.
Basis: 4 kmoles HCl gas.
O
2
needed = 1 kmole
O
2
supplied = 1.3 kmoles

79
N
2
entering
= 1.3

= 4.89 kmoles

O
2
remaining = (1.3 0.8) = 0.5 kmole
HCl un-reacted = (4 0.2) = 0.8 kmole
Cl
2
formed = (2 0.8) = 1.6 kmoles
Composition of dry gases leaving is presented in the following table
Gas mole mole %
HCl 0.80 10.27
O
2
0.50 6.42
N
2
4.89 62.77
Cl
2
1.60 20.54
Total 7.79 100.00
3.37 A mixture of NH
3
and air at 730 mm Hg and 30 C contains 5.1% NH
3
. The gas is passed
through an absorption tower at the rate of 100 m
3
/h where NH
3
is removed. The gases leave the tower
at 725 mm Hg and 20 C having 0.05% NH
3
. Calculate (a) the rate of flow of gas leaving the tower
and (b) weight of NH
3
absorbed in kg/h.
0.05% NH
3
,
Abs. 20 C
100 m
3
/h,
Tower 725 mm Hg 30 C,
730 mm Hg
5.1% NH
3
Basis: One hour of operation
Moles of gas entering per hour =

100
730
273

22.414

303
= 3.86 kmoles
NH
3
entering = 3.86 0.051 = 0.197 kmole
Air entering = (3.86 0.197) = 3.663 kmoles
3.663 kmoles of air contains 0.05% NH
3
while leaving the absorber Therefore the total moles of
gases leaving the absorber is
=
3.663
= 3.665 kmoles
0.9995
Hence, NH
3
leaving the tower = 0.002 kmole.
(b) NH
3
absorbed = (0.197 0.002) 17 = 3.317 kg
Volumetric flow rate of exit gas
= 3.665

22.414

760 293

= 92.42 m3/h

3.38 The analysis of a flue gas, from a fuel gas containing no N
2
has CO
2
: 4.62%, CO : 3.08%, O
2
:
8.91% and N
2
: 83.39%. Calculate (a) kmole of dry air supplied per kmole of dry flue gas (b) %
excess air (c) analysis of the fuel gas which is a mixture of CH
4
and C
2
H
6
.
Basis: 100 kmoles of dry flue gas.
(a) Air supplied =
83.39
= 105.56 kmoles (from nitrogen balance)
0.79
kmole of dry air/kmole of dry flue gas = 1.0556
CH
4

CO2
C2H6
CO Reactions are:
Air

O
2
CH
4
+ 2O
2
CO
2
+ 2H
2
O N
2
C
2
H
6
+ 3
1
/
2
O
2
2CO
2
+ 3H
2
O
(b) O
2
supplied = 105.56 0.21 = 22.17 kmoles
O
2
consumed = (22.17 8.91) = 13.26 kmoles
O
2
needed for conversion of CO to CO
2
=
3.08
= 1.54 kmoles
2
\ O
2
needed for complete combustion = 14.80 kmoles Excess oxygen = (8.91 1.54) = 7.37 kmoles
7.37
% Excess air =

100 = 49.8%

(c) Let CH
4
be x kmole and C
2
H
6
be y kmole Making a CO
2
balance, x + 2y = (4.62 + 3.08) =
7.70 O
2
needed (by stoichiometry) 2x + 3.5y = 14.8 Solving for x and y, we get x = 5.3 and y = 1.2
Gas Weight, kmole mole %
CH
4
5.3 81.54
C
2
H
6
1.2 18.46
Total 6.5 100.00
3.39 A furnace is fired with coke containing 90% carbon and 10% ash. The ash pit residue after being
washed with water analyze 10% carbon; 40% ash and rest water. The flue gas analysis shows CO
2
:
14%, CO : 1%, O
2
: 6.4% and the rest N
2
Calculate the following:
(a) Volume of flue gas produced at 750 mm Hg and 250 C per tonne of coke charged.
(b) % Excess air used
(c) % Of carbon charged which is lost in the ash.
Basis: 100 kmoles of exit gas.
N
2
= 100 (14 + 1 + 6.4) = 78.6 kmoles
From the foregoing, air supplied = 78.6/0.79 = 99.5 kmoles; O
2
in air supplied is = 20.9 kmoles
Furnace
Flue gas
Coke (F)
Ash (P)
O
2
reacted = 20.9 6.4 = 14.5 kmoles.
Let F be the coke supplied and P be the ash in the pit (in kg) Total carbon reacted = Total carbon in
flue gas = 15 katoms Carbon balance: 0.9F = (15 12) + 0.1P (1)
Ash balance: 0.1F = 0.4P (2) (i.e.) F = 4P
Substituting for (1) from (2), we get
(0.9 4P) = 180 + 0.1P
(3.6P 0.1P) = 180
180
= 51.43 kg (ash)\ P =
3.5
F = 205.72 kg (coke)
2C + O
2
2CO
C + O
2
CO
2
;
CO + O
2
CO
2
Carbon lost in ash: 10% = 51.43 0.1 = 5.143 kg (for 205.72 kg of coke fed)
O
2
needed theoretically:
O
2
supplied: 20.9 kmoles
O
2
needed (theoretically):
Total Carbon fed = 205.72 0.9
= 185.148 kg
= 15.429 katoms
O
2
needed for conversion of C to CO
2
is 15.429 kmoles (by stoichiometry) Excess O
2
= 20.9
15.429 = 5.471 kmoles
5.471
(b) % Excess air =

100 = 35.46 %

(a) Total carbon fed = (0.9 205.72) = 185.148 kg

205.72 kg of coke gives 100 kmoles of gas
100
1000 kg of coke gives 1000

= 486.1 kmoles of the gas

Aliter
For 1000 kg of coke fed, carbon in coke: 1000 0.9 = 900 kg
Carbon lost in ash = 5.143 kg
1000
= 25 kg
205.72
\ Carbon reacted = 900 25 = 875 kg = 72.916 katoms
15 katoms of carbon reacted 100 kmoles of flue gas
72.916 katoms reacted 486.1 kmoles flue gas
Volume of flue gas produced
760 523
= 486.1 22.414
750 273

= 21,151.2 m
3
/ton of coke.
51.43
(c) Carbon lost =



0.1
100 = 2.78%

3.40 Hot air is being used to dry a wet wallboard. The hot air enters the drier at 768 mm Hg and
166.7 C. The partial pressure of water vapour in this air is 25 mm Hg. At the exit partial pressure of
water is 100 mm Hg. For a total pressure of 760 mm Hg at 111.1 C in this process, calculate the
volume of exit air per cubic metre of inlet gas.
Basis: 1 m
3
of inlet air = 1000 litres = 10
6
cc
Moles of air entering =
1 768 273
= 0.02799 kmole
22.414 439.7
In the incoming stream, moles of water/mole of wet air
=
25
= 0.0326
768

In the outgoing stream, moles of water/mole of wet air =
100
= 0.1316
768
moles of dry air entering = 0.02799 (1 0.0326)
= 0.02707 kmole
moles of wet air leaving = 0.02707 (1 + 0.1316)
= 0.03063 kmole
384.1

Volume of exit air = 0.03063 22.414

= 0.9659 m
3
3.41 Applying Ideal gas law find out the maximum temperature which 20 kg of CO
2
enclosed in 20 m
3
chamber may be heated to with pressure not exceeding 20 bar.
Basis: 20 kg of carbon dioxide =
20
= 0.454 kmole
44
Volume at standard conditions: 0.454 22.414 = 10.19 m
3
P
1
= 1 bar, V
1
= 10.19 m
3
, T
1
= 273 K P
2
=
20 bar, V
2
= 20 m
3
, T
2
= ?
PVPV

2 2
We know that
11


12
Thus T
2
is found to be 10,716.3 K = 10,433.3 C
3.42 A telescopic gas holder contains 1000 m
3
of gas saturated with water
vapour at 20 C and a pressure of water 155 mm Hg above
atmosphere. The barometer reads 725 mm Hg. Find the weight of water in the gas. Vapour pressure of
water is 20 mm Hg.
Basis : 1000 m
3
of the gas at the given conditions
155 mm of water = 11.39 mm Hg.
Given pressure = 725 + 11.39 = 736.39 mm Hg.
Volume at standard conditions
=

1000
273

736.39
= 902.79 m
3
.
293760

20
902.79

Amount of water =
725
= 1.111 kmole = 20 kg of water
22.414
3.43 A gaseous mixture has the following three components X, Y, Z and the composition is as
expressed below. Find the molecular weight of Y component.
Component mole % Weight % Molecular weight Weight X 35 85 3585 Y 20.0 ? 40 M Z 25
60 2560
Total 4475 + 40M Basis: 100 moles of mixture
Let M be the molecular weight of component Y
Therefore, mole % of Y = 40%
100 Weight, % of Y = 20 = (40 M)
(35 85) (40 M)
(25
60)
89500 + 800 M = 4000 M
Therefore, M = 27.97
3.44 One hundred m
3
of mixture of N
2
, CO
2
and H
2
in the ratio of 4 : 3 : 1 is at 150 C and 2 atm
pressure. Find the mole fraction, weight % of each, average molecular weight, and total weight of the
mixture.
4
Partial pressure of N
2
=

2 = 1 atm

Partial pressure of CO
2
=
3
2 = 0.75 atm

Partial pressure of H
2
=
1
2 = 0.25 atm

8
T

v 1
Number of moles of N
2
= p TP
22.414
=
1


100 273 1 = 2.88 kmoles

v 1
Number of moles CO
2
=
p TP

22.414

= 0.75 100 2731 = 2.16 kmoles

Number of moles of H
2
=
0.25
100
273

= 0.72 kmole
473 1 22.414

Compound Weight, Molecular Weight, Weight mole kmoles weight kg % %
N
2
2.88 28 80.676 45.531 0.500
CO
2
2.16 44 95.080 53.66 0.375
H
2
0.72 2 1.441 0.81 0.125
Total 5.76 177.197 00.00 1.000
Average molecular weight = 2 (0.125) + 28 (0.5) + 44 (0.375) = 30.75
Total weight = 177.197 kg
EXERCISES
3.1 A liquefied mixture of n-butane, n-pentane and n-hexane has the following composition in percent.
n-C
4
H
10
: 50
n-C
5
H
12
: 30
n-C
6
H
14
: 20
Calculate the weight fraction, mole fraction and mole percent of each component and also the average
molecular weight of the mixture. 3.2 A steel tank having a capacity of 25 m
3
holds carbon dioxide at
30 C and 1.6 atm. Calculate the weight of the carbon dioxide in grams. 3.3 A steel container has a
volume of 200 m
3
. It is filled with nitrogen at
22 C and at atmospheric pressure. If the container valve is opened and the container heated to 200
C, calculate the fraction of the nitrogen which leaves the container.
3.4 Natural gas has the following composition in volumetric percent: CH
4
: 80%, C
2
H
6
: 15% and N
2
: 5%
Calculate (a) composition in mole %, (b) composition in weight % (c) Average molecular weight,
and (d) density at standard condition.
3.5 A typical flue from a chimney is found to contain the following composition by weight: Oxygen :
16%, Carbon monoxide : 4%, Carbon dioxide : 17% and rest nitrogen. Calculate average molecular
weight and density of the gas at NTP.
3.6 A mixture of gases analyzing 20% methane, 50% ethane and rest hydrogen by volume at a
temperature of 283 K and a pressure of 5 atmosphere, flows through a pipe line at the rate of 60 m
3
/h.
The internal pipe diameter is 50 mm. Express the concentration in kmole/m
3
, velocity in pipeline and
density of the gas mixture.
3.7 Air contains 79% nitrogen and 21% oxygen by volume. Estimate its density at 20 C and 741 mm
Hg pressure.
3.8 One kilogram of benzene is stored at a temperature of 50 C and a pressure of 600 atmospheres.
Calculate the volume.
3.9 Find the maximum temperature to which 20 kg of CO
2
enclosed in 20 m
3
chamber may be heated
without exceeding a pressure of 20 bars.
3.10 A gas contains 81.8% carbon and 18.2% hydrogen by weight. If 369 ml of the gas at 22 C and
748 mm Hg weighs 0.66 g, what is the formula of the gas?
3.11 A gas analyzes 60% methane and 40% ethylene by volume. It is desired to store 12.3 kg of this
gas mixture in a cylinder having a capacity of 514 10
2
m
3
at a maximum temperature of 45 C.
Calculate the pressure inside the cylinder by assuming that the mixture obeys the ideal gas laws.
3.12 The flue gas of a burner at 800 C and a pressure 2.5 atm has the following composition by
weight.
Nitrogen : 65%
CO
2
: 15%
H
2
O : 12%
O
2
:7%
CO : 1%
Find (a) composition by volume
(b) the average density of the flue gas
(c) mole fraction of the components
3.13 How many kilogram of liquid propane will be formed by liquefaction of 6 m
3
of the gas at 500
kPa and 300 K?
3.14 The following is the analysis of a mixture of gases by weight: chlorine : 65%, bromine : 27%
and rest oxygen. Calculate the composition by volume %, mole % and the average molecular weight.
3.15 A natural gas having CH
4
: 94%, C
2
H
6
: 3% and N
2
: 3% is piped from the well at 298 K and 3
atm pressure. Find (a) partial pressure of N
2
, (b) volume of N
2
per 100 m
3
of gas and (c) density of
the gas.
3.16 A gas flowing at 1000 litres/s has the following composition: CH
4
: 10%, C
2
H
6
: 30% and H
2
:
60% at 303 K and 2000 mm Hg pressure. Calculate (a) The mole fraction of each component, (b) the
concentration of each component, g mole/cc, (c) partial pressure of each component, (d) the molar
density of the mixture, (e) mass flow rate of the gas and (f) average molecular weight.
3.17 Two hundred eighty kg of nitrogen and 64.5 kg of hydrogen are brought together and allowed to
react at 550 C and 300 atm. It is found that there are 38 kmoles of gases present at equilibrium. (a)
What is the limiting reactant, (b) what is the % excess of excess reactant, and (c) % conversion of
hydrogen to ammonia.
3.18 A natural gas containing 90% methane, 5% ethane and 5% nitrogen is piped from a well at 25 C
and 1 atm pressure. Assuming the validity of ideal gas law, find:
(a) Partial pressure of nitrogen
(b) Volume of nitrogen/100 m
3
of gas
(c) Density of mixture
(d) Average molecular weight of mixture
3.19 Acetylene gas is produced according to the reaction
CaC
2
+ 2 H
2
O C
2
H
2
+ Ca (OH)
2
Calculate the number of hours of service that can be got from 2.5 kg of carbide in air lamp burning
100 m
3
of gas/hour at 25 C and 760 mm Hg.
3.20 The following is the analysis of a mixture of gases by weight:
Chlorine: 60%, bromine: 25% and rest nitrogen.
Calculate (a) the composition by mole %, (b) average molecular weight, and (c) density at 298 K and
740 mm Hg.
3.21 In the manufacture of nitric acid, ammonia gas and air are mixed at 7 atm pressure and 650 C
and passed over a catalyst. The composition of this gas mixture on weight basis is nitrogen: 70.5%,
oxygen 18.8%, water vapour: 1.2% and ammonia 9.5%. Assuming the validity of the ideal gas law,
find (a) composition in mole % and (b) density in kg/m
3
.
3.22 Calculate the volume occupied by 30 g of chlorine at a pressure of 743 mm Hg and 21.1 C.
3.23 Propane is liquefied for storage in cylinders. How many kilograms of it will be formed by
liquefying 500 litres of the gas at standard conditions?
Vapour Pressure
4
Whenever we come across a liquid system, it is generally in contact with its own vapour over the
liquid surface. This vapour exerts a pressure like gases, which is called vapour pressure. When the
liquid is at its boiling condition the vapour pressure will be equal to the surrounding pressure. When
that pressure becomes equal to the atmospheric pressure, the boiling point is referred as normal
boiling point (NBP). Whenever we have a binary system, if the sum of their partial pressures equals
the surrounding pressure then the system will boil.
4.1 EFFECT OF TEMPERATURE ON VAPOUR PRESSURE
Illustrated by the effect of temperature on vapour pressure is Clapeyron equation

l
dT

dp =
T V()

GL
where, p represents vapour pressure, T : absolute temperature, l: heat of vaporization at T, V
G
:
volume of gas and V
L
: volume of liquid. If the volume of liquid is neglected and applicability of the
ideal gas law assumed, the above reaction reduces to ClausiusClapeyron equation. dp
=
ldT
p RT
2
or
d
(ln
p
) =
-l
d
1

R

T
where R is gas law constant and l, molal latent heat of vaporization.
When the temperature does not vary over a wide range, it may be assumed that the molal latent heat of
vaporization is constant and the above equation may be integrated between the limits p
0
and p and T
0
and T.
74

ln

= 00
or
log

= 00
Effect of Temperature on V.P:
Antoine equation, log p* (mm Hg) = A
B
(where, p* is the vapour pressure and
A
,
B
,
C
are constants)
TC
+
Limitations:
(i) Applicable only in the range of applicability of A, B, C. (ii) Pressures below 10 bar.
4.2 HAUSBRAND CHART
Steam distillation takes place at point of intersection of the curves at which
p
A
= p p
W
\ p = p
A
+ p
W
Total pressure = vapour pressure of component + vapour pressure of water
pp
W
p
A
Vapour pressure
Temperature
WORKED EXAMPLES
4.1 The vapour pressure of ethyl ether at 0 C is 185 mm Hg. Latent heat of vaporization is 92.5 cal/g.
Calculate vapour pressure at 20 C and 35 C.
Molecular weight of ethyl ether = 74.
l = (92.5 74) = 6845 cal/g mole
R = 1.99 cal/g mole K
T
0
= 273 K, T
1
= 293 K, T
2
= 308 K
At 20 C,
p 6845 1 1
2.303

273

log 185

Therefore, p = 437 mm Hg.
At 35 C,
p

6845 1 1
log 185
2.303
Hence, p = 773 mm Hg.
4.2 It is proposed to purify benzene from small amount of non-volatile
solutes by subjecting it to distillation with saturated steam under
atmospheric pressure of 745 mm Hg. Calculate the temperature at which the distillation will proceed
and the weight of steam accompanying 1 g of benzene vapour.
Temperature, C Vapour pressure of Vapour pressure Total pressure, benzene, mm Hg of water,
mm Hg mm Hg
60 390
65 460
68 510
69 520
150 540 190 650 215 725 225 745 distillation temperature, 69 C
70 550 235 785
pp
W
p
B
Vapour
pressure
Temperature
Basis: 1 g mole of mixed vapour.

g mole of C H66 Vapour pressure of C H66 520 2.31
g mole of water Vapour pressure of water 225

gC H66 2.31 78 10.01
gwater 18

g water 0.1
g benzene
4.3 It is decided to purify myristic acid (C
13
H
27
COOH) by steam distillation under 740 mm Hg
pressure. Calculate the temperature and the weight of steam to be used per kg of acid.
At 99 C: Vapour pressure of H
2
O = 740 mm Hg
Vapour pressure of acid = 0.032 mm Hg
\ The distillation temperature can be taken as 99 C Basis: 1 kmole of mixed vapour.
Moles of the acid
0.032
:


1 = 4.3 10
5
kmoles = 0.0098 kg
Mole of water
Moles of water = 1 kmole = 18 kg
Weight of steam
18

1840 kg
kg of acid

4.4 The acid given in example 4.3 is to be distilled at 200 C by use of superheated steam. It may be
assumed that the relative saturation of the steam with acid vapours will be 80% (a) Find the weight of
steam required per kg of acid distilled at 740 mm Hg. (b) Calculate the weight of steam per kg of acid
if 26 inches of Hg vacuum is maintained.
(a) Vapour pressure of acid at 200 C = 14.5 mm Hg Partial pressure of acid (80% saturation) =
(14.5 0.8) = 11.6 mm Hg Basis: 1 kmole of mixed vapour

11.6
Weight of acid =

1 = 0.0157 kmole = 3.58 kg

Weight of water = (1 0.0157) = 0.9843 kmole = 17.70 kg Steam

17.7
=


= 4.95 kg
kg of acid
(b) 26 inches of Hg. vacuum = 740 (26 25.4) = 80 mm Hg
11.6
Weight of acid =

1 = 0.145 kmole = 33.1 kg

Weight of water (steam) = 0.855 kmole = 15.4 kg Steam

15.4
=

= 0.465 kg
kg of acid

Discussion on examples 4.3 and 4.4: When ordinary steam is used at atmospheric pressure, 1840 kg
of steam is needed. When superheated steam at 200 C is used, 4.95 kg is needed. Due to low
pressure and hence low boiling point under vacuum, quantity of steam needed is 0.465 kg only.
4.5 Calculate the total pressure and the composition of the vapours
in contact with a solution at 100 C containing 35% Benzene, 40% Toluene and 25% Xylene by
weight. At 100 C, the vapour pressures of benzene (molecular weight : 78) is 1340 mm Hg, toluene
(Molecular weight : 92) is 560 mm Hg and Xylene (molecular weight : 106) is 210 mm Hg.
Basis: 100 kg of solution.
Composition of vapours and their partial pressure
Component Mol. Vapour Weight Weight, Mole
wt pressure, % kmole fraction mm Hg in liquid phase
Partial Mole pressure, fraction
mm Hg in vapour phase
Benzene (C
6
H
6
)
Toluene (C
7
H
8
)
Xylene (C
8
H
10
)
78 1340 35 35/78 = 0.449 0.401 0.401 1340 = 536 0.673
92 560 40 40/92 = 0.435 0.388 0.388 560 = 217 0.272
106 210 25 25/106 = 0.236 0.211 0.211 210 = 44 0.055
Total 100 1.12 1.000 797 1.000
Total pressure = 797 mm Hg. 4.6 An aqueous solution of NaNO
3
having 10 g moles of salt/1 kg of
water boils at 108.7 C at 760 mm Hg. Assume that the relative vapour pressure of the solution is
independent of temperature. Find the vapour pressure of the solution at 30 C and the boiling point
elevation.
Since the solution boils at 108.7 C, the vapour pressure of solution = 760 mm Hg.
Vapour pressure of water at 108.7 C = 1030 mm Hg (from Steam Tables)
k Vapour pressure of solution 760 0.74.
Vapour pressure of solvent 1030
Vapour pressure of water at 30 C = 31.8 mm Hg (from Tables) Vapour pressure of solution at 30 C
= (31.8 0.74) = 23.5 mm Hg,
from Cox chart
Boiling point of water at 23.5 mm Hg = 24.8 C


Boiling point elevation
= (Boiling point of solution Boiling point of solvent) = 30 24.8 = 5.2 C
4.7 The following table gives vapour pressure data:
Temperature C 69 70 75 80 85 90 95 99.2
Hexane (A), mm Hg 760 780 915 1060 1225 1405 1577 1765
Heptane (B), mm Hg 295 302 348 426 498 588 675 760
Assuming Raoults law is valid, use the above data to calculate for each of the above temperature the
mole percent x of hexane in the liquid and the mole percent y of hexane in vapour at 760 mm Hg.
p
A
= x
A
P
A
; p
B
= x
B
P
B
; (x
A
+ x
B
) = 1
where P
A
, P
B
are vapour pressures of hexane (A) and heptane (B) respectively.
p
A
= y
A
P; p
B
= y
B
P; (y
A
+ y
B
) = 1
p
A
+ p
B
= P; x
B
= (1 x
A
)
(x
A
P
A
) + (1 x
A
)P
B
= P
x
A
(P
A
P
B
) = (P P
B
)
x
A
760 + (1 x
A
)295 = 760
At 69 C, (Boiling point of hexane)
x
A
(760 295) = (760 295); \ x
A
= 1
y
760
= 1
A
=
760
At 70 C x
A
(780 302) = (760 302); \ x
A
= 0.96
p
A
= (0.96 780) = 748.8; \ y
A
= 748.8/760 = 0.985 At 75 C x
A
(915 348) = (760 348); \ x
A
=
0.73
p
A
= (0.73 915) = 668; \ y
A
= 668/760 = 0.880 At 80 C x
A
(1060 426) = (760 426); \ x
A
= 0.53
p
A
= (0.53 1060) = 562; \ y
A
= 562/760 = 0.740 At 85 C x
A
(1225 498) = (760 498); \ x
A
= 0.36
p
A
= (0.36 1225) = 441; \ y
A
= 441/760 = 0.58 At 90 C x
A
(1405 588) = (760 588); \ x
A
= 0.21
p
A
= (0.21 1405) = 295; \ y
A
= 295/760 = 0.39 At 95 C x
A
(1577 675) = (760 675); \ x
A
=
0.0945 p
A
= (0.0945 1577) = 149; \ y
A
= 149/760 = 0.196 At 99.2 C Boiling point of heptane
x
A
(1765 760) = (760 760); \ x
A
= 0 = y
A
4.8 A solution of methanol in water containing 0.158
mole fraction alcohol boils at 84.1 C (760 mm Hg). The resulting vapour contains 0.553 mole
fraction of alcohol. How does the actual composition of the vapour compare with composition
calculated from Raoults Law? Temperature, C 80 100
Vapour pressure, mm Hg 1340 2624
To get vapour pressure at 84.1 C, the equation
ln p = A B/(T 43)
can be used, ( p, vapour pressure in mm Hg and T, temperature in Kelvin A and B are constants)
Solving A = 18.2 and B = 3420;
Vapour pressure at 84.1 C = 1520 mm Hg.
According to Raoults law; p
A
= x
A
P
A
= (0.158 1520) = 240;
y
A
=
240
= 0.316
760
% Error =
Actual value
Calculated value

100

0.553 - 0.316
=

100 = 42.8%

4.9 Methane burns to form CO

2
and water. If 1 lb mole is burnt with 10% excess pure O
2
and the
4.9 Methane burns to form CO
2
and water. If 1 lb mole is burnt with 10% excess pure O
2
and the
resulting gas mixture is cooled and dried, calculate (a) volume of dry exit gas at 70 F and 750 mm
Hg. (b) Partial pressure of O
2
in exit (c) Weight of water removed.
Basis : 1 lb mole of methane.
CH
4
+ 2O
2
CO
2
+ 2H
2
O
O
2
supplied = 2 1.1 = 2.2 lb moles
Gases leaving after drying: CO
2
: 1.0 lb mole; O
2
: 0.2 lb mole.
530 760
(a) Volume of dry exit gas = 1.2 359
492 750
= 470.26 ft
3
(b) Partial pressure of O
2
in exit =
0.2 750
= 125 mm Hg
1.2
(c) Water removed = 2 lb moles = 36 lb
4.10 Bottled liquid gas is sold. Determine (a) the pressure of the system;
(b) vapour composition. The composition in mole % in liquid phase is
given as follows:
n-Butane : 50%, Propane : 45%, and Ethane : 5%
Vapour pressure (in bar) at 30 C are n-butane: 3.4, propane: 10.8 and ethane: 46.6
Gas n-Butane Propane Ethane Total
Mole % 50 45 5 100
Vapour pressure at 30 C (bar) 3.4 10.8 46.6 Partial pressure (bar) 1.70 4.86 2.33 8.89
(3.4 0.5) (10.8 0.45) (46.6 0.05) Vapour composition % 19.12 54.67 26.21 100
4.11 A solvent recovery system delivers a gas saturated with benzene vapour which analyzes on a
benzene free basis as follows:
CO : 15%, O
2
: 4% and N
2
: 81%. This gas is at 21.1 C and 750 mm Hg. It is compressed to 5 atm
and cooled to 21.1 C after compression. How many kilograms of benzene are condensed by this
process per 1000 m
3
of original mixture? The vapour pressure of benzene at 21.1 C is 75 mm Hg.
Basis: 1000 m
3
of original mixture

1000 750 273
Moles of original mixture =

22.414

294.1
= 40.87 kmoles
75
Benzene present originally = 40.87

= 4.087 kmoles

Moles of gas other than benzene = 40.87 4.087 = 36.783 kmoles Vapour pressure of benzene = 75
mm Hg = 75/760 = 0.0987 atm; (other gas is Tie element)
0.0987

Benzene after compression = 36.783

50.0987
= 0.741 kmole
Benzene condensed = (4.087 0.741) 78 = 261 kg
4.12 N
2
from a cylinder is bubbled through acetone at 840 mm Hg and 323 K at the rate of 0.012
m
3
/h. The N
2
saturated with acetone vapour, leaves at 760 mm Hg and 308 K at 0.023 m
3
/h. Find the
vapour pressure of acetone at 308 K.
0.012
= 5 10
4
kmole/h 22.414

760 323
Molar flow rate of N
2
=

840



(N
2
+ CH
3
COCH
3
) =
0.023
= 9.09 10
4
kmole/h
1.013 308
22.414 1.013

Let y be the mole fraction of N

2
in leaving stream.
Then, 9.09 10
4
y = 5 10
4
Solving, we get y = 0.55
Thus, mole fraction of acetone = 0.45
(P
T
) (y) = (Partial pressure of acetone) = (VP)
acetone
(y)
acetone
(760)(0.45) = (VP) (1.0) = 342 mm
Hg
4.13 Determine the pressure of the system and equilibrium VP at 30
o
C. Assuming all ethane is
removed, estimate the pressure and vapour phase composition components of the system at 30
o
C.
Compound Mole fraction, x, in liquid phase n-butane 0.50
n-propane 0.45
Ethane 0.05
Compound
n-butane n-propane Ethane
Total
Mole fraction, VP at 30 C, Partial pressure, Y, mole fraction x, in liquid phase mm Hg mm Hg 100
0.50 3.4 1.7 19.12
0.45 10.8 4.86 54.67
0.05 46.6 2.33 26.21
8.89 100.00
y
(Mole fraction) =

Partial pressure
Total pressure
1.7
=

100 = 19.12 for n-butane

54.67 for n-propane

26.21 for ethane. When ethane is removed, total moles will be 0.95 kmole.
Compound Mole fraction, VP at 30 C, Partial pressure, Y, mole fraction x, in liquid phase mm Hg mm Hg 100
n-butane 0.50/0.95 = 0.5263 3.4 1.789 25.91
n-propane 0.4737 10.8 4.86 74.09
Total 6.904 100.00
4.14 Estimate the liquid phase composition of a mixture of benzene and toluene at 80
o
C when their
gas phase compositions are 80% benzene and 20% toluene. Vapour pressures of benzene and toluene
are 1340 mm Hg and 560 mm Hg respectively at 80
o
C.
Vapour pressure of benzene is 1340 mm Hg at 80
o
C
Vapour pressure toluene is 560 mm Hg at 80
o
C
At equilibrium, partial pressure of benzene
= (Mole fraction, x
B,
of benzene) (1340)
= (Total pressure) (Mole fraction in vapour phase)
= P
T
(0.8)
i.e. (x
B
) (1340) = P
T
(0.8)
Similarly for toluene,
x
T
(560) = P
T
(0.2)
P
T
(0.8) + P
T
(0.2) = P
T
We also know that, x
B
+ x
T
= 1
4 (1 x
B
) (560) = 4 P
T
(0.2)
x
B
(1340) = P
T
(0.8)
4 (1 x
B
) 560 = x
B
(1340)
2240 1340x
B
2240x
B
= 0
Solving, x
B
= 0.6
4.15 A certain quantity of an organic solvent (molecular weight 125 and density 1.505 g/cc) is kept in
an open flask and boiled long enough so that the vapour fills the vapour space completely by
displacing all the air. The flask is closed, evacuated and the contents reach equilibrium at 30 C.
Vapour pressure of solvent at 30 C is 240 mm Hg. It is observed that only 10 ml of liquid solvent is
present finally.
(i) What is the pressure in the flask at equilibrium?
(ii) What is the total mass in grams of organic liquid in the flask?
(iii) What fraction of the organic liquid present in the flask is in vapour phase at equilibrium?
Equilibrium vapour pressure = 240 mm Hg at 30 C and the pressure in the system is 240 mm Hg.
Volume of vapour space = 4000 10 = 3990 ml
T = 303 K; P = 240 mm Hg
Moles at NTP =
3990 240 273 1
= 0.05065 g mole
303 t tt
760
22414
Molecular weight = 125
Weight = 0.05065 125 = 6.331 g
Mass of liquid left behind = 10 ml 1.505 g/cc = 15.05 g Total weight = 15.05 + 6.331 = 21.381 g
Mole fraction of vapour = (6.331/21.381) = 0.2961
4.16 Benzene and toluene form an ideal solution. If vapour pressure of benzene is 70 mm Hg and that
of toluene is 20 mm Hg and their mole fractions in liquid phase are 0.7 and 0.3 respectively, calculate
their vapour phase composition.
Let A be benzene and B be toluene
Let PP and P
T
be partial pressure and total pressure respectively PP
A
= (P
T
) (y
A
) = x
A
P
A
PP
B
= (P
T
)(y
B
) = x
B
P
B
P
T
(y
A
+ y
B
) = x
A
(P
A
) + (1 x
A
) P
B
= P
P
P
T
= PP
A
+ PP
B
P
T
= (0.7)(70) + (0.3)(20)
= 49 + 6 = 55 mm Hg
Hence, y
A
= (0.7)(70)/55 = 0.89
y
B
= (0.3)(20)/55 = 0.11
4.17 Vapour pressure of pure benzene and toluene are 960 mm Hg and 380 mm Hg respectively at
86.0 C. Calculate the liquid phase and vapour phase composition at that temperature.
Total pressure = 760 mm Hg
Let x and y be the liquid and vapour phase compositions respectively. Suffix B and T denote benzene
and toluene respectively Then, by Raoults law,
P
Tot
= (x
B
) (P
B
) + (x
T
) (P
T
)
760 = (x
B
) (960) + (1 x
B
) 380
Solving,
x
B
= 0.655
x
T
= 0.345
Px

y
B
=
BB 960 t0.655
= 0.827
PTot760

In the same way, y
P

Px 380t 0.345
= 0.173
T
=
TT
760Tot
4.18 Vapour pressure of benzene is 3 atm and that of toluene is 1.333 atm. A liquid fuel containing
0.4 mole benzene and 0.6 mole toluene is vaporized. Estimate the mole fraction of benzene in vapour
phase.
Partial pressure of benzene = (3)(0.4) = 1.2
Partial pressure of toluene = (1.333)(0.6) = 0.8
Total pressure = 2.0 atm
y
benzene
= 1.2/2.0 =0.6
EXERCISES
4.1 The vapour pressure of benzene can be calculated from the Antoine equation.
ln ( p*) = 15.9008 [2788.51/(52.36 + T)]
where p* is in mm Hg and T is in K. Determine the latent heat of vaporization of benzene at its normal
boiling point of 353.26 K, and compare with the experimental value.
4.2 Prepare a Cox chart for ethyl acetate. The vapour pressure of ethyl acetate is 200 mm Hg abs. at
42 C and 5.0 atm at 126.0 C. By using the chart estimate the boiling point of ethyl acetate at 760 mm
Hg and compare with the experimental value (77.1 C).
4.3 The following data gives the vapour pressure (VP) for benzene (A) toluene (B) system. Compute
the vapour-liquid equilibrium data at a total pressure of 760 mm Hg.
VP
A
, 760 811 882 957 1037 1123 1214 1310 1412 1530 1625 1756 mm Hg
VP
B
, 314 345 378 414 452 494 538 585 635 689 747 760 mm Hg
4.4 The following data gives the vapour pressure data for a binary system. Compute the VLE vapour
liquid equilibrium data at a total pressure of 760 mm Hg.
Vapour pressure of A, mm Hg 760 860 1002 1160 1262
Vapour pressure of B, mm Hg 433 498 588 698 760
4.5 It is desired to purify nitrobenzene by steam distillation under a pressure of 760 mm Hg.
Distillation takes place at 99 C. Vapour pressure of nitrobenzene is 20 mm Hg. Estimate the weight
of nitro benzene associated per kg of steam in distillate. Assuming the vaporization efficiency to be
75%, estimate the weight of nitrobenzene per kg of steam in distillate.
4.6 Methyl alcohol and ethyl alcohol at 100 C have vapour pressures of 2710 mm Hg and 1635 mm
Hg respectively. Calculate the total pressure and composition of the vapour in contact with a liquid
containing 30 weight % of methyl alcohol and 70 weight % of ethyl alcohol at 100 C.
4.7 A liquefied fuel has the following analysis: C
2
H
6
: 2%, n-C
3
H
8
: 40%, i-C
4
H
10
: 7%, n-C
4
H
10
:
47% and C
5
H
12
: 4%. It is stored in cylinders for sale. (a) Calculate the total pressure in cylinder at
21 C and the composition of the vapour evolved. (b) Find the total pressure at 21 C if all C
2
H
6
were removed.
Vapour pressure data (mm Hg):
C
2
H
6
: 28500, n-C
3
H
8
: 6525, i-C
4
H
10
: 2250, n-C
4
H
10
: 1560 and C
5
H
12
: 430.
4.8 Calculate the total pressure and the composition of the vapours and liquid in molar quantities at
100 C for a solution containing 45% benzene, 40% toluene and 15% xylene by weight. At 100 C,
the vapour pressures are benzene (C
6
H
6
) (molecular weight: 78) : 1340 mm Hg; Toluene (C
7
H
8
)
(molecular weight: 92) : 560 mm Hg, xylene (C
7
H
8
) (molecular weight: 106) : 210 mm Hg.
4.9 The partial pressure of actetaldehyde in a solution containing 0.245 kg of CH
3
CHO in 20 kg of
water is 190 mm Hg at 93.5 C. Calculate the partial pressure of CH
3
CHO over 0.15 molal solution
in water.
4.10 Ethyl acetate at 30 C exerts a vapour pressure of 110 mm Hg. Calculate the composition of the
saturated mixture of ethyl acetate and air at a temperature of 30 C and an absolute pressure of 900
mm Hg pressure. Express the composition by (a) volume %, and (b) weight %.
Psychrometry 5
5.1 HUMIDITY
Humidification operation is a classical example of an interphase transfer of mass and energy, when a
gas and a pure liquid are brought into intimate contact. The term humidification is used to designate a
process where the liquid is transferred to gas phase and dehumidification indicates a process where
the transfer is from the gas phase to the liquid phase. The matter transferred between phases in both
the cases is the substance constituting the liquid phase, which either vaporizes or condenses
indicating respectively the humidification process or the dehumidification process.
5.2 DEFINITIONS
Dry bulb temperature (DBT): The temperature measured by a bare thermometer or thermocouple is
called the dry bulb temperature.
Wet bulb temperature (WBT): The temperature measured by a thermometer or thermocouple with a
wet wick covering the bulb, under equilibrium condition, is called the wet bulb temperature.
Absolute humidity (n
v
): The substance that is transferred (vapour) is designated by A and the main
gas phase is designated by B.
It is defined as the moles of vapour carried by unit mole of vapour free gas.

yp p moles of A (5.1)
v
[]
y ppp moles of B

When the quantities are expressed in mass, then it is called mass absolute humidity (n) or Grosvenor
humidity.
pMM
nn
[]
vAA


vv
mass of A
(5.2)

M pp M

mass of B
BvB

87
Relative humidity or relative saturation ( y
r
%): It is normally expressed in percentage. If p
v
is the
partial pressure under a given condition and p
s
is the vapour pressure at DBT of the mixture, then
Relative saturation = y
r
% =
pv
100 (5.3)
ps
Percentage saturation or percentage absolute humidity ( y
P
): It is defined as the percentage of the
ratio of humidity under given condition to the humidity under the saturated condition.
Percentage saturation = y
P
% =
nv
100 (5.4)
ns
Dew point: This is the temperature at which a vapour-gas mixture becomes saturated when cooled at
constant total pressure out of contact with a liquid. The moment the temperature is reduced below the
dew point, the vapour will condense as a liquid dew.
Humid heat: The humid heat C
S
is the heat required to raise the temperature of unit mass of gas and
its accompanying vapour by one degree centigrade at constant pressure.
C
S
= C
A
n
v
+ C
B
(5.5) where C
A
and C
B
are specific heats of vapour and gas respectively.
Enthalpy: The enthalpy H of a vapour-gas mixture is the sum of the enthalpies of the gas and the
vapour content. For a gas at a DBT of t
G
, with a humidity of n
v
, the enthalpy relative to the reference
state t
0
is,
H = enthalpy of gas + enthalpy of vapour component.
= C
B
(t
G
t
0
) + n
v
[C
A
(t
G
t
DP
) + l
DP
+ C
A,L
(t
DP
t
0
)] (5.6) where
l
DP
= Latent heat of vaporization at dew point.
C
A,L
= Specific heat of component A (vapour) in liquid phase. The above Eq. (5.6) will reduce to
Eq. (5.7) when t
DP
itself is taken as the reference temperature, t
0
H = C
B
(t
G
t
0
) + n
v
[C
A
(t
G
t
0
) + l
0
]
= C
S
(t
G
t
0
) + n
v
l
0
(5.7)
Humid volume: The humid volume v
H
of a vapour-gas mixture is the volume of unit mass of dry gas
and its accompanying vapour at the prevailing temperature and pressure. The expression for humid
volume in m
3
/kg is

2731105 v MM 273 p



=+
nt
(5.8)


where, p= total pressure N/m
2
A typical psychrometric chart is shown at the end of the chapter.
Various properties of air-water system can be obtained from the chart.
Alternatively, the equations given can be used to determine the properties.
Saturated vapour: When a gas or gaseous mixture remains in contact with a liquid surface it will
acquire vapour from the liquid until the partial pressure of the vapour in the gas mixture equals the
vapour pressure of the liquid at its existing temperature when the vapour concentration reaches this
equilibrium concentration, the gas is said to be saturated with the vapour.
Partial saturation: If a gas contains a vapour in such proportions that its partial pressure is less than
the vapour pressure of the liquid at the existing temperature, the mixture is partially saturated.
Relative saturation: The relative saturation of such a mixture may be defined as the percentage ratio
of the partial pressure of the vapour to the vapour pressure of the liquid at the existing temperature.
The relative saturation is therefore a function of both the composition of the mixture and its
temperature as well as of the nature of the vapour.
Relative saturation also represents the following ratios: (a) The ratio of the percentage of the vapour
by volume to the percentage by volume that would be present if the gas were saturated at the existing
temperature and total pressure, (b) the ratio of the weight of vapour per unit volume of mixture to the
weight per unit volume present at saturation at the existing temperature and total pressure.
Percentage saturation: It is defined as the percentage ratio of the existing weight of vapour per unit
weight of vapour free gas to the weight of vapour that would exist per unit weight of vapour free gas
if the mixture were saturated at the existing temperature and pressure.
This represents the ratio of the existing moles of vapour per mole of vapour free gas to the moles of
vapour that would be present per mole of vapour free gas if the mixture were saturated at the existing
temperature and pressure.
Relative saturation % = y
r
=
pv
100
ps
where,
p
v
= Partial pressure of vapour p
s
= Vapour pressure of pure liquid Percentage saturation = y
p
=
nv

100
ns
where,
n
v
= moles of vapour per mole of vapour free gas actually present n
s
= moles of vapour per mole of
vapour free gas at saturation. If p is the total pressure, then from Daltons law,
v
, and n
s
=
s
n
v
=

-v -s
np pp vv s- = ss v
y
p
= (
y
r
)

v

-v
WORKED EXAMPLES
5.1 An air (B)-water (A) sample has a dry bulb temperature of 50 C and a wet bulb temperature of
35 C. Estimate its properties at a total pressure of 1 atm.
1 atm = 1.0133 10
5
N/m
2
Molecular weight of air = 28.84
(i) n
v
(chart) = 0.03 kg w.v/kg.d.a = 0.04833 kmole of w.v/kmole of d.a.
(ii) % humidity (chart) = 35%
(iii) % relative saturation = partial pressure/vapour pressure
Partial pressure under the given condition is given by
pA
molal humidity (0.0483) =
pp
-A
pA
0.0483 =
1.0133 105
pA


5

20.69 =

1
where,
p
A
= 4.672 10
3
N/m
2
p
A
= Partial pressure of water p = Total pressure
Vapour pressure of water (Steam Tables) at 50 C = 92.51 mm Hg = 12.332 10
3
N/m
2
\
% R.H. = 4.672

10
3

12.332
10
3
= 37.88%
(iv) Dew point = 31.5C
(v) Humid heat = C
S
= C
B
+ C
A
n (Eq. 5.5) = 1.005 + 1.884 (0.03)
= 1.062 kJ/kg of dry air C
(vi) Enthalpy
(For a reference temperature of 0 C)
(a) H = C
S
(t
G
t
0
) + n l
0
(Eq. 5.7)
l
0
= 2502 kJ/kg
H = 1.062 (50 0) + (0.03) (2502) = 128.16 kJ/kg da (b) Enthalpy of saturated air = 274 kJ/kg
Enthalpy of dry air = 50 kJ/kg
\ Enthalpy of wet air = 50 + (274 50)(0.35) = 128.4 kJ/kg (vii) Humid volume v
H

(a) vH = (8315)




1(325) n

= (8315)

= 0.969 m
3
mixture/kg of dry air
Alternatively,
(b) Specific volume of saturated air = 1.055 m
3
/kg of dry air
Specific volume of dry air = 0.91 m
3
/kg of dry air By interpolation v
H
= 0.91 + (1.055 0.91)(0.35)
= 0.961 m
3
/kg of dry air
5.2 Ether at a temperature of 20 C exerts a vapour pressure of 442 mm Hg. Calculate the
composition of a saturated mixture of nitrogen and ethyl ether vapour at 20 C and 745 mm Hg and
express the same in the following forms.
(a) Percentage composition by volume
(b) Composition by weight
(c) lb of vapour/ft
3
of mixture
(d) lb of vapour/lb of vapour free gas
(e) lb moles of vapour/lb mole of vapour free gas
(a) Basis: 1ft
3
of gas mixture
Percentage of ethyl ether =
442 1
= 0.593 ft
3
= 59.3 Volume %;
745

Nitrogen = 40.7% = 0.407 ft
3
(b) Basis: 1 lb mole of mixture Component Molecular lb mole Weight, lb Weight % weight
Ether 74 0.593 (0.593 74) = 43.9 79.4
Nitrogen 28 0.407 (0.407 28) = 11.4 20.6
Total 1.000 55.3 100.0
(c) Volume of gas mixture = 1

359

760 293
= 393 ft
3


43.9
\
lb of vapour/ft
3
=

= 0.112

(d) lb of vapour/lb of vapour free gas =
43.9
= 3.85
11.4

(e) lb mole vapour/lb moles vapour free gas =
0.593
= 1.457
0.407
5.3 A mixture of acetone vapour and nitrogen contains 14.8% acetone by volume. Calculate y
r
and y
p
at 20 C and 745 mm Hg
Vapour pressure of acetone at 20 C = 184.8 mm Hg
Partial pressure of acetone = (0.148 745) = 110 mm Hg
110
y
r
= relative saturation =

100 = 59.7%

0.148

= 0.174
v
=

184.8


0.248
= 0.329
s
=

n
560.2 0.752

y
p
=
nv 0.174
= 52.9%
ns 0.329
Always y
r
> y
p
5.4 Moist air is found to contain 8.1 grains of water vapour per ft
3
at 30 C. Calculate the temperature
to which it must be heated in order that its relative saturation will be 15% (7000 grains = 1 lb)
Basis: 1 ft
3
of water vapourair mixture
Amount of water =
8.1
= 1.16 10
3
lb 6.42 10
5
lb moles
7000
Pure component volume of water at 30 C
303
= 6.42

10
5
359

= 0.0256 ft
3


0.0256

= 19.4 mm HgPartial pressure of water vapour = 760

Vapour pressure of water vapour =
19.4
= 130 mm Hg
0.15
This corresponds to a temperature of 57 C.
5.5 A stream of gas at 70 F and 14.3 psi and 50% saturated with water vapour is passed through a
drying tower, where 90% of water vapour is removed. Calculate the pound of water removed per
1000 ft
3
of entering gas. Vapour pressure of water at 70 F = 0.36 psi.
Basis: 1000 ft
3
of entering gas 70 F and 14.3 psi

1000 14.3 492
lb mole of gas mixture =


= 2.52 lb moles
y
p
= 0.5 =
n
v
n
s
where n
v
= lb mole of water/lb mole of vapour free gas. 0.36
n
v
= 0.5

n
s
= 0.5

14.3


= 0.013 mole of water/mole of dry gas
0.013
Amount of water entering = 2.52

= 0.032 lb mole

Amount of water removed = 0.032 0.9 = 0.0288 lb mole Weight of water removed = (0.0288 18) =
0.518 lb.
5.6 A mixture of benzene vapour and air contains 10.1% benzene by volume. (a) Calculate the dew
point of the mixture when at a temperature of 25 C and 750 mm Hg.
(b) Calculate the dew point when the mixture is at a temperature of 30 C and 750 mm Hg.
(c) Calculate the dew point when the mixture is at a temperature of 30 C and 700 mm Hg.
Basis: 1 mole of mixture.
(a) Partial pressure of benzene = 0.101 750 = 75.7 mm Hg From the vapour pressure data for
benzene, it is found that this pressure corresponds to a temperature of 20 C, the dew point.
(b) Partial pressure of benzene remains same, i.e. 75.7 mm Hg. Hence dew point also remains same,
i.e. 20 C (only temperature of gas mixture has changed.)
(c) Partial pressure of benzene = 0.101 700 = 70.7 mm Hg. Dew point for this partial pressure is
18.7 C. From these results,
it is seen that the dew point does not depend on the temperature but does vary with total pressure.
5.7 It is proposed to recover acetone which is used as a solvent in an extraction process by
evaporation into a stream of nitrogen. The nitrogen enters the evaporator at 30 C containing acetone
such that its dew point is 10 C. It leaves at a temperature of 25 C with a dew point of 20 C. The
atmospheric pressure is 750 mm Hg. (a) Calculate the vapour concentration of the gases entering and
leaving the evaporator expressed in moles of vapour/mole of vapour free gas.
(b) Calculate the moles of acetone evaporated per mole of the vapour free gas passing through the
evaporator.
(c) Calculate the weight of acetone evaporated per 1000 ft
3
of gases entering.
(d) Calculate the volume of gases leaving the evaporator per 1000 ft
3
of gases entering.
Data: Vapour pressure of acetone:
At 10 C = 116 mm Hg and at 20 C = 185 mm Hg.
(a) Entering gases: partial pressure of acetone = 116 mm Hg partial pressure of N
2
= 634 mm Hg
mole of acetone/mole of N
2
=
116
= 0.183
634
Leaving gases: partial pressure of acetone = 185 mm Hg partial pressure N
2
= 750 185 = 565 mm
Hg
mole of acetone/mole of N
2
=
185
= 0.328
565
Basis: for (b), (c) and (d): 1 lb mole of N
2
passing through evaporator. (b) Moles of acetone
evaporated = (0.328 0.183) = 0.145 (c) Total moles entering = (1 + 0.183) = 1.183 lb moles
760 303
= 477 ft
3
Volume of entering gas = 1.183 359

750 273
Weight of acetone evaporated = (0.145 58) = 8.4 lb
Acetone evaporated per 1000 ft
3
=
8.41000
= 17.6 lb
477
(d) Total moles of gas leaving = (1 + 0.328) = 1.328 lb moles

760 303
Volume of gases leaving = 1.328 359 = 526 ft
3
Volume of gases leaving per 1000 ft
3 =
5261000
= 1102 ft3
477
5.8 Air at a temperature of 20 C and pressure 750 mm Hg has a relative humidity of 80%
(a) Calculate the molal humidity of air.
(b) Calculate the humidity of this air if its temperature is reduced to 10 C and its pressure increased
to 35 psi, condensing out some of the water.
(c) Calculate the weight of water condensed from 1000 ft
3
of gas. (d) Calculate the final volume of
wet air leaving.
Data: Vapour pressure of H
2
O at 20 C =17.5 mm Hg and at 10 C = 9.2 mm Hg.
(a) Initial partial pressure of water = (17.5 0.8) = 14 mm Hg

14
Initial humidity =
750 -14
= 0.019 kmole of water vapour (w.v.)/kmole of dry air (d.a.) (b) Final partial pressure of water = 9.2
mm Hg (saturated)
Final total pressure =
35 760
= 1810 mm Hg
14.7

9.2
Final humidity =

-

= 0.0051 kmole of water vapour/kmole of dry air Basis: 1000 ft
3
of wet air, 20 C and 750 mm Hg.
(c) Volume at standard condition and hence weight of mixture in lb mole 1000
750

273
= 2.56 lb moles
359 293
736

= 2.51 lb moles

lb mole of dry air = 2.56

lb mole of water vapour initially = (0.019 2.51)

= 0.0477 lb mole
lb mole of water finally = (0.0051 2.51) = 0.0127 lb mole
\ water condensed = 0.035 lb moles = 0.63 lb.
(d) Total moles finally present = (2.51 + 0.0127) lb moles = 2.5227 lb moles
760 283
= 395 ft
3
Volume of wet air = 2.5227 359

5.9 A mixture of dry flue gases and acetone at a pressure of 750 mm Hg has a dew point of 25 C. It
is proposed to condense 90% of the acetone by cooling to 5 C and compressing. Calculate the final
pressure in psi for acetone.
Vapour pressure at 25 C = 229.2 mm Hg.
Vapour pressure at 5 C = 89.1 mm Hg.
Basis: 1 lb mole of mixture of gases.
Partial pressure of acetone = 229.2 mm Hg; (equal to vapour pressure as it is at dew point)
lb moles of acetone in it = 229.2/750 = 0.306 lb mole
Dry flue gases = (1 0.306) = 0.694 lb mole
Acetone finally present = 0.306 0.1 = 0.0306 lb mole Final gas = 0.694 + 0.0306 = 0.7246 lb mole
lb mole of acetone in final gas/lb mole of final gas mixture
0.0306
= 0.0422=
0.7246
Final pressure of acetone = 89.1 mm Hg

89.1
= 2110 mm Hg\ Final pressure of gas mixture =
0.0422
= 40.8 psi.
5.10 Air at a temperature of 20
o
C and 750 mm Hg has a relative humidity of 80%. Calculate,
(i) The molal humidity of the air
(ii) The molal humidity of this air if its temperature is reduced to 10 C and pressure increased to
2000 mm Hg condensing out some of the water and
(iii) Weight of water condensed from 1000 litre of the original wet air. Vapour pressure of water at
20 C = 17.5 mm Hg
Vapour pressure of water at 10 C = 9.2 mm Hg
At 20 C and 750 mm Hg,
pp
y
r
= 0.8 =

vv
p
=
17.5
s
where, partial pressure of H
2
O vapour = p
v
= 14 mm Hg.

pv 14
(i) Molal humidity at 20 C, 750 mm Hg =
ppv
=-
14
= 0.019 g mole of water vapour/g mole of dry air (ii) Molal humidity at 10 C, 2000 mm Hg
(when saturated, vapour pressure = partial pressure, we have, p
s
= p
v
= 9.2 mm Hg)
p
s

=

pp
2000
9.2--

= 4.6 10
3
g mole of water vapour/g mole of dry air (iii) Basis: 1000 litres of original wet air

1000 750273
g mole of wet air =

= 41.02
g mole of dry air = 41.02
1
= 40.25

\ water condensed = (difference in humidity) (flow rate of dry air) (molecular weight of water) =
(0.019 4.6 10
3
) 40.25 18 = 10.43 g 5.11 A material is to be dried from 16% moisture by
weight (wet basis) to
0.5% by circulation of hot air. The fresh air contains 0.02 kg of water/kg of dry air. Find the volume
of fresh air required if 1000 kg/h of dried material is to be produced. The exit humidity of air is 0.09
kg of water/kg of dry air. The air enters at 301 K and at atmospheric pressure.
301 K Air 0.02 0.09
16% wet solid
Drier
Dried solid 0.5%
Basis: 1000 kg/h product.
Dry solid = 995 kg
Moisture = 5 kg
995
= 1184.5 kg\ feed =
0.84
Water in feed = 189.5 kg
Dry solid is the Tie Element
Water removed = 1184.5 1000 = 184.5 kg
1 kg of dry air removes = (0.09 0.02) = 0.07 kg H
2
O
184.5
= 2636 kg/h\ Weight of dry air needed =
0.07
2636
Dry air needed =

= 91.40 kmoles

Water in entering air =
2636 0.02
= 2.93 kmoles
18
\ Total moles of wet air = 94.33 kmoles
301
Volume of wet air = 94.33

22.414

= 2331.17 m
3

5.12 A tunnel drier is used to dry an organic paint. 1000 lb/h of feed having 10% water is to be dried
to 0.5%. Air is passed counter current
to the flow of paint. Air enters at 760 mm Hg. 140 F and 10% humidity while it leaves at 750 mm Hg
95 F and 70% humidity. What flow rate of air is needed?
Air 10% Air 70%
Dry product 0.5%
Drier
1000 lb/h; 10% moisture
Basis: 1000 lb/h of feed Dry material = 900 lb
Moisture = 100 lb
Product =
900
= 904.5 lb
0.995
Water removed = (1000 904.5) = 95.5 lb/h
From humidity chart the following details are obtained: Humidity of entering air = 0.025 lb mole
water vapour/lb mole dry air Humidity of leaving air 0.035 lb mole water vapour/lb mole dry air 1 lb
mole of dry air removes 0.01 lb mole H
2
O = 0.18 lb
95.5
Dry air needed =

= 530.5 lb mole/h

\ Total air entering = 530.5 1.025 = 543.77 lb mole/h

600
Volumetric flow rate of air = (543.77

359)

= 2,38,065 ft
3
/h.
5.13 Air at 100
o
F and 20% relative humidity is forced through a cooling tower. The air leaves at 85
F and 70% relative humidity. Atmospheric pressure is 29.48 inches of Hg. Calculate the following.
(a) The pounds of water evaporated per pound of dry air. (b) Volume of air leaving per 1000 ft
3
of
entering air.
Vapour pressure of water at 100 F = 1.9325 inches of Hg and at 85F = 0.8754 inches of Hg. (a)
Partial pressure of H
2
O in entering air = 1.9325 0.2 = 0.3865 inches of Hg
Partial pressure of H
2
O in exit air = 0.8754 0.7
= 0.6128 inches of Hg
(lb mole H
2
O/lb mole dry air) in entering air
=
0.3865
= 0.01328
29.48 0.3865
(lb mole H
2
O/lb mole dry air) in outgoing air
=
0.6128
= 0.02123
29.48 0.618
lb mole H
2
O evaporated/lb mole of dry air = 0.00795
18
lb H
2
O/lb of dry air = 0.00795

= 5 10
3
lb = 0.005 lb

(b) 1000 ft
3
of entering air =
1000
43.2



= 2.447 lb moles

For 1.01328 lb moles of wet air entering, 1.02123 lb moles of wet air leaves
\ for 2.447 lb moles of wet air entering
= 2.447
1.02123
= 2.466 lb moles of wet air leaves
1.01328
535

= 962.8 ft
3
Volume of air leaving = 2.466 359

5.14 Leather containing 100% of its own weight of water is dried by means of air. The dew point of
entering air is 40 F while that of leaving air is 55 F. If 2000 lb of wet air is forced through the drier
per hour, how many lb of water is removed per hour. Total pressure 750 mm Hg.
Vapour pressure of water at 40 F = 6.3 mm Hg
and at 55 F = 11 mm Hg.
Basis: One lb mole of dry air
Water in entering air
=
6.3
750 6.3
= 0.00847 lb mole of water vapour/lb mole of dry air = 0.00527 lb of water vapour/lb of dry air
Water in leaving air =
11
750 11
= 0.01488 lb mole of water vapour/lb mole of dry air = 0.00926 lb of water vapour/lb of dry air
\ water vapour removed = 0.00926 0.00527
= 0.00399 lb of water vapour/lb of dry air
2000
Dry air entering per hour =

= 1989.52 lb

Weight of water removed/h = 1989.52 0.00399 = 7.938 lb. 5.15 Acetone is used as a solvent in a
certain process. Recovery of the
acetone is accomplished by evaporation into a stream of N
2
followed by cooling and compression of
the final gas mixture. In the solvent recovery unit 50 lb of acetone are removed per hour. The N
2
is
admitted at 100 F and 750 mm Hg partial pressure of acetone in incoming nitrogen is 10 mm Hg. The
nitrogen leaves at 85 F, 740 mm Hg and 85% saturation.
(a) How many ft
3
of incoming gas must be admitted per hour to
obtain the required rate of evaporation of the acetone? (b) How many ft
3
of gases leave the unit per
hour?
N
2
, Acetone 100 F 750 mm Hg N
2
, Acetone
Drier
partial pressure of acetone 10 mm Hg 85F, 740 mm Hg 85% saturation
(Molecular weight of Acetone (CH
3
)
2
CO is 58. Vapour pressure of acetone at 85 F = 287 mm Hg)
Basis: 100 lb moles of gas mixture entering
Acetone removed =
50
= 0.862 lb mole
58
N
2
in entering mixture =
750
10

100 = 98.67 lb moles

Acetone entering = 100 98.67 = 1.33 lb moles
1.33

lb mole of acetone/lb mole of N

2
in entering stream =

= 0.0135
p v287yp = 0.85 = 740 p287

where
y
p
(percentage saturation) = 85%
p
v
(partial pressure) = 258 mm Hg
lb mole of acetone/lb mole of N
2
in leaving stream =
258 740 258 = 0.5385 \ 1 lb mole of N
2
removes: (0.5385 0.0135)
= 0.525 lb mole of acetone
lb mole N
2
needed/h =
0.862
= 1.642 lb mole
0.525
Total moles of gas entering = 1.642 1.0135 = 1.664 lb moles

560 760
(a) Volume of gases admitted = 1.664 359 = 689.0 ft
3
(b) Total moles of exit gas = 1.642 1.5385 = 2.526 lb moles

545 760
Volume of exit gases = 2.526 359
= 1031.6 ft
3
5.16 By adsorption in silica gel you are able to remove all the weight (0.93 kg) of water from moist
air at 15 C and 98.6 kPa. The same air measures 1000 m
3
at 20C and 108 kPa when dry. What was
the relative humidity of the air?
Basis: 1000 m
3
of dry air at the given conditions.
108


kmole of the dry air:

= 44.895
Water removed: 0.93 kg =
0.93
= 0.052 kmole

Total wet air = 44.895 + 0.052 = 44.947 kmoles

p
98.6
= 0.114 kPa
v
= Partial pressure of water =
p
s
= Vapour pressure of water = 15 mm Hg = 2 kPa

pv
, y
r
=
0.114
100 = 5.7%,
Q
Relative humidity, y
r
=
ps
5.17 At 297 K and 1 bar, the mixture of N
2
and C
6
H
6
has a relative humidity of 60%. It is desired to
recover 90% C
6
H
6
present by cooling to 283 K and compressing to a suitable pressure. What is the
pressure to which the mixture should be pressurised? Vapour pressures of benzene at 283 K and 297
K are 6 kN/m
2
and 12.2 kN/m
2
respectively.
Relative humidity = 0.6 = Partial pressure/Vapour pressure
12.2

60
10
3
Partial pressure =

= 7.32 10
3
N/m
2
100
7.32

10

3

Humidity =
78
= 0.217 kg of w.v./kg of d.a.
101.3 1033

28 10

Final humidity = 0.10 0.217 = 0.0217 kg of w.v./kg of d.a.
3
78
0.0217
610
=
3 28PT 610
Therefore, P
T,
the total pressure = 7.642 10
5
N/m
2
5.18 Humid air at 75 C, 1.1 bar and 30%
relative humidity is fed at a rate of 1000 m
3
/h. Determine the molar flow rates of water and dry air
entering the process, molar humidity, absolute humidity, percentage humidity and dew point.
Vapor pressure at 75 C = 289 mm Hg
Partial pressure of water vapour
= Vapour pressure of water Relative humidity = 86.7 mm Hg
Total pressure = 1.1 bar = 1.1 10
5
N/m
2
1 atm = 760 mm Hg = 1.013 10
5
N/m
2
Therefore, 1.1 bar = 825.36 mm Hg
Mole fraction of water vapour = (86.7/825.36) = 0.105 Volumetric flow rate = 1000 m
3
/h at 75 C
and 1.1 bar 1000 825 273 1
38 kmoles/h348 t tt
760
22.414
Water flow rate = 38 0.105 = 3.99 kmoles/h
Dry air rate = 38 3.99 = 34.01 kmoles/h
Humidity =
86.7
= 0.117 kmole w.v./kmole d.a.
825.36 86.7

Mass humidity = 0.117
18
= 0.073 kg w.v./kg d.a.
28.84

Percentage humidity = 0.117
100
= 21.7%
289 /(825289)
Dew point = 49 C
5.19 A piece of wood entering furnace at 0.15 kg/s containing 60% moisture is dried in a
countercurrent dryer to give a fixed product containing 5% moisture content. The air used is at 100 C
and is having water vapour at a partial pressure of 10
3
N/m
2
. The air leaves the dryer at 70% RH and
at 40 C. Estimate the air required to remove the moisture. The vapour pressure of water at 40 C =
7.4 10
3
N/m
2
Water in incoming wood = 0.15 0.6 = 0.09 kg/s Weight of dried wood = 0.15 0.4 = 0.06 kg/s
Weight of water in dried wood is 5%
Weight of final product =
0.06
= 0.0632 kg/s
0.95
Weight of water removed = 0.15 0.0632 = 0.0868 kg/s
10

3
Humidity of entering air =
1.013 10 5310
= 9.97 10
3

18
28.84 = 0.00623 kg w.v./kg d.a. Humidity of leaving air,
Relative humidity = Partial pressure/Vapour pressure 0.7 = Partial pressure/7.4 10
3
Partial pressure = 5.18 10
3
N/m
2
10

3
Humidity = 5.18
101.3 1033
= 0.0336 kg w.v./kg d.a.
10
Increase in humidity = 0.0336 0.00662 = 0.02738 kg w.v./kg d.a. Weight of water in kg to be
removed
Dry air needed = Water removed per kg of dry air

=
0.0868
= 3.17 kg/s
0.02738
Weight of wet air needed = 3.17 (1.00622) = 3.1897 kg/s Weight of wet air leaving = (3.17)
(1.0336) = 3.277 kg/s
5.20 Air at 740 mm Hg at 30 C contains water vapour at a partial pressure of 22 mm Hg. 1000 m
3
of
the air is cooled to 15 C and the partial pressure of water vapour is brought to 12.7 mm Hg. During
this process, water gets partially condensed. Estimate the amount of air at new condition
Moles of humidified air at initial condition

1000
760
303
=


22.414 740 273
= 39.14 kmoles

Mole fraction of water vapour in original air (30 C) =
22
= 0.02973
740
Mole fraction of water vapour
in original air when cooled to 15 C
=
12.7
= 0.017
740
Therefore, mole fraction of dry air = 0.983
Moles of wet air at 15 C =
37.976
= 38.63 kmoles
0.983
Volume of dry air at new condition (assuming ideal behaviour)
=
38.63




760 288
= 938.11 m
3
/kg dry air
Water removed is (39.14) (0.02973) (38.63 0.017) = 0.507 kmole
= 0.547 18 kg
= 9.126 kg
5.21 Air with humidity of 0.004 kg of water vapour per kg of dry air is bubbled through water at a
rate of 0.1 kg/s. The air leaves with a humidity of 0.014 kg of water vapour per kg of dry air.
Estimate the time needed to vaporize 0.1 m
3
of water.
Weight of water evaporated = 0.1 1000 = 100 kg (since the density is 1000 kg/m
3
)
Weight of water removed/kg of dry air = 0.014 0.004 = 0.01 kg
Water removed per second by using 0.1 kg of air
= 0.01 0.1 = 0.001 kg/s
Hence, time needed to evaporate 100 kg of water
=
100
= 100000 s
0.001

=
100000
= 27.7 h
3600
5.22 Air containing 0.01 kg of water vapour per kg of dry air is passed through a bed of silica gel to
get air containing 0.001 kg of water vapour per kg of dry air for a specific application. The column
has 2.1 kg of silica gel initially and after 5 h of operation, the weight of silica gel is found to be 2.2
kg. Calculate the flow rate of air both at inlet and outlet.
Water adsorbed by silica gel in 5 h = 2.2 2.1 = 0.1 kg
Water adsorbed/h =
2.2 2.1
= 0.02 kg/h
5
Making a balance for water:
Water in incoming air = Water in leaving air + Water adsorbed Let G be the flow rate of dry air in
kg/h.
(G) (0.01) = (G) (0.001) + 0.02
G (0.01 0.001) = 0.02
G =
0.02
= 2.222 kg/h
0.009
i.e. the flow rate of dry air in kg/h = 2.222 kg/h
Flow rate of wet air at inlet = 2.222[1 + 0.01] {since G = G
s
(1 + x)} = 2.244 kg/h
Flow rate of wet air at outlet = 2.222 (1 + 0.001)
= 2.224 kg/h
EXERCISES
5.1 Tolueneair mixture is available such that the partial pressure of the vapour is 1.33 kPa. The total
pressure is 99.3 kPa and the temperature is 21 C. Calculate (a) the relative humidity, (b) The moles
of toluene per mole of vapour free gas, (c) the weight of toluene per unit weight of vapour free gas,
(d) the percent saturation and (e) the percentage of toluene by volume.
5.2 Air is available at a DBT of 50 C and a wet bulb temperature of 30 C. Estimate its humidity, %
saturation and humid volume using humidity chart.
5.3 A material is to be dried from 20% moisture by weight (wet basis) to 1.0% by circulation of hot
air. The fresh air contains 0.02 kg of water/kg of dry air. Find the volume of fresh air required if 1000
kg/h of dried material is to be produced. The exit humidity of air is 0.09 kg water vapour/kg dry air.
The air enters at 300 K and at atmospheric pressure.
5.4 A mixture of benzeneair is saturated at 1 atm and 50 C. The vapour pressure of benzene is 275
mm Hg at 50 C. Estimate the mass humidity and molal humidity.
5.5 A mixture of benzeneair is available at 750 mm Hg and 60 C. The partial pressure of benzene is
150 mm Hg at 50 C. Estimate the mass humidity and molal humidity.
5.6 Air-water vapour mixture is available at a DBT of 35 C and a relative saturation of 70%.
Estimate its humidity, dew point, humid volume, adiabatic saturation temperature, humid heat and
enthalpy.
5.7 Air at 50% relative humidity (RH) is to be used for a specific operation. Air is available at a
DBT of 35 C and 27 C. What should be the final temperature to which it should be heated? It is
found that a DBT of 30 C will be quite comfortable to the labourers. How will you obtain this
condition? Indicate the exact temperature to which it should be taken before bringing it to 30 C and
50% RH. If it is necessary to use 5000 m
3
/h of air at the final condition mentioned above, estimate the
quantity of air needed at its original condition.
5.8 Air at 80% saturation is to be maintained in a weaving room. Air at a DBT of 41 C and WBT of
24 C is available. This air for weaving room is obtained by saturating it initially and then heating it
to 80% saturation. Estimate the final temperature of the air and its humidity.
5.9 Air at a temperature of 60 C and a pressure of 745 mm Hg and a % humidity of 10 is supplied to
a drier at a rate of 120 m
3
/h. Water is evaporated in the drier at a rate of 25 kg/h. The air leaves at a
temperature of 35 C and a pressure of 742 mm Hg. Calculate (a) percentage humidity of air leaving
the drier and (b) volume of wet air leaving the drier per hour. (use vapour pressure data from Steam
Tables).
5.10 Air at a temperature of 30 C and a pressure of 100 kPa has a relative humidity of 80%.
Calculate (a) the molal humidity of air, (b) molal humidity of this air if its temperature is reduced to
15 C and its pressure increased to 200 kPa, condensing out some of the water, (c) weight of water
condensed from 100 m
3
of the original wet air in cooling to 15 C and compressing to 200 kPa, and
(d) the final volume of the wet air of part (c)
Data: Vapour pressure of water at 30 C = 4.24 kPa
Vapour pressure of water at 15 C = 1.70 kPa
5.11 Air at 85 C and absolute humidity of 0.03 kg water vapour per kg dry air, 1 std. atm is
contacted with water at the adiabatic saturation temperature and is thereby humidified and cooled to
70% saturation. What are the final temperature and humidity of the air?
5.12 An air-water vapour sample has a dry bulb temperature (DBT) of 55 C and an absolute
humidity 0.030 kg water/kg dry air at 1 std. atm pressure. Using humidity chart, calculate (a) the
relative humidity, if vapour pressure of water at 55 C is 118 mm Hg and (b) the humid volume in
m
3
/kg dry air.
5.13 A drier is used to remove 100 kg of water per hour from the material being dried. The available
air has a humidity of 0.010 kg bone dry air, and a temperature of 23.9 C and is heated to 68.3 C
before entering the drier. The air leaving the drier has a wet-bulb temperature of 37.8 C and a dry-
bulb temperature of 54.4 C. Calculate (a) air consumption rate, (b) humid volume of air before and
after preheating, (c) wet-bulb temperatures (WBT) of air before and after preheating, and (d) dew
point of the air leaving the drier.
5.14 The air supply for a drier has a dry-bulb temperature of 23 C and a wet-bulb temperature of 16
C. It is heated to 85 C by heating coils and introduced into the drier. In the drier, it cools along the
adiabatic cooling line and leaves the drier fully saturated.
(a) What is its humidity?
(b) What is the dew point of the initial air?
(c) How much water will be evaporated per 100 cubic metre of entering air?
(d) How much heat is needed to heat 100 cubic metre air to 85 C? (e) At what temperature does the
air leave the drier?
5.15 A mixture of carbon disulphide vapour and air contains 23.3% carbon disulphide (CS
2
) by
volume. Calculate the relative saturation and percent saturation of the mixture at 20 C and 740 mm
Hg pressure. Vapour pressure of CS
2
at 20 C = 300 mm Hg
5.16 Air at 60 C and 745 mm Hg having a percent humidity of 10% is supplied to a drier at the rate
of 1100 m
3
/h. Water at the rate of 20 kg/h is to be removed from the wet material. The air leaves the
drier at 35 C and 742 mm Hg. Calculate (a) percent humidity of leaving air and (b) volumetric flow
rate of leaving air.
5.17 Air is available at a DBT of 310 K and a WBT of 305 K. Estimate humidity, % saturation, dew
point, humid volume and enthalpy using humidity chart. Estimate humid volume and enthalpy using
equations and compare the results.
5.18 One thousand m
3
/min of methane saturated with water vapour at 1 atm, 49 C is cooled to 10 C,
so that part of water vapour is condensed. The mixture is then reheated to 24 C at 1 atm. What is (a)
the volumetric flow rate of leaving mixture, and (b) amount of water condensed?
Data: Vapour pressure of water at 49 C, 24 C and 8 C are 100 mm Hg, 27 mm Hg and 8 mm Hg
respectively.
5.19 Air at a temperature of 30 C and pressure 760 mm Hg has a relative humidity of 60%,
calculate:
(a) The absolute humidity of air
(b) The humidity of this air if its temperature is reduced to 20 C and
the pressure increased to 2600 mm Hg, condensing out some of the water.
(c) The weight of water condensed from 1000 m
3
of the original wet air. VP of water at 30 C and 20
C are 32 mm Hg and 17.5 mm Hg respectively.
5.20 A mixture of air water vapour is present at 40 C and 762 mm Hg.
The volume of the mixture is 5 litres and the partial pressure of water vapour in the mixture is 27.7
mm Hg. The mixture is heated to 60 C at constant volume. Compute the following:
(a) Partial pressure of water vapour
(b) Partial pressure of dry air
(c) Total pressure, and
(d) Molal humidity.
5.21 A mixture of acetone vapour and nitrogen contains 15% acetone by volume. Calculate molal
humidity, partial pressure of acetone, relative saturation and % saturation at 20 C and 745 mm Hg.
Vapour pressure of acetone at 20 C = 184.8 mm Hg.
5.22 Air at 60 C and pressure of 745 mm Hg and a % humidity of 20 is supplied to a dryer at 1500
m
3
/h. Water is removed at a rate of 2.5 kg/h. Air leaves at 35 C at 742 mm Hg, vapour pressure at 35
C = 43 mm Hg, and vapour pressure at 60 C = 149.38 mm Hg Estimate:
(a) Percentage humidity of air leaving
(b) Volumetric flow rate of wet air leaving
Psychrometric chart for airwater system at 760 mm Hg pressure.
Crystallization 6
Crystallization is a process in which the solid particles are formed from a homogeneous phase.
During crystallization, the crystals form when a saturated solution gets cooled. The solution left
behind after the separation of crystals is known as mother liquor which will also be a saturated
solution. The mixture of crystals and mother liquor is known as magma.
A simple illustration of a crystallization process is shown below.
Water evaporated, E kg/h
xE
Feed, F kg/h
x
F
Crystallizer
Mother liquor, M kg/h xM
Crystal, C kg/h
xC
Feed rate of solution of concentration, x
F
: F kg/h Amount of water evaporated
(x
E
= 0 as salt in water evaporated will be zero) : E kg/h Amount of mother liquor of concentration
x
M
: M kg/h (Mother liquor will always be a saturated solution)
Weight of crystal formed of concentration, x
C
: C kg/h Total mass balance gives, F = C + M + E (6.1)
Component balance gives, Fx
F
= Cx
C
+ Mx
M
+ Ex
E
(6.2)
Since we normally know F, E, x
F
x
M
x
E
we can find C and M by solving the Eqs. (6.1) and (6.2). x
E
will always be zero as it is free from salt.
When we get anhydrous salt, x
C
is 1.0. Some times we get hydrated salt during crystallization process.
Under such circumstances x
C
will not be 1.0 but will be less than unity and this can be obtained by
molecular weight of anhydrous salt divided by the molecular weight of hydrated salt. The above
principles are explained through the following problems.
111
WORKED EXAMPLES
6.1 A solution of sodium chloride in water is saturated at a temperature of 15 C. Calculate the
weight of NaCl that can be dissolved by 100 kg of this solution if it is heated to 65 C.
Solubility of NaCl at 15 C = 6.12 kg mole/1000 kg H
2
O
Solubility of NaCl at 65 C = 6.37 kg mole/1000 kg H
2
O Basis: 1000 kg of water
NaCl in saturated solution at 15 C = (6.12 58.5) = 358 kg NaCl in saturated solution at 65 C =
(6.37 58.5) = 373 kg NaCl that may be dissolved further = (373 358) = 15 kg
1000
Water in 100 kg of saturated solution at 15 C = 100

1358
= 73.6 kg \ amount of additional NaCl that will be dissolved
=
15 73.6
= 1.1 kg
1000
6.2 After a crystallization process, a solution of calcium chloride in water contains 62 kg CaCl
2
per
100 kg of water. Calculate the weight of this solution necessary to dissolve 250 kg of CaCl
2
6H
2
O at
25 C (solubility = 7.38 kg mole CaCl
2
/1000 kg H
2
O)
Basis: x kg of water is present in original solution
CaCl
2
6H
2
O has the molecular weight = 111 + 108 = 219 250 kg of solution will have 126.7 kg of
CaCl
2
and 123.3 kg of 6H
2
O Total CaCl
2
entering the process = (0.62x + 126.7) kg (1) Water
entering the process = (x + 123.3) kg
Solubility of CaCl
2
at saturated condition for 1000 kg water
= 7.38 kmoles = 819.18 kg
\ CaCl
2
leaving the process along with (x + 123.3) kg of water
=
819.18
(x + 123.3) kg (2)

1000
Equating (1) and (2), we get
(0.62x + 126.7) = 0.81918 (x + 123.3)
0.62x + 126.7 = 0.81918x + 101 0.19918x = 25.7
\ x = 129.03 kg
100 kg of water is equivalent to 162 kg of solution
162
129.03 kg of water is equivalent to 129.03
100
= 209 kg of solution
Original solution needed = 209 kg.
6.3 A solution of sodium nitrate in water at a temperature of 40 C contains 49% NaNO
3
by weight.
(a) Calculate the percentage saturation of this solution (b) Calculate the weight of NaNO
3
that may be
crystallized from
1000 kg of solution by reducing the temperature to 10 C (c) Calculate the percentage yield of the
process.
Solubility of NaNO
3
at 40 C = 51.4% by weight.
Solubility of NaNO
3
at 10 C = 44.5% by weight.
Basis: 1000 kg of original solution
(a)
kg of NaNO
3
49
= 0.96kg of water 51
kg of NaNO
at 40 C,

3


51.4 = 1.06

saturation
48.6
0.96
% saturation of given solution =

100 = 90.8%

(b) Let a kg be NaNO

3
crystallized out
NaNO
3
balance = (1000 0.49) = (1000 a) (0.445) + a; Solving, a = 81 kg
81
(c) % Yield =

100 = 16.53%

6.4 A solution of K
2
Cr
2
O
7
in water contains 13% by weight. From 1000 kg of this solution is
evaporated 640 kg of water. The remaining solution is cooled to 20 C. Calculate the amount and the
percentage yield of K
2
Cr
2
O
7
crystals formed.
Solubility at 20 C = 0.39 kmole/1000 kg H
2
O
Basis: 1000 kg of original solution
K
2
Cr
2
O
7
= 130 kg;
Water = 870 kg
Water present finally = (870 640) = 230 kg
0.39

294 = 26.4 kg

K
2
Cr
2
O
7
present then = 230

\ K
2
Cr
2
O
7
crystallized = 130 26.4 = 103.6 kg
% Yield =
103.6
= 79.7%
130
6.5 A solution of sodium nitrate in water contains 100 g of salt per 1000 g of water. Calculate the
amount of ice formed in cooling 1000 g of this solution to 15 C (solubility at 15 C = 6.2 g
mole/1000 g H
2
O)
Basis: 1000 g of original solution

100

= 91 g

NaNO
3
present initially = 1000

Water present initially = 909 g

Water retained along with NaNO
3
=
1000 91
= 172.6 g
6.2 85
\ Ice formed = Original water water retained along with NaNO
3
= (909 172.6) = 736.4 g
6.6 1000 kg of a 30% aqueous solution of Na
2
CO
3
is slowly cooled to 20 C. During cooling, 10%
water originally present evaporates. The crystal is Na
2
CO
3
10H
2
O. If the solubility of anhydrous
Na
2
CO
3
at 20 C is 21.5 kg/100 kg of water, what weight of salt crystallizes out?
Basis: 1000 kg of solution.
Salt = 300 kg
Water = 700 kg
Water evaporated = 700 0.1 = 70 kg
Let a kg of salt crystallize out. Let the weight of mother liquor be b kg Molecular weight of Na
2
CO
3
=
106 and that of Na
2
CO
3
10H
2
O = 286 a + b = (1000 70) = 930 kg
106 21.5
= 300 kg
2
CO
3
balance = abNa


Solving, a = 700 kg; b = 230 kg
Check (water balance):
180

700




100 = 630 kg


6.7 A batch of saturated Na
2
CO
3
solution of 100 kg is to be prepared at
50 C. The solubility is 4.48 g mole/1000 g H
2
O at 50 C. (i) If the monohydrate were available, how
many kg of water would be required to form the solution?
(ii) If the decahydrate is available how many kg of salt will be required? Basis: 100 kg of saturated
solution at 50 C.
Solubility at 50 C = (4.48 106) kg Na
2
CO
3
/1000 kg H
2
O i.e. 474.88 kg Na
2
CO
3
/1474.88 kg
solution.
100 474.88
In 100 kg of solution, Na
2
CO
3
present =
1474.88
= 32.2 kg
water present = (100 32.2) = 67.8 kg
Molecular weight of Na
2
CO
3
H
2
O = 106 + 18 = 124 kg Molecular weight of Na
2
CO
3
10H
2
O =
106 + 180 = 286 kg (i) Water needed for monohydrate = Actually needed-water from
hydrated salt
= (67.8)

32.2
18


= 62.33 kg
(ii) Weight of decahydrate needed = 32.2
286
= 86.88 kg
106
Discussion: In case (ii), water available in the salt is
32.2
180
= 54.68 kg
106
The additional water needed hence is 13.12 kg, thus making the total water to 13.12 + 54.68 = 67.8 kg
(which corresponds to solubility data) 6.8 10,000 kg/hr of 6% solution of salt in water is fed to an
evaporator. Saturated solution is produced and some salt crystallizes out. The hot crystals with some
adhering solution are centrifuged to remove some of the solution. Then the crystals are dried to
remove the rest of water. During an hour test, 837.6 kg of concentrated solution was removed in
evaporator, 198.7 kg of solution was separated in the centrifuge and 361.7 kg of dried crystals got.
Previous test on the centrifuge show that it removed 60% of adhering solution. Calculate (a) the
solubility of the salt; (b) water removed in evaporator; (c) water removed in drier; and (d) water
leaving the evaporator.
Discussion: The solution leaving the evaporator and centrifuge maintains the same concentration and
is saturated. From evaporator, the various streams leaving are water vapour, saturated solutions and
crystals with adhering solution.
Basis: One hour.
60% adhering solution (removed in centrifuge) = 198.7 kg \ Total adhering solution entering
centrifuge (along with crystal) =
198.7
= 331.2 kg
0.6

Water vapour
10,000 kg/hr
Centrifuge6% solution Evaporator
Adhering
Water
solution
+ Dry crystal crystal
Drier
361.7 kg
837.6 kg solution 198.7 kg
Let s be the solubility of salt, which is given by (s kg of salt/kg of solution) Making salt balance,
(10,000 0.06) = (837.6 + 198.7)s + 361.7
Solving, (a)
s = 0.23 kg of salt/kg of solution.
1 kg solution = 0.23 kg salt/0.77 kg H
2
O = 0.3 kg salt/kg H
2
O
(b) Weight of adhering solution entering drier = (331.2 198.7) = 132.5 kg
(c) Water in it (removed in drier) = 132.5 0.77 = 102 kg (since, 1 kg of solution contains 0.77 kg
water and 0.23 kg of salt)
(d) Weight of material entering drier = Final dry salt + Water evaporated
= (361.7 + 102) = 463.7 kg
Weight of material entering centrifuge = (463.7 + 198.7) = 662.4 kg
Weight of water leaving the evaporator = 10,000 (837.6 + 662.4) = 8,500 kg
Check:
Water balance = 8,500 + 102 + (837.6 + 198.7) (0.77)
= 8,500 + 102 + 798 = 9,400 kg
6.9 In a solution of naphthalene in benzene, mole fraction of naphthalene is 0.12. Calculate the weight
of this solution necessary to dissolve 100 kg of naphthalene at 40 C (solubility of naphthalene is
57% by weight)
100 kg
X kg solution (100 + X) kg
0.817 wt fr. of benzene
Tank
0.183 wt fr. of naphthalene
0.57 wt. fr. of naphthalene
Basis: 1 mole of feed solution
Component mole Molecular Weight, kg Weight weight fraction
Naphthalene (C
10
H
8
) 0.12 128 15.4 0.183
Benzene (C
6
H
6
) 0.88 78 68.6 0.817
Total 84.0 1.000
Let us assume that X kg of feed solution enters the tank. Naphthalene balance in tank gives, 0.183X +
100 = (100 + X)0.57 X = 111 kg of original feed solution.
6.10 A crystallizer is charged with 7,500 kg of aqueous solution at 104 C containing 29.6% by
weight of anhydrous Na
2
SO
4
. The solution is then cooled to 20 C. During this operation 5% of water
is lost by evaporation. Glauber salt crystallizes out. Find the yield of crystals.
Solubility at 20 C = 194 g Na
2
SO
4
/100 g water
Molecular weight of Glaubers salt (Na
2
SO
4
10H
2
O) = 142 + 180 = 322 Basis: 7,500 kg of aqueous
solution.
Na
2
SO
4
present = 7500 0.296 = 2220 kg
H
2
O present = (7500 2220) = 5280 kg
H
2
O lost in evaporation = 5280 0.05 = 264 kg
H
2
O remaining = (5280 264) = 5016 kg
Let a kg of Glauber salt crystallize and b kg be the weight of the solution.

ab

Na2SO4 balance: 2220 = 142

ab


H
2
O balance: 5016 =
180


Solving, a = 3749.5 kg and b = 3486.5 kg
Weight of Glauber salt = 3749.5 kg
Weight of solution = 3486.5 kg
Check: (total balance) 3749.5 + 3486.5 + 264 = 7500 kg
6.11 An evaporator-crystallizer is to produce 13,000 kg dry salt/h from a feed solution having 20%
NaCl. The salt removed carries 20% of its weight of brine containing 27% NaCl (All Composition in
Weight %). Calculate the feed rate kg/h.
Water
20% NaCl
Evaporator
Feed F
crystallizer
13,000 kg dry salt/h
Basis: 1 h of operation
13,000 kg of salt with 20% brine
Weight of feed brine = 13,000 0.2 = 2,600
NaCl in this solution = 2,600 0.27 = 702
NaCl balance gives, 0.2F = (13,000 + 702)
\ Feed = 13,702/0.2 = 68,510 kg/h.
6.12 5000 kg of KCl are present in a saturated solution at 80 C. The solution is cooled to 20 C in an
open tank. The solubilities of KCl at 80 C and 20 C are 55 and 35 parts per 100 parts of water.
(a) Assuming water equal to 3% by weight of solution is lost by evaporation, calculate the weight of
crystals obtained. (b) Calculate the yield of crystals neglecting loss of water by evaporation; KCl
crystallizes without any water of crystals.
3% Water
5000 kg KCl Crystallizer 20 C
80 C
Saturated solution
Saturated solution
Crystal
Basis: 5,000 kg of KCl salt in a solution at 80
o
C
(a) Solubility at 80 C = 55 kg salt/100 kg water
or, solubility of KCl = 55 kg/155 kg solution = 0.355 kg/kg solution 5000 kg KCl is equivalent to
5000/0.355 = 140,90.91 kg of solution Water present = 140,90.91 5000 = 9090.91 kg
Water evaporated = 3% weight if solution = 140,90.91 0.03 = 422.73 kg Water remaining =
9,090.91 422.73 = 8668.18 kg
35
KCl in leaving solution at 20C = 8668.18

= 3033.86 kg

\ KCl crystallized out = 5000 3033.86 = 1966.14 kg (b) KCl in solution at 20 C = 9090.91 0.35 =
3181.82 kg \ KCl crystallized out = 1818.18 kg
% Yield of crystals = 1818.18
100
= 36.37%
5000
6.13 A crystallizer is charged with 6,400 kg of an aqueous solution containing 29.6% of anhydrous
sodium sulphate. The solution is cooled and 10% of the initial water is lost by evaporation.
Na
2
SO
4
.10H
2
O crystallizes out. If the mother liquor (after crystallization) is found to contain 18.3%
Na
2
SO
4
, calculate the weight of the mother liquor.
10% water
6,400 kg 18.3% Na2SO4Crystallizer
Mother liquor M
29.6%
Na
2
SO
4
10H
2
O (142 + 180) = 322
Basis: 6,400 kg solution.
Weight of Na
2
SO
4
= 6,400 0.296 = 1,894.4 kg
Water present in feed = 4,505.6 kg
Let M be the weight of mother liquor and C the weight of crystal formed.
Water lost by evaporation = 10% of 4505.6 kg = 450.56 kg
142
Overall balance of Na
2
SO
4
gives, 1894.4 =
C

+ (0.183 M)
322
C + M = (6400 450.56) = 5949.44 kg
Solving, M = mother liquor = 2826.7 kg
C = Crystal = 3122.7 kg
Check:
(water balance) 450.56 +

2826.7

81.7 180


322 = 4505.6 kg
6.14 What will be the yield of Glauber salt if pure 32% solution is cooled
to 20 C from hot condition? There is no loss of water. The solubility of Na
2
SO
4
in water at 20 C is
19.4 g per 100 g of water.
Feed 32%
Crystallizer
Mother Liquor, Y
Crystals, X
Basis: 1,000 g of the feed solution.
Na
2
SO
4
.10H
2
O (142 + 180 = 322)
Na
2
SO
4
present in the feed = 320 g
Water present in the feed = 680 g
Overall balance is X + Y = 1000 g
142
XY
Na
2
SO
4
balance =

= 320

180
XY

Water balance =

= 680

322 119.4
Solving, we get X = Weight of crystals = 566.761 g and Y = Weight of mother liquor = 433.239 g
Yield of the crystals =
566.761
= 56.68%
1000
EXERCISES
6.1 Feed to a crystallizer contains 6,420 kg of aqueous solution containing 29.6% anhydrous sodium
sulphate by weight at 104 C. The solution is cooled to 20 C to crystallize out the desired Glaubers
salt. The mother liquor is found to contain 16.1% anhydrous sodium sulphate. Estimate the weight of
mother liquor.
6.2 A vacuum crystallizer is to produce 10,000 kg of FeSO
4
.5H
2
O crystals per hour. The feed
solution contains 38.9 parts FeSO
4
/100 parts water. The feed enters at 70 C and is cooled to 27 C.
The solubility at 27 C is 30.3 parts FeSO
4
/100 parts water. Determine the quantity of feed and water
lost as vapour.
6.3 10,000 kg of a 30% aqueous solution of Na
2
CO
3
is slowly cooled to 20 C. During cooling, 3%
water originally present evaporates. The crystal is Na
2
CO
3
.10H
2
O. If the solubility of anhydrous
Na
2
CO
3
at 20 C is 21.5 kg/100 kg of water, what is the weight of Na
2
CO
3
.10H
2
O formed?
6.4 1000 kg of a solution containing 25% of Na
2
CO
3
by weight is slowly cooled to 20 C. During
cooling 15% water originally present evaporates. The crystal formed is Na
2
CO
3
.10H
2
O. If the
solubility of anhydrous Na
2
CO
3
at 20 C is 21.5 kg/100 kg of water, what is the weight of
Na
2
CO
3
.10H
2
O crystals formed?
6.5 1500 kg of a solution containing 20% of Na
2
SO
4
and 80% water by weight is subjected to
evaporative cooling and 20% of original water evaporates. Calculate the yield of Na
2
SO
4
.10H
2
O
crystals formed from solution, if the temperature of solution is reduced to 20 C. The solubility of
anhydrous Na
2
SO
4
in water at 20 C is 19.4 gm per 100 gm of water.
6.6 An evaporator concentrates 10,000 kg/h of 20% KNO
3
solution to 50% KNO
3.
The concentrated
liquor is sent to a crystallizer where crystals of KNO
3
are formed and separated. The mother liquor
from the crystallizer is recycled and mixed with the evaporator feed. The recycle stream is a
saturated solution containing 0.6 kg KNO
3
/kg water. The crystals carry 4% water. Compute water
evaporated and crystals obtained.
6.7 A crystallizer is charged with 9000 kg of an aqueous solution of 20% Na
2
SO
4
and it is subjected
to evaporative cooling and 10% of original water evaporates. Glaubers salt crystallizes. The mother
liquor leaves with 16% salt. Calculate the weights of (a) water loss (b) the mother liquor leaving and
(c) crystals formed.
6.8 A solution of sodium sulphate in water is saturated at a temperature of 40 C. Calculate the
weight of crystals formed and the percentage yield obtained by cooling 100 kg of this solution to a
temperature of 5 C.
Solubility Data: At 40 C : 32.6% Na
2
SO
4
At 5 C : 5.75% Na
2
SO
4
6.9 A solution of K
2
Cr
2
O
7
in water contains 16% K
2
Cr
2
O
7
by weight. 1000 kg of this solution are
evaporated to remove some water. The resulting solution is cooled to 20 C. If the yield of K
2
Cr
2
O
7
crystals is 80%, calculate the amount of water evaporated.
Solubility of K
2
Cr
2
O
7
at 20 C = 0.39 k mole/1000 kg H
2
O 6.10 A saturated solution of MgSO
4
at 80
C is cooled to 25 C. During this
process 5% of the original water is lost. Find the weight of water lost, mother liquor leaving and
feed, if 1500 kg of MgSO
4
.7H
2
O crystallizes. Solubility data: At 80 C : 64.28 g MgSO
4
per 100 g
water At 25 C : 40.88 g MgSO
4
per 100 g water
6.11 Hypo crystals Na
2
S
2
O
3
5H
2
O are to be produced at the rate of 2000 kg/h. A 60% Na
2
S
2
O
3
solution is cooled to 293 K from 333 K. The solubility at 293 K is 70 parts anhydrous salt per 100
parts of water. Estimate the amount of feed needed.
Mass Balance
7
This chapter deals with the mass balance both with and without chemical reactions. The principles
given in Chapter 2 still hold good. The application of mass balance in unit operations and processes
is illustrated through worked examples and exercise problems.
WORKED EXAMPLES
7.1 Soyabean seeds are extracted with hexane in batch extractors. The seeds contain 18.6% oil, 69%
solids and 12.4% moisture. At the end of the extraction process, the residual cake is separated from
hexane. The analysis of cake reveals 0.8% oil, 87.7% solids and 11.5% moisture. Find the %
recovery of oil.
Basis: 100 kg of seeds
Solids free from oil is the tie element
Weight of solids in feed = 69 kg = 87.7% of cake \ cake = 78.68 kg
Oil extracted = (18.6 78.68 0.008) = 17.971 kg
% oil extracted =
17.971
100 = 96.6%

18.6
7.2 A multiple effect evaporator handles 100 tonnes/day of pure cane sugar. The feed to the
evaporator contains 30% solids. While the concentrate is leaving with 75% solids concentration,
calculate the amount of water evaporated per day.
?
30% solids 75% solids
Evaporator
Basis: 100 tonnes of feed = 10
5
kg Solids in the feed = 30,000 kg
122
\ Concentrated liquid leaving =
30,000
= 40,000 kg
0.75
Water evaporated/day = (1,00,000 40,000) = 60,000 kg 7.3 A water soaked fabric is dried from
44% moisture to a final moisture
of 9%. Calculate the weight of water removed per 200 kg of dried
fabric.
?
44% moisture 9% moisture Drier
200 kg
Basis: 200 kg of product.
Dry fabric = (200 0.91) = 182 kg

182
Wet fabric entering =

= 325 kg

Water evaporated = (325 200) = 125 kg

7.4 The exit gas from a phosphate reduction furnace analyzes P
4
: 8%, CO : 89% and N
2
: 3%. This
gas is burnt with air under conditions selectively to oxidize phosphorus. From the flue gas, the oxides
of phosphorus precipitate on cooling and is separated from the remaining gas. Analysis of the latter
shows CO
2
: 0.9%, CO : 22.5%, N
2
: 68.0% and O
2
: 8.6%. Assume oxidation of phosphorus is
complete and that it exists in the flue gas partly as P
4
O
6
and partly as P
4
O
10
. Calculate:
(a) % of CO entering the furnace that is oxidized to CO
2
and (b) % of P
4
that is oxidized to P
4
O
10
P
4
+ 3O
2
P
4
O
6
P
4
+ 5O
2
P
4
O
10
CO + O
2
CO
2
Exit gas
from phosphate
reduction furnace
Burner
CO
2
, O
2
,
Air
CO, N
2
Oxides of P
Basis: 100 g moles of exit gas from phosphate reduction furnace P
4
is 8 g moles.
Let x g mole of P
4
get converted to P
4
O
10
\ (8 x) g mole of P
4
gets converted to P
4
O
6
Carbon is the tie element
89 g atoms of C 23.4% of final gas. (Total carbon in CO and CO
2
)
89
= 380.342 g moles\ Total final gas moles =
0.234
(a) % CO oxidized to CO
2
= (380.342 0.009/89) 100 = 3.852 g moles
(b) N
2
in final gas = (380.342 0.68) = 258.632 g moles N
2
from air = (258.632 3) = 255.632 g
moles
O
21
= 67.953 g moles
2
from air = 255.632
79
O
2
for formation of P
4
O
10
= 5x g mole
O
2
for formation of P
4
O
6
= 3(8 x) g mole
O
2
for formation of CO
2
= 380.342 0.009 0.5 = 1.712 g moles O
2
leaving = 380.342 0.086 =
32.71 g moles
O
2
reacted = (67.953 32.71) = 35.243 g moles
Making a balance for oxygen,
(5 x + 24 3x + 1.712) = 35.243
\ x = 4.7654 g moles
\ P
4
converted to P
4
O
10
= (4.7654 100/8) = 60%
7.5 A tank of weak H
2
SO
4
contains 12.43% acid. If 200 kg of 77.7% H
2
SO
4
are added to the tank and
the final acid is 18.63%, how many kg of weak acid is used?
Let the weight of weak acid be x kg and the weight of final acid be y kg.
Overall balance is x + 200 = y
Acid balance is given as 0.1243x + (200 0.777) = 0.1863y Solving, x = 1,905.5 kg and y = 2,105.5
kg
7.6 A cotton mill dries a water soaked fabric in a drier from 54% to 9% moisture. How many
kilogram of water are removed by drying operation per 1200 kg of feed.
Basis: 1200 kg of feed.
Dry fabric = (1200 0.46) = 552 kg

Water
54% moisture 9% moisture Drier

Weight of product =
552
= 606.6 kg
0.91
Water removed = 1200 606.6 = 593.4 kg
Alternative method:
Water in feed = 1200 0.54 = 648 kg
Water in product = 606.6 0.09 = 54.6 kg
Water removed = 648 54.6 kg
= 593.4 kg
7.7 A gas containing 2% NH
3
, 25.4% N
2
and the rest H
2
is flowing in a pipe. To measure the flow
rate an ammonia rich gas containing 96%
NH
3
, 3% H
2
and 1% N
2
is sent at a rate of 100 cc/min. The concentration of NH
3
in the down stream
is 6%. Find the flow rate of gas at inlet.
Basis: Let x cc/min of feed gas enter the pipe
Ammonia rich gas entering = 100 cc/min
\ Exit gas = (100 + x) cc/min.
Making a balance for ammonia: 0.02x + 96 = (100 + x) 0.06 Solving, x = 2250 cc/min.
x cc/min. gas Exit (100 + x) Pipe
6% NH3
NH
3
rich gas
(96%) 100 cc/min.
7.8 A lime stone analysis shows CaCO
3
: 94.52%, MgCO
3
: 4.16% and rest insoluble. (a) How many
kg of CaO could be obtained from 4 tonnes of limestone? (b) How many kg of CO
2
are given off per
kg of limestone?
(a) Basis: 4 tonnes of limestone = 4,000 kg
CaCO
3
= 0.9452 4000 = 3,780.8 kg
MgCO
3
= 0.0416 4000 = 166.4 kg
CaCO
3
CaO + CO
2
100 56 44
MgCO
3
MgO + CO
2
84.3 40.3 44
CaO got =
3780.8 56
= 2,117.3 kg
100
(b) Basis: 1 kg of limestone
CaCO
3
= 0.9452 kg, MgCO
3
= 0.0416 kg

44 44
CO
2
produced =
0.9452 +


= 0.4376 kg (by stoichiometry)
7.9 The gases from a sulphur burner have the following analysis: SO
2
: 9.86%, O
2
: 8.54%, N
2
: 81.6%.
After passage of gases through a catalytic converter, the analysis is 0.605% SO
2
; 4.5% O
2
; 94.895%
N
2
. What percentage of SO
2
entering the converter has been oxidized to SO
3
?
Basis: 100 g moles of gas entering the converter
N
2
is the tie element.
Exit stream =
81.6
= 86 g moles
0.94895
SO
2
leaving = 86 0.00605 = 0.5203 g moles
SO
2
converted to SO
3
= SO
2
entering SO
2
leaving the converter
= (9.86 0.52) = 9.34 g moles
% SO
2
converted = 9.34
100
= 94.7%
9.86
7.10 Hydrochloric acid is commercially prepared in a Mannheim furnace by the reaction between
NaCl and H
2
SO
4
. The HCl gas is absorbed in water. Calculate (a) the weight of HCl formed when 2
tonnes of 98% salt reacts; (b) How much sodium sulphate is produced and how many kg of 40% acid
will be produced?
Basis: 2 tonnes of salt = 2000 kg
NaCl = 2000 0.98 = 1960 kg

2NaCl + H SO
Na SO
+ 2HCl
24 24

(2 58.4) 98142 (2 36.4)
2
36.4
(a) HCl formed = 1960

2 58.4
= 1221.6 kg

(b) Na
2
SO
4
formed = 1960
142
= 2382.9 kg
2

40% acid formed = 1221.6/0.4 = 3054 kg
7.11 Dolomite chiefly a mixture of calcium and magnesium carbonates is to be leached with
concentrated H
2
SO
4
to recover Mg as MgSO
4.
The rock analysis indicates 20% Ca, 10% Mg and 5%
SiO
2.
After reaction the soluble material is filtered off and the solid are washed and discarded.
Analysis of the sludge cake shows 50% moisture, 2% SiO
2
; 0.5% Mg and 1% Al. What fraction of
Mg was extracted? Basis: 100 g of dolomite
SiO
2
is the tie element
5 g SiO
2
2% sludge cake
\ weight of sludge cake =
5
= 250 g
0.02

Mg in sludge cake = 250
0.5
= 1.25 g
100
Mg extracted = (10 1.25) = 8.75 g
Fraction Mg extracted =
8.75
= 0.875
10
7.12 A certain soap contains 50% moisture on the wet basis when raw. The moisture is reduced to
20% before the soap is pressed into cakes. How many 300 g cakes can be pressed from 1 tonne of
raw soap?
Basis: 1 tonne of raw soap = 1000 kg
Dry soap = 500 kg 80% after drying

500
= 625 kg\ Weight of dried soap =
0.8
625
No. of cakes pressed =

= 2083

(The number of cakes has to be an integer)

7.13 Phosphate rock at ` 80/tonne is being added to a cheap fertilizer to enrich it. If the cheap
fertilizer costs ` 32/tonne and the final blended product including 30% profit is to be marketed at `
64/tonne, how much phosphate rock should be added to each tonne of cheap fertilizer?
Basis: 1 tonne of cheap fertilizer and x tonne of phosphate rock. Blended fertilizer = (1 + x) tonne
Final cost of blended fertilizer = ` 64/tonne
Actual cost (30% profit) =
64
= ` 49.23 = cost of production
1.3
Cost balance: 32 + 80x = (1 + x) 49.23
Solving, x = 0.56 tonne (Phosphate rock)
7.14 Limestone is a mixture of Ca and Mg carbonates. Lime is made up calcining the carbonates, i.e.
driving away all CO
2
gas. When pure limestone is calcined, 44.8 g of CO
2
is got per 100 g of
limestone. What is the composition of limestone?
Basis: 100 g of limestone (pure)
Let x g be the weight of CaCO
3
and y g be the weight of MgCO
3
CaCO
3
CaO + CO
2
100 56 44
MgCO
3
MgO + CO
2
84.3 40.3 44
Overall balance: x + y = 100 (since pure)
CO
2
balance = 0.44x + 0.52y = 44.8
Solving, x = 90 g (CaCO
3
) and y = 10 g (MgCO
3
) 7.15 The feed to a fractionating system is 30,000
kg/h of 50% benzene, 30% toluene and 20% xylene. The fractionating system consists of two towers
No. I and No. II. The feed enters tower I. The overhead product from I is x kg/h of 95% benzene, 3%
toluene and 2% xylene. The bottom product from I is feed to II resulting in an overhead product of y
kg/h of 3% benzene, 95% toluene and 2% xylene while the bottom from II tower is z kg/h of 1%
benzene, 4% toluene and 95% xylene. Find x, y and z.
x y
Feed I II
z
Overall balance yields
x + y + z = 30,000
Individual balance yields:
For benzene, 0.95x + 0.03y + 0.01z = 15,000 For toluene, 0.03x + 0.95y + 0.04z = 9,000 For xylene,
0.02x + 0.02y + 0.95z = 6,000 Solving, x = 15,452.2 kg/h
y = 8,741.3 kg/h
z = 5,806.5 kg/h
Total 30,000.0 kg/h
7.16 A sample of fuel has the following composition by mass: C : 84%, H
2
: 15.2% and rest
comprising noncombustibles. The fuel was completely burnt with excess air in an internal combustion
engine. The dry exhaust gas has 8.6% CO
2
by volume. Estimate the amount of air supplied per kg of
fuel and find the products of combustion (air contains 23.1% oxygen by weight).
Basis: 1 kg of fuel
C : 0.84 kg = 0.07 kmole; H
2
: 0.152 kg = 0.076 kmole; Noncombustibles 0.008 kg
C+O
CO ; H +O

nn H O
222 2 2
12 32 44 2 16 18
CO
2
formed 0.07 kmole
H
2
O formed = 0.076 kmole
Total kmole of exhaust stream =
0.07
= 0.814 (dry)
0.086
O
2
needed for forming CO
2
and H
2
O =
0.076
= 0.108 kmole
N
2
entering (along with stoichiometrically needed O
2
) = 0.108
79
21
= 0.4063 kmole
Air needed (stoichiometric) =
0.108
= 0.5143 kmole
0.21
Exhaust gas contains CO
2
, N
2
and O
2
Excess air in exhaust = Total moles in exhaust stream (dry)
(N
2
entering as per stoichiometry + CO
2
formed) = 0.814 (0.4063 + 0.07)
= 0.814 0.4763 kmole
= 0.3377 kmole
We know what air contains
O
2
= 0.071 kmole (21%) N
2
= 0.2667 kmole (79%)
N
2
total = 0.4063 + 0.2667 = 0.673 kmole
Total air supplied = (0.5143 + 0.3377) = 0.8520 kmole
0.3377
% excess air =

100 = 65.6%

Weight of air supplied/kg of fuel = (0.852 28.84) = 24.57 kg

Components Weight, kmole Composition of dry exhaust gas
CO
2
0.0700 8.6
O
2
0.0710 8.7
N
2
0.6730 82.7
Total 0.8140 100.0
7.17 A company buys its paper from the manufacturer at the contract price of ` 3/kg on a specification
that the paper should not have more than 5% moisture. It is also agreed that the price can be suitably
adjusted if the moisture content differs from the specified value.
A shipment of 5,000 kg of paper was found to contain 7.86% moisture. (a) Find the price to be paid
to manufacturer as per contract. (b) If it were agreed that the freight was to be borne by the company
and adjusted according to the moisture content, what would the company pay to the manufacturer if the
freight rate is ` 40/1000 kg of dry paper.
Basis: 100 kg of 5% moist paper.
Dry paper 95 kg; moisture 5 kg
Cost of dry paper = 100
3
= ` 3.16
95
In the case of 5,000 kg paper with 7.86% moisture Weight of dry paper = 4,607 kg
and weight of moisture = 393 kg
(a) Cost of paper = 4,607 3.16 = ` 14,558.12
(b) Freight charge = 4,607
40
= ` 185
1000
Total cost including freight = ` 14,743.12
7.18 A mixture of 5% ethylene and 95% air is passed through a suitable catalyst in a reactor. Some of
the ethylene does not react, some form oxide, some turn to CO
2
and water. The entire gas mixture
enters an absorption tower where water is sprayed. The oxide is converted to glycol. The gas leaving
the absorber analyzes C
2
H
4
: 1.085%, CO
2
: 4.345%, O
2
: 13.055% and N
2
: 81.515% on dry basis.
The partial pressure (pp) of H
2
O in this gas is 15.4 mm Hg while total pressure is 745 mm Hg. If one
mole of water is sprayed per 100 mole of gas mixture, calculate the composition of ethylene glycol
water product formed.
5% C
2
H
4
Reactor
95% air Gases Ethylene, CO
2
, Absorber O
2
, N
2
pp.H
2
O 15.4 mm Hg
Ethylene glycolwater
Reactions:
1.
2C H + O
24 2 Ethylene
2C H O 24
Ethylene oxide
2. C
2
H
4
+ 3O
2
2CO
2
+ 2H
2
O
3. 24 2
C H O+HO (CHOH)
2 2 Ethylene glycol
Basis: 100 kmoles of feed gas.
C
2
H
4
: 5 kmoles; O
2
: (95 0.21) = 20 kmoles; N
2
: 75 kmoles
N
75
= 92 kmoles
2
balance: Moles leaving the absorber =
0.81515
C
2
H
4
: 92 0.01085 = 1 kmole
CO
2
: 92 0.04345 = 4 kmoles
O
2
: 92 0.13055 = 12 kmoles
H
2
O =
92 15.4
= 1.94 kmoles
74515.4
C
2
H
4
reacted : 5 1 = 4 kmoles
C
2
H
4
converted to CO
2
:
4
= 2 kmoles
2
C
2
H
4
converted to C
2
H
4
O : 4 2 = 2 kmoles
Water formed by reaction 2 = 4 mole CO
2
kmole [oxygen sent] [used up oxygen] = 20 [1 + 6] =
13 kmoles
Moles of gases entering absorber: C
2
H
4
: 1; CO
2
: 4; C
2
H
4
O : 2; H
2
O:4; O
2
: 12; N
2
:75
Total number of moles = 98.
Water sprayed at the top of absorber = 98
1
= 0.98
100
Total moles of water entering absorber = (4 + 0.98) = 4.98 kmoles Water in exit gas = 1.94 kmoles
Water reacted in absorption column = 2.00 kmoles
Ethylene glycol formed = 2 kmoles
Water leaving along with ethylene glycol = (4.98 2 1.94) = 1.04 kmoles
Composition of liquid stream:
Component moles Molecular weight Weight Weight % (CH
2
OH)
2
2.00 62 124.00 86.88
Ethylene glycol
(H
2
O) 1.04 18 18.72 13.12
Water
Total 3.04 142.72 100.00
7.19 The first step in the manufacture of H
2
SO
4
from pyrites consists of burning pyrites in air. The
reactions taking place are:
FeS
2
+ 2.5O
2
FeO + 2SO
2
(1) 2FeS
2
+ 5.5O
2
Fe
2
O
3
+ 4SO
2
(2)
The flue gas analysis shows SO
2
: 10.2%; O
2
: 7.8%; N
2
: 82% on dry basis at 600 C and 780 mm Hg.
(a) In what ratio does the two reactions take place?
(b) How much excess air was fed if the reaction (2) is desired?
Basis: 100 kmoles of flue gas
SO
2
: 10.2%; O
2
: 7.8%; N
2
: 82%
Let x kmole of FeS
2
by reaction (1) and
y kmole of FeS
2
by reaction (2) be reacted.
(a) O
21
= 21.8 kmoles (using nitrogen balance)
2
fed = 82
79
O
2
leaving = 7.8 kmoles; O
2
used = 14 kmoles
SO
2
balance = 2x + 2y = 10.2; \ x + y = 5.1 (a) O
2
used = 2.5x + 2.75y = 14.0 (b) Solving (a) and (b),
we get
x = 0.1 and y = 5; ratio of
x 0.1
= 0.02
y 5
(b) Total FeS
2
reacted = 5.1 moles
O
2
needed by Reaction (2) = 5.1
5.5
= 14.025 moles
2
Excess O
2
supplied = 21.8 14.025 = 7.775 moles
7.775
% excess air =

100 = 55.4%

7.20 A producer gas contains CO

2
: 9.2%, C
2
H
4
: 0.4%, CO : 20.9%, H
2
: 15.6%, CH
4
: 1.9% and N
2
:
52%, when it is burnt, the products of combustion are found to contain CO
2
: 10.8%, CO : 0.4, O
2
:
9.2%, N
2
: 79.6%. Calculate the following:
(a) m
3
of air used per m
3
of producer gas (b) % excess air
(c) % N
2
that has come from producer gas. Basis: 100 g mole of producer gas
Component Weight, g mole C atom
CO
2
9.2 9.2
C
2
H
4
0.4 0.8
CO 20.9 20.9
H
2
15.6 CH
4
1.9 1.9
N
2
52.0
Total 100.0 Reactions
C
2
H
4
+ 3O
2
2CO
2
+ 2H
2
O CO + 0.5O
2
CO
2
H
2
+ 0.5O
2
H
2
O
CH
4
+ 2O
2
CO
2
+ 2H
2
O
Carbon is the tie element
C entering = 32.8 g atoms 11.2% exit.
Oxygen needed for combustion

0.4 3 = 1.2
20.9 0.5 = 10.45 15.6 0.5 = 7.8 1.9 2 = 3.8
23.25
\ Total moles of exit gas =
32.8
= 293 g moles
0.112
N
2
from air: N
2
in exit = 293 0.796 = 233 g moles
N
2
in feed = 52 g moles
N
2
from air = 181 g moles
O
2
from air = 181

21
= 48; Total air = 229 g moles m
3
of air/m
3
79
feed = g mole of air/g mole of feed =
229
= 2.29
100
(b) O
2
supplied = 48 g moles
needed = 23.25 g moles
Excess O
2
supplied = (48 23.25) = 24.75 g moles
% excess air = 24.75
100
= 106.45%
23.25
(c) Total N
2
leaving = 233 g moles
% N
100
= 22.3%
2
from air =
233
7.21 Formaldehyde is manufactured by the catalytic oxidation of methanol using an excess of air. A
secondary reaction also takes place:
CH
3
OH + 0.5O
2
HCHO + H
2
O (1) HCHO + 0.5O
2
HCOOH (2)
The product gases have the following composition. CH
3
OH : 8.6%; HCHO : 3.1%; HCOOH : 0.6%;
H
2
O : 3.7%; O
2
: 16%; N
2
: 68%. Find the following:
(a) the percentage conversion of CH
3
OH to HCHO
(b) % methanol lost in second reaction and
(c) molar ratio of feed to air and the % excess air used. Basis: 100 g moles of product gases.
[From the product gas analysis, total quantity of HCHO formed is equivalent to the sum of free HCHO
available + HCOOH formed by the secondary reaction (2)]
HCHO formed = HCHO formed by reaction (1) + HCOOH formed from HCHO by reaction (2) = (3.1
+ 0.6) = 3.7 g moles CH
3
OH supplied = reacted by reaction (1) + unconverted at the end = (3.7 +
8.6) = 12.3 g moles
(a) % conversion of CH
3
OH to HCHO = 3.7
100
= 30%
12.3

(b) % lost in second reaction = 0.6
100
= 4.9%
12.3

(c) Air fed (using nitrogen balance) =
68
= 86 g moles; O
2
= 18 g moles
0.79

Moles of feed/moles of air =
12.3
= 0.143
86.0

O
2
needed for converting CH
3
OH to HCHO =
12.3
= 6.15
2
Excess O
2
supplied = (18 6.15) = 11.85 g
moles

100
= 192.7%% excess air = 11.85
6.15
7.22 A rich copper ore analysis gives the following constituent percent: CuS : 10%; FeS
2
: 30% and
inert : 60%. By crushing and floating, 2/3 inert is eliminated. The ore is roasted with carbon. Inert are
unchanged. In the reduction of the Cu
2
O to Cu, there is 5% loss. Find the weight of copper obtainable
from 1 tonne of ore.
2CuS + 2.5O
Cu O + 2SO

295 22 2 (1)
64
2FeS
2
+ 5.5O
2
Fe
2
O
3
+ 4SO
2
(2)
2
Cu O + C 2Cu + CO
(3)142 12 126 28
Basis: 1 tonne of ore = 1000 kg
Ore
Crushing and
P
1
Roaster
P
2 Cu, COFlotation
Inert (2/3) CuS : 100 : 16.67% FeS
2
: 300 : 50.00% Inert : 200 : 33.33%
600
Inert in ore = 600 kg. Removed = 600
2
= 400 kg
3
Inert remaining = 200 kg = 0.333 P
1
\ P
1
= 600 kg
CuS in P
1
= 600 0.166 = 100 kg; FeS
2
= 600 0.5 = 300 kg
(a) Cu
2
O got from CuS = 100
142
= 74.74 kg
190

(b) Cu
2
O reacted = 74.74 0.95 = 71.0 kg
(c) Cu got from Cu
126
= 63 kg
2
O = 71
142
7.23 Pyrites is roasted in producing SO
2
. The gases leaving the roaster have a temperature of 500 C
with composition SO
2
: 9%, O
2
: 8.6% and N
2
: 82.4%. Composition of pyrites by weight is Fe : 35%,
S : 40% and gangue 25%. Calculate for 100 kg of pyrites roasted.
(a) Excess air
(b) Volume of air supplied
(c) Volume of burner gas leaving.
Basis: 100 kg of pyrites
weight of FeS
2
= Total weight weight of inert = 100 25 = 75 kg
4FeS
+ 11O

2Fe O + 8SO
22 23 2
480 352 320 512
FeS
75
= 0.625 kmole
2
= 75 kg =
120

SO
2
produced = 0.625
8
= 1.25 kmoles
4
SO
2
= 1.25 kmoles 9% of exit gas.

1.25
= 13.89 kmoles\ Total exit gas in mole =
0.09
O
2
in exit gas = 13.89 0.086 = 1.19 kmoles N
2
in exit gas = 13.89 0.824 = 11.44 kmoles
O
11
= 1.72 kmoles
2
consumed = 0.625
4

(a) % excess air = 1.19
100
= 69.2%
1.72

(b) Air supplied =
1.19 1.72
= 13.86 kmoles
0.21

Volume of air supplied = 13.86 22.414 = 310.6 m
3
at NTP.

773
= 881.5 m
3
(c) Volume of exit gas = 13.89 22.414
273
7.24 A fuel oil with the following composition C : 84%, H
2
: 13%, O
2
: 1%, S : 1% and H
2
O : 1%; is
burnt and the flue gas obtained gives the following analysis: CO
2
: 9.9%, CO : 1.6%, H
2
O : 10.75%,
SO
2
: 0.05%, O
2
: 3.7% and N
2
: 74%. Calculate the % excess air used.
Basis: 100 g of oil
g g atoms O
2
needed Reaction
C 84 7.00 7.00 C + O
2
CO
2
H
2
13 6.50 3.25 H
2
+ O
2
H
2
O
S 1 0.03 0.03 S + O
2
SO
2
10.28
O
2
1 0.03 0.03
H
2
O 1 0.06
Net oxygen needed 10.25
Carbon in exit stream = (9.9 + 1.6) = 11.5%
7
= 60.87 g moles\ g moles of exit gas =
0.115
N
2
in exit = (60.87 0.74) = 45.04 g moles
45.04
Air supplied =

= 57.02 g moles

\ O
2
supplied = 11.98 g moles and
excess O
2
= 11.98 10.25 =1.73 g moles
Hence % excess air = 1.73
100
= 16.9%
10.25
7.25 Pure sulphur is burnt in air. Even when 20% excess dry air is passed only 30% of the S burns to
SO
3
and the remaining goes to SO
2
. S to SO
3
is the desired reaction
(a) What is the analysis of resulting gases?
(b) The gases from the burner are passed through a converter where
SO
2
is converted to SO
3
(without addition of any more air) if the gases leaving the converter has
4.3% SO
2
. Calculate the molar ratio of SO
3
to SO
2
in the exit gas.
Basis: 1 g atom of S = 32 g
S+O SO S + 1.5O

SO
22 23
32 32 64 32 48 80
O
2
needed = 1.5 g mole
O
2
supplied = 1.5 1.2 = 1.8 g moles
N
2
supplied = 1.8 79/21 = 6.8 g moles
O
2
reacted = 0.7 + (0.3 1.5) = 1.15 g moles
Exit gas stream:
Component SO
2
SO
3
O
2
N
2
Total Weight, g mole 0.7 0.3 (1.8 1.15) = 0.65 6.8 8.45
Mole % 8.28 3.55 7.70 80.47 100.0
Let x moles of SO
2
react to form SO
3
SO
2
+ 0.5 O
2
SO
3
Exit gas stream consists of the following:
SO
2
= 0.7 x
SO
3
= 0.3 + x
O
2
= 0.65 0.5x
N
2
= 6.8
Total = 8.45 0.5x
SO
0.7 x
0.043
2
=
8.45 0.5x
Solving, we get x = 0.34
SO 0.64

SO = 1.78
exit

7.26 500 kg/h of pure sulphur is burnt with 20% excess air (based on S to SO
2
) 5% S is oxidized to
SO
3
and rest to SO
2
. Find the exit gas analysis.
Basis: 500 kg sulphur =
500
= 15.625 katoms
32
S+O

SO
22
32 32 64
S+1.5O

SO 23 32 48 80
1 katom of sulphur requires 1 kmole of oxygen to form SO
2
Therefore oxygen supplied = 15.625 1.2
= 18.75 kmoles
N
79
= 70.54 kmoles
2
entering = 18.75
21
S to SO
2
= 15.625 0.95 = 14.845 kmoles
S to SO
3
= 15.625 0.05 = 0.780 kmole
Total O
2
consumed = [14.845 + (1.5 0.78)] = 16.015 kmoles O
2
remaining = (18.75 16.015) =
2.735 kmoles
Exit gas SO
2
SO
3
O
2
N
2
Total Weight, kmole 14.845 0.78 2.735 70.54 88.9 mole % 16.70 0.88 3.08
79.34 100.00
7.27 The composition of the gas entering a converter is SO
2
: 7.2%, O
2
: 13.2% and N
2
: 79.6% and
that of the gas leaving is SO
2
: 2.8%, O
2
: 11.7% and N
2
: 85.5%. Determine the % of SO
2
oxidized to
SO
3
Basis: 100 g moles entering
79.6
\ Total moles in exit =
0.855
= 93.1 g moles (making nitrogen balance) \ SO
2
in exit stream = 93.1 0.028 = 2.61 g moles
SO
2
converted to SO
3
= moles of SO
2
entering moles of SO
2
in exit stream = 7.2 2.61 = 4.59 g moles
% SO
100
= 63.75%
2
oxidized = 4.59
7.2
7.28 Limestone containing (on dry basis) 42.5% CO
2
is burnt with coal having an analysis of 81% C;
4.7% H
2
; 1.8% N
2
; 4.6% O
2
and 7.9% ash. The stack gas analyzes 24.4% CO
2,
4.1% O
2
and 71.5%
N
2
. Compute
(a) Ratio of lime produced to coal burnt
(b) Stack gas produced/tonne of lime produced.
Reactions:

CaCO +C +O

CaO +2CO 32 2
100 12 32 56 88
MgCO
+ C + O

MgO + 2CO 32 2 84.3 12 32 40.3 244
Stack gas
Limestone
z coal Burner
y Air CaO Lime
Basis: 100 kmoles of stack gas
Let z kg of coal and y kg of air enter the burner (air contains 23% O
2
; 77% N
2
by weight %)
C + O
2
CO
2
H
2
+ 0.5O
2
H
2
O
On weight basis,
N
2
balance gives, 0.018z + 0.77y = 71.5 28 = 2002 O
2
balance gives,
32
16
(0.046
z
+ 0.23
y
)
0.81
zz

= (4.1 32) = 131.2

Solving the above equations, we get

z = 187 kg
y = 2,595.6 kg
CO
2
balance gives: 24.4 kmoles CO
2
= 1,073.6 kg 12 kg C gives 44 kg CO
2
Carbon in coal = 187

0.81 kg C gives

44
187
0.81 12 = 555.4 kg of CO
2
\ CO
2
obtained from limestone = total CO
2
CO
2
from coal = (1,073.6 555.4) = 518.2 kg

518.2
= 1,219.3 kg\ Limestone needed =
0.425

Lime obtained from limestone = 518.2
56
= 659.5 kg
44

(a) Lime produced/coal burnt =
659.5
= 3.5
187

N
2
O
2
CO
2
(b) Weight of stack gas 2,002 + 131.2 + 1,073.6 = 3,206.8 kg \ 659.5 kg lime produces 3,206.8 kg
stack gas
Hence, for 1 tonne or 1000 kg lime, the stack gas produced is 4,862.5 kg
7.29 A gas containing 80% ethane and 20% oxygen is burnt with 200% excess air. 80% ethane goes
to CO
2
; 10% to CO; and 10% remains unburnt. Calculate the stack gas composition.
Basis: 100 g moles of gas
we have,
C
2
H
6
: 80 g moles
O
2
: 20 g moles
C
2
H
6
+ 3.5O
2
2CO
2
+ 3H
2
O
C
2
H
6
+ 2.5O
2
2CO + 3H
2
O
O
2
needed = 80 3.5 = 280 g moles
O
2
available in gas = 20 g moles
O
2
theoretically needed = 260 g moles
200% excess oxygen is supplied
\ O
2
supplied = (260 3) = 780 g moles
Total O
2
available = 20 + 780 = 800 g moles
N
2
entering = (780 79/21) = 2,934 g moles
CO
2
formed = 80 0.8 2 = 128 g moles
CO formed = 80 0.1 2 = 16 g moles
O
2
used = (80 0.8 3.5) + (80 0.1 2.5) = 244 g moles
O
2
remaining = Oxygen available oxygen used = (800 244) = 556 g moles
H
2
O formed = (80 0.8 3) + (80 0.1 3) = 216 g moles C
2
H
6
remaining = 80 0.1 = 8 g moles
Composition of stack gases:
Gases g moles mole %
CO
2
128 3.318
CO 16 0.415
O
2
556 14.412
N
2
2,934 76.050
H
2
O 216 5.598
C
2
H
6
8 0.207
Total 3,858 100.000
7.30 Pure CO
2
may be prepared by treating limestone with sulphuric acid. The limestone used in the
process contains CaCO
3
, MgCO
3
and inert compounds. The acid used contains 12% H
2
SO
4
by
weight. The residue from the process had the following composition: CaSO
4
: 8.56%, MgSO
4
:
5.23%, H
2
SO
4
: 1.05%, Inert : 0.53%, CO
2
: 0.12%, H
2
O : 84.51%. During the process, the mass
was warmed where CO
2
and H
2
O got removed. Calculate the following:
(a) The analysis of limestone
(b) The % excess acid used
(c) The weight and analysis of the material distilled from the reaction mass per 1000 kg of limestone
treated.
Basis: 100 kg of residue
Inert : 0.53 kg, CaSO
4
: 8.56 kg, MgSO
4
: 5.23 kg
CaCO
3
+ H
2
SO
4
CaSO
4
+ CO
2
+ H
2
O
100 98 136 44 18
MgCO
3
+ H
2
SO
4
MgSO
4
+ CO
2
+ H
2
O
84.3 98 120.3 44 18
8.56 kg of CaSO
4
obtained from 8.56
100
= 6.3 kg of CaCO
3

136
5.23 kg of MgSO
4
obtained from 5.23
84.3
= 3.67 kg of MgCO
3

120.3
(a) Limestone analysis CaCO
3
MgCO
3
Inert Total Weight, kg 6.3 3.67 0.53 10.50 Weight % 60
34.95 5.05 100.0
98
kg of H
2
SO
4
= 6.174 kg
3
requires

(b) 6.3 kg of CaCO

3.67 kg of MgCO
3
requires


98
kg of H
2
SO
4
= 4.27 kg
84.3
Total acid needed = 6.174 + 4.27 = 10.444 kg
Excess acid remaining = 1.05 kg
% Excess acid used =



100 = 10.05%

Total acid used = (10.444 + 1.05) = 11.494 kg

11.494
(i.e.) 12% acid supplied =

= 95.78 kg

44 44
= 4.689 kg
2
formed = 6.3

CO


H
2
O formed =
6.3
18


18 = 1.918 kg
84.3
H
2
O in acid = (95.78 11.494) = 84.286 kg
Total water = water from acid + water formed from reaction
= (84.286 + 1.918) = 86.204 kg
H
2
O in residue = 84.51 kg
CO
2
in residue = 0.12 kg
\ Amount of H
2
O vapours = (86.204 84.51) = 1.694 kg
and CO
2
in gas phase = (4.689 0.12) = 4.569 kg vapours: H
2
O 1.694 kg 27 % (weight %) 47.56
mole % CO
2
4.569 kg 73 % (weight %) 52.44 mole % Total 6.263 kg 100 100
Check Limestone + acid = (10.5 + 95.78) = 106.28 kg
Residue + vapours = (100 + 6.263) = 106.263 kg
For 10.5 kg limestone, vapours formed = 6.263 kg
(c) \ 1000 kg limestone, vapours formed = 6.263
100
= 596.5 kg
10.5
7.31 A coal containing 87% C
and 7% unoxidized hydrogen is burnt in air. If 40% excess air is used;
(a) Calculate kg of air per kg of coal burnt
(b) Assuming complete combustion calculate the composition of gases
by weight %
Basis: 1 kg of coal
Carbon = 0.87 kg = 0.0725 katom
H
2
= 0.07 kg = 0.035 kmole
32 16
= 2.88 kg [by stoichiometry]
2
needed = 0.87 (a) O


O
2
supplied = (2.88 1.4) = 4.032 kg
Air supplied =
4.032
= 17.38 kg
0.232
kg of air/kg of coal = 17.38
(b) Gases leaving are: CO
2
, H
2
O, O
2
and N
2
CO
44
= 3.19kg = 17.41 wt %
2
produced = 0.87
12

H
2
O produced = 0.07
18
= 0.63kg = 3.44 wt %
2
O
2
remaining = (4.032 2.88) = 1.152 kg = 6.29 wt % N
2
leaving = (17.38 4.032) = 13.348 kg =
72.86 wt % Total 18.32 kg 100.00 7.32 A furnace using hydrocarbon fuel oil has a dry stack gas
analysis as follows:
CO
2
: 10.2%, O
2
: 8.3%, N
2
: 81.5%; Find the following: (a) % excess air used
(b) the composition of fuel oil in weight %
(c) m
3
of air supplied/kg of fuel.
Basis: 100 kmoles dry stock gas
N
2
in stack gas = 81.5 kmoles
Air supplied =
81.5
= 103.16 kmoles
0.79
O
2
entering = 81.5
21
= 21.66 kmoles
79
O
2
leaving = 8.3 kmoles
O
2
consumed = (21.66 8.3) = 13.36 kmoles
8.3
(a) % excess air =

100 = 62.13%

(b) Let the fuel be C

x
H
y
C
x
H
y
+ (x + y/4)O
2
xCO
2
+ y/2H
2
O x = 10.2 kmoles (CO
2
);
x + y/4 = 13.36 kmoles (O
2
reacted)
\ y = 12.64 katoms
and x = 10.2 katoms
Composition of fuel:
Element katom Weight, kg Weight %
C 10.20 122.40 90.64 H 12.64 12.64 9.36 Total 135.04 100.00
(c) Air supplied = 103.16 kmoles
m
3
of air/kg of fuel =
22.414
= 17.12 at NTP

7.33 The waste acid from a nitrating process contains 23% HNO
3
; 57% H
2
SO
4
; 20% water. This
acid is to be concentrated to 27% HNO
3
, 60% H
2
SO
4
by addition of 93% H
2
SO
4
and 90% HNO
3
.
Calculate the weight of acids needed to obtain 1000 kg of desired acid. Basis: 1000 kg of desired
acid
Let x kg be the weight of waste acid;
y kg be the weight of H
2
SO
4
and
z kg be the weight of HNO
3
Overall balance: x + y + z = 1000
Balance for H
2
SO
4
gives, 0.57x + 0.93y = 1000 0.60 = 600 Balance for HNO
3
gives, 0.23x + 0.9z =
1000 0.27 = 270 Solving, x = waste acid = 418 kg
y = con. H
2
SO
4
= 390 kg
z = con. HNO
3
= 192 kg
Total = 1,000 kg
Check (using water balance):
(0.2 418) + (0.07 390) + (0.1 192) = (1000 0.13) = 130
7.34 In order to obtain barium in a form that may be put into solution, the natural sulphate (barites)
containing only pure barium sulphate and infusible matter is fused with an excess of pure anhydrous
soda ash. Upon analysis of the fusion mass it is found to contain 11.3% barium sulphate, 27.7%
sodium sulphate and 20.35% sodium carbonate. The remainder is barium carbonate and infusible
matter. Calculate the following:
(a) % conversion of barium sulphate to the carbonate.
(b) composition of the original barites
(c) % excess of the sodium carbonate used in excess of the theoretically needed amount for all the
barium sulphate. Basis: 100 kg of fusion mass.
Fused
BaSO
4
+ IM + Na
2
CO
3
BaCO
3
+ Na
2
SO
4
+ IM (IM = infusible matter)
Analysis of product: 11.3% BaSO
4
; 27.7% Na
2
SO
4
; 20.35% Na
2
CO
3
Therefore, (BaCO
3
+ IM) =
100 (11.3 + 27.7 + 20.35) = 40.65%
BaSO
+ Na CO

BaCO + Na SO

423 3 24
233 106 197 142

Na
2
SO
4
= 27.7 kg
Weight of
BaSO
4
reacted = 27.7
233
= 45.45 kg
142

Na
2
CO
3
reacted = 27.7
106
= 20.68 kg
142

BaCO
197
= 38.43 kg
3
formed = 27.7
142
BaSO
4
initially present = (45.45 + 11.3) = 56.75 kg
Na
2
CO
3
supplied = (20.68 + 20.35) = 41.03 kg
45.45
(a) % conversion of BaSO
4
to BaCO
3
=

100 = 80%

(b) Composition of original barites

BaSO
4
= 56.75, IM = (40.65 38.43) = 2.22 kg
Also, total mass of products = total mass of reactants = 100 kg Therefore, IM = 100 [56.75 + 41.03]
= 2.22 kg
Therefore original barites = 56.75 + 2.22 = 58.97 kg
2.22
Hence %IM =

100 = 3.76%

56.75
%BaSO
4
=

100 = 96.24%

(c) Excess Na
2
CO
3
:
Na
2
CO
3
needed for all BaSO
4
= 56.75
106
= 25.82 kg
233
Excess Na
2
CO
3
= (41.03 25.82) = 15.21
15.21
% excess =

100 = 58.9%

7.35 A fuel oil containing 88.2% C and 11.8% H

2
is burnt with 20% excess air. 95% of carbon is
burnt to CO
2
and the rest to CO. All the Hydrogen is converted to water. Determine the orsat analysis
of the flue gas (dry flue gas).
Basis: 100 kg of fuel oil
Component Weight, kg kmole or katom C 88.2 7.35 katoms H
2
11.8 5.90 kmoles Total 100.0
C + O
2
CO
2
C + 0.5O
2
CO
H
2
+ 0.5O
2
H
2
O
95% C is converted to CO
2
= 7.35 0.95 = 6.9825 katoms Oxygen used for this reaction = 6.9825
kmole
5% C is converted to CO = (7.35 6.9825) = 0.3675 katoms
Oxygen used for this reaction is =
0.3675
= 0.18375 kmoles
2
Conversion of H
2
to H
2
O = 5.9 kmoles
Oxygen used for this reaction is =
5.9
= 2.95
2
O
2
needed (theoretically) = (7.35 + 2.95) = 10.3 kmoles O
2
supplied = 10.3 1.2 = 12.36 kmoles
O
2
remaining = [12.36 (6.9825 + 0.18375 + 2.95)] = 2.24375 kmoles
N
79
= 46.5 kmoles
2
entering = 12.36
21
Component CO
2
CO O
2
N
2
Total mole 6.9825 0.3675 2.24375 46.50 56.0937
mole % 12.45 0.6600 4.00000 82.89 100.0000
7.36 A furnace uses a natural gas which consists entirely of hydrocarbons. The flue gas analysis is:
CO
2
: 9.5%, O
2
: 1.4%, CO : 1.9% and rest is N
2
. Calculate the following:
(a) the atomic ratio of hydrogen to carbon in the fuel
(b) % excess air
(c) the composition of the fuel gas in the form C
x
H
y
Basis: 100 mole of the flue gas
Let us assume the hydrocarbon (HC) to be C
x
H
y
Let a g mole of HC get oxidized to CO
2
and b g mole of HC get oxidized to CO
The reactions to take place are
a (C
x
H
y
) + a(x + y/4)O
2
axCO
2
+ ay/2H
2
O
b(C
x
H
y
) + b(x/2 + y/4)O
2
bxCO + by/2H
2
O
The composition in percentage of the gases are:
CO
2
: 9.5%, O
2
: 1.4%, CO : 1.9%, N
2
: 87.2%, Total = 100.0%
Carbon balance = a + b = (9.5 + 1.9) = 11.4; ax = 9.5; bx = 1.9
ax 9.5
= 5bx 1.9
a = 5b
By nitrogen balances oxygen supplied =
87.2
0.21 = 23.18 kmoles
0.79
Oxygen left = 1.40 kmoles Oxygen reacted = 21.78 kmoles
Oxygen reacted = ax +
aybx by

= 21.78
424
Oxygen reacted, 9.5 +
ayby

= 21.78
y
(i.e.)

(a + b) = 11.33

\ y(11.4) = 45.32; \ y = 3.975

a + b = 11.4 = 6b; \ b = 1.9; a = 9.5
since ax = 9.5; x = 1
(a) Atomic ratio of
H 3.975
= 3.975
C1
(b) For % of excess air, let us consider the following:
(c) CO + 0.5O
2
CO
2
One kmole of CO requires 0.5 kmole of oxygen
Therefore, 0.95 mole of O
2
will be used for converting CO to CO
2
Excess O
2
remaining = 1.4 0.95
= 0.45 kmole
Theoretical O
2
required = 11.4 (from CO and CO
2
values) + 11.33 (for H
2
O formation) = 22.78
kmoles
0.45
\
Excess air =

100 = 1.98%

Hence, Hydrocarbon = C
1
H
3.975
= CH
4
(methane)
7.37 The analysis of gas entering the converter in a contact H
2
SO
4
plant is SO
2
: 4%, O
2
: 13% and N
2
:
83%. The gas leaving the converter contains 0.45% SO
2
on SO
3
free basis. Calculate the % of SO
2
entering the converter getting converted to SO
3
.
Basis: 100 g mole of gas entering the converter
Let x g mole SO
2
get converted to SO
3
SO
2
: 4 SO
2
: 0.45% O
2
: 13 Converter O
2N2 : 83 N2

SO
+ 0.5O

SO 22 3
xx/2 x
gases leaving SO
2
(4 x) (SO
3
free basis) O
2
(13 x/2) N
2
83
Total (100 1.5x)
% SO
2
in exit =
40.45


of exit gas.
1001.5x
Solving the above equations, we get x = 3.57
% SO
100
= 89.25%
2
converted to SO
3
= 3.57
4
7.38 A producer gas made from coke has the composition CO : 28%, CO
2
: 3.5%, O
2
: 0.5% and N
2
:
68%. This gas is burnt with 20% excess of the net O
2
needed for combustion. If the combustion is
98% complete, find the weight and volumetric composition of gases produced per 100 kg of gas
burnt.
Basis: 100 kmoles of fuel gas
Component mole Molecular weight Weight, kg CO 28.0 28 28 28 = 784
CO
2
3.5 44 3.5 44 = 154
O
2
0.5 32 0.5 32 = 16
N
2
68.0 28 68 28 = 1,904
Total 100.0 2,858
we have CO + 0.5O
2
CO
2
Oxygen balance
O
2
needed = 28 0.5 = 14 kmoles
O
2
available in feed = 0.5 kmoles
Net O
2
needed = 13.5 kmoles
O
2
supplied = 13.5 1.2 = 16.2 kmoles
O
2
consumed = 14 0.98 = 13.7 kmoles
O
2
remaining = (16.2 + 0.5 13.7) = 3 kmoles
Carbon balance
CO
2
formed = (28 0.98) = 27.44 kmoles CO
2
total = (27.44 + 3.5) = 30.94 kmoles CO unreacted =
(28 0.02) = 0.56 kmole Nitrogen balance
N
2
from air = 16.2
79
= 60.9 kmoles
21
N
2
in exit = (68 + 60.9) = 128.9 kmoles
Exit gas kmole Molecular mole % = Weight, Weight % weight volume % kg
CO
2
30.94 44 18.93 1,359.0 26.60
CO 0.56 28 0.34 15.7 0.31
O
2
3.00 32 1.84 96.0 1.88
N
2
128.90 28 78.89 3,637.0 71.21
Total 163.40 100.00 5,107.7 100.00 100 kmoles of fuel gas = 2,858 kg
\ Weight of product/100 kg of feed = 5,107.7
100
= 178.7 kg
2,858
7.39 In the manufacture of soda ash by Le Blanc process, sodium sulphate is heated with charcoal and
calcium carbonate. The resulting black ash has the following composition: Na
2
CO
3
: 42%; other water
soluble material : 6% and insoluble 52%. The black ash is treated with water to extract the sodium
carbonate. The solid residue left behind has the composition Na
2
CO
3
: 4%; other water soluble
material : 0.5%; insoluble : 85% and moisture : 10.5%
(a) Calculate the weight of residue remaining from the treatment of
1 tonne black ash.
(b) Calculate the weight of Na
2
CO
3
extracted per tonne of black ash.
Black
Water
ash Residue x
Feed I Unit II Unit Na
2
CO
3
: 4% Water solubles: 0.5% Insoluble: 85%
Na2CO3
Moisture: 10.5% Solution y
Basis: 1 tonne (1000 kg) of black ash
Let x be the weight of residue and y be the weight of solution. Insoluble: (0.52 1000) = 0.85x \ x =
612 kg
Na
2
CO
3
extracted = (0.42 1000) (612 0.04) = 395.5 kg
7.40 A laundry can purchase soap containing 30% water at the rate of ` 7 per 100 kg f.o.b. the factory.
The same manufacturer offers another soap having 5% water. If the freight rate is ` 0.6 per 100 kg of
soap what is the maximum price that the laundry should pay the manufacturer for the soap with 5%
water? (f.o.b.: freight on board) Basis: 100 kg of dry soap
Case I: (30% water) water present = 100
30
= 42.85 43 kg
70
Total weight = (100 + 43) = 143 kg
Cost of 100 kg dry soap including freight at laundry = 143
7.6
100 = ` 10.88
Case II: (5% water) water present = 100
5
= 5.25 kg
95
Total weight = 105.25 kg
Freight charge alone = 105.25
0.6
= ` 0.63
100
Cost of 100 kg dry soap = (10.88 0.63) = ` 10.25 = cost of 105.25 kg of wet soap
\ Cost of 100 kg wet soap = 10.25
100
= ` 9.72
105.25
7.41 Phosphorus is prepared by heating in an electric furnace a thoroughly mixed mass of calcium
phosphate, sand and charcoal. It may be assumed that in a charge the following conditions exist. The
amount of silica used is 10% in excess. Charcoal is 40% in excess of that required to combine with
P
2
O
5
liberated, to form CO.
(a) Calculate the weight % of feed
(b) Calculate the weight of phosphorus obtained per 100 kg of charge when the reaction I is 90%
complete and reaction II is 70% complete. I
Ca (PO ) + 3SiO

3CaSiO + P O 342 2 3 25 310 (3 60) (3 116) 142

II 5C + P O
25
2P + 5CO
(5 12)
142
(2 31) (5 28)
(a) Basis: 1 kmole of calcium phosphate = 310 kg Silica charged = 3 1.1 = 3.3 kmoles Carbon
charged = 5 1.4 = 7.0 kmoles
Feed Weight, Mol.wt Weight, kmole or katom or At.wt kg
Ca
3
(PO
4
)
2
1.0 310 310
SiO
2
3.3 60 198
C 7.0 12 84
Total 11.3 592
Composition in weight %
52.3
33.5
14.2
100.0
(b) Basis: 100 kg of charge: calcium phosphate present = 52.3 kg Calcium phosphate consumed =
(52.3 0.9) = 47.07 kg
P
142
= 21.6 kg
2
O
5
formed = 47.07
310

Phosphorus produced = (21.6 0.7)
62
= 6.6 kg
142
7.42 In the Deacon process for the manufacture of chlorine, a dry mixture of HCl gas and air is passed
over a hot catalyst, which promotes oxidation of the acid. 30% excess air is used. Calculate the
following.
(a) The weight of air supplied per kg of acid.
(b) The composition (weight %) of gases entering
(c) The composition (weight %) of gases leaving, assuming that 60%
of the acid is oxidized in the process

4HCl
+
O

2Cl + 2H O

22 2
(4 36.5)=146 (2 16)=32 (2
71)=142
(2 18)=36
Basis: 4 kmoles of HCl 146 kg
HCl
Cl
2
HCl
O
2
Converter O
2
N2N2
H
2
O
(a) Oxygen supplied = 1 1.3 = 1.3 kmoles

100
Weight of air supplied = 1.3

28.84 = 178.5 kg

Weight of air/weight of acid =
178.5
= 1.22 kg of air
146
(b) O
2
entering = 1.22 0.23 = 0.281 kg
N
2
entering = (1.22 0.281) = 0.939 kg
Gases Weight, kg Weight %
HCl 1.000 45.0
O
2
0.281 12.7
N
2
0.939 42.3
2.220 100.0
(c) HCl consumed = 0.6 kg HCl remaining = 0.4 kg

32
= 0.1495 kg
2
remaining =

Cl
2
formed = 0.6
142
= 0.585 kg
146

H
36
= 0.148 kg
2
O formed = 0.6
146
Gases Weight, kg Weight %
HCl 0.4000 18.0 Cl
2
0.5850 26.33 O
2
0.1495 6.73 N
2
0.939 42.27 H
2
O 0.1480 6.66
2.2215 100.00
7.43 In the manufacture of H
2
SO
4
by contact process, iron pyrites are burnt in dry air. Iron is oxidized
to Fe
2
O
3
. SO
2
formed is further oxidized to SO
3
by passing the gases mixed with air over hot catalyst.
Air supplied is 40% in excess of the sulphur actually burnt to SO
3
. Of the pyrites charged 15% is lost
in grate and not burnt. Calculate the following:
(a) Weight of air to be used/100 kg of pyrite charged
(b) In the burner 40% of S burnt is converted to SO
3
. Calculate the composition (by weight %) of
gases leaving I unit. (c) The catalyst converts 96% of SO
2
to SO
3
. Calculate the weight of
SO
3
formed.
(d) Calculate the composition (by weight %) of gases leaving the II
unit.
(e) Calculate the overall degree of completion of sulphur to SO
3
FeS2 Unit I SO3,SO2 Unit II Gases
Air
(Burner)
O2,N2
(Converter)
FeS
2
Fe
2
O
3
Basis: 100 kg of iron pyrites
Pyrites burnt = 85 kg
lost = 15 kg
(1)
2FeS + 5.5 O

Fe O + 4SO 22 23 2
(2 120) (5.5 32)
160
(4 64)
(2)
4SO + 2O

4SO
22 3
(4 64)(2 32) (480)
(3)
2FeS + 7.5O Fe O
4SO [Reaction (1) + Reaction (2)]
22 23 3+

(2 120)(7.5 32) 160 (480)
In Reaction (3) equal weight of oxygen is needed for FeS
2
.
(a) Air supplied =
85 1.4
= 517.4 kg; (40% excess oxygen)
0.23
O
2
= 119 kg; N
2
= 398.4 kg
(b) SO
3
produced (Unit I) = (85 0.4)
320
= 45.3 kg
240

SO
256
= 54.4 kg
2
produced (Unit I) = (85 0.6)
240
O
2
used for forming SO
3
=

32
= 34.0 kg

O
2
used for forming SO
2
=

32
= 37.4 kg

Total oxygen used = 71.4 kg

O
2
remaining (entering Unit II) = (119 71.4) = 47.6 kg
Gases Weight, kg Weight % SO
2
54.4 9.97
SO
3
45.3 8.30
O
2
47.6 8.72
N
2
398.4 73.01
Total 545.7 100.00
(c) SO
3
produced (II Unit) =

320
= 65.28 kg
256
\ Total SO
3
produced = (45.3 + 65.28) = 110.58 kg
232
(d) O
2
consumed =

= 13.05 kg

O
2
remaining = (47.6 13.05) = 34.55 kg
SO
2
remaining = (54.4 0.04) = 2.176 kg
Gases Weight, kg Weight % SO
2
2.176 0.400
SO
3
110.580 20.264
O
2
34.550 6.332
N
2
398.400 73.004
Total 545.706 100.000
(e) Sulphur in FeS
2
= 100
64
= 53.3 kg
120

Sulphur in SO
32
= 44.32 kg
3
= 110.58
80

% conversion of S to SO
3
= 44.32
100
= 83.4%
53.3
7.44 In the common process for the production of nitric acid sodium nitrate is treated with 95%
H
2
SO
4
. In order that the resulting niter cake may be fluid, it is desirable to use excess acid, so that
final cake contains 34% sulphuric acid. It may be assumed that the cake will contain 1.5% water and
that the reaction will go to completion. 2% of HNO
3
formed will remain in the cake.
(a) Calculate the composition of niter cake by weight %, formed per 100 kg of sodium nitrate
charged.
(b) Calculate the weight of sulphuric acid to be used.
(c) Calculate the weight of HNO
3
and water vapour distilled from the niter cake.

2NaNO
+ H SO
Na SO
+ 2HNO

324 24 3
(2 85) (98)
(142)
(2 63)
Basis: 100 kg of NaNO
3
charged.
Na
142
= 83.5 kg
2
SO
4
formed = 100
170

HNO
126
= 74.0 kg
3
formed = 100
170

H
2
SO
4
required = 100
98
= 57.65 kg
170
HNO
3
remaining in cake = 74 0.02 = 1.48 kg
(H
2
SO
4
+ H
2
O)% in cake = (34 + 1.5) = 35.5%
Niter cake has Na
2
SO
4
, H
2
SO
4
, HNO
3
and H
2
O \ (Na
2
SO
4
+ HNO
3
) % cake = 100 35.5 = 64.5%
(83.5 + 1.48) = 84.98 kg 64.5% cake. \ Weight of niter cake = 84.98/0.645 = 131.75 kg (a)
Composition of niter cake:
Components Weight, kg Weight %
HNO
3
1.48 1.12
Na
2
SO
4
83.50 63.38
H
2
SO
4
44.80 34.00
H
2
O 1.97 1.50
Total 131.75 100.00
(b) H
2
SO
4
in the cake = 131.75 0.34 = 44.8 kg H
2
SO
4
for the reaction = 57.65 kg
Total acid to be supplied = 102.45 kg
95% acid needed =
102.45
= 107.84 kg
0.95
(c) Water in the acid = (107.84 102.45) = 5.39 kg Water remaining in cake = 1.97 kg
Water distilled off = (5.39 1.97) = 3.42 kg
HNO
57.65
= 74.12 kg
3
formed = 126
98
HNO
3
in cake = 1.48 kg
HNO
3
distilled off = 72.64 kg
Composition of vapours removed:
Components Weight, kg Weight %
HNO
3
72.64 95.50 H
2
O 3.42 4.50 Total 76.06 100.00
7.45 Barium carbonate is a commercially important chemical. In its manufacture, BaS is first
prepared by heating the barites the natural sulphate with carbon. The BaS is extracted from this mass
with water and the solution treated with Na
2
CO
3
to precipitate BaCO
3
.
In such a process, it is found that the solution of BaS formed also contains some CaS originating from
impurities in barites. The solution is treated with Na
2
CO
3
and the precipitated mass of CaCO
3
,
BaCO
3
is filtered off. It is found that 16.45 kg of dry precipitate is removed from each 100 kg of
filtrate collected. The analysis of the precipitate is BaCO
3
90.1% and CaCO
3
9.9%. The analysis of
filtrate is reported to be Na
2
S : 6.85%, Na
2
CO
3
: 2.25% and H
2
O : 90.9%. The Na
2
CO
3
for the
precipitation used contained CaCO
3
as impurity.
(a) Determine the percentage excess Na
2
CO
3
used above than that required for BaS and CaS.
(b) Calculate the composition of the original solution of BaS and CaS (c) Calculate the composition
of dry soda ash used.
Barites
H
2
O Na2CO3
(X)
Carbon
(CaS
impurity)
Cake Filter
Filtrate
Reactions in (X): BaS + Na
2
CO
3
BaCO
3
+ Na
2
S CaS + Na
2
CO
3
CaCO
3
+ Na
2
S
Molecular weights Na
2
CO
3
: 106, BaCO
3
: 197.4, BaS : 169.4, CaCO
3
: 100, CaS : 72, Na
2
S : 78.
Basis: 100 kg of filtrate
Precipitate 16.45 kg
Amount of BaCO
3
in precipitate = 16.45 0.901 = 14.82 kg Amount of CaCO
3
in precipitate = (16.45
14.82) = 1.63 kg (a) Na
2
CO
3
required for forming 14.82 kg BaCO
3
= 14.82
106
= 7.96 kg
197.4

Na
2
S formed along with BaCO
3
= 14.82
78
= 5.85 kg
197.4
\ Na
2
S formed along with CaCO
3
= (6.85 5.85) = 1.00 kg
CaCO
100
= 1.28 kg
3
formed along with Na
2
S = 1
78
CaCO
3
impurity in soda ash = (1.63 1.28) = 0.35 kg
Na
2
CO
3
required for 1.28 kg CaCO
3
= 1.28
106
= 1.357 kg
100
Na
2
CO
3
present in filtrate = 2.25 kg (2.25% in filtrate) Total Na
2
CO
3
needed = (7.96 + 1.357) =
9.317 kg

100
= 24.1%\ Excess Na
2
CO
3
= 2.25
9.317

(b) BaS formed = 14.82
169.4
= 12.72 kg
197.4

CaS formed = 1.28
72
= 0.9216 kg
100
Components of original solution
Components Weight, kg Weight %
BaS 12.7200 12.17
CaS 0.9216 0.82
Water 90.9000 87.01
Total 104.5416 100.00
Total Na
2
CO
3
= Na
2
CO
3
used in reaction + Na
2
CO
3
in filtrate = 9.317 + 2.25 = 11.567 kg
We have CaCO
3
as impurity in Na
2
CO
3
= 0.35 kg
Composition of dry Na
2
CO
3
is shown as follows:
Components Weight, kg Weight % Na
2
CO
3
11.567 97.06 CaCO
3
0.350 2.94 Total 11.917 100.00
7.46 In the manufacture of straw pulp for the production of cheap straw board paper, a certain amount
of lime is carried into the beater. It is proposed to neutralize this lime with acid of 67% H
2
SO
4
. In a
beater containing 5000 gallons of pulp it is found that there is lime equivalent to 0.5 g of CaO per
litre.
(a) Calculate the kmole of lime in the beater.
(b) Calculate kmole and kg of H
2
SO
4
that must be added to beater in order to provide an excess of
1% above needed to neutralize the lime.
(c) Find the weight of acid.
(d) Find CaSO
4
formed in kg (1 gallon = 4.4 litres).
Basis: 5000 gallons = (5000 4.4) = 22,000 litres
CaO + H SO
CaSO

24
+
4 2
H O

56 98 136 18
(a) Lime in this solution = 22,000 0.5 = 11,000 g 11,000 g = 196.43 g moles
(b) Acid needed to neutralize = 196.43 g moles
Acid used is, 1% excess = (196.43 1.01) = 198.4 g moles = 198.4 98 = 19.4432 kg
(c) 67% acid needed =
19.4432
= 29.02 kg
0.67

(d) CaSO
4
formed = 11,000
136
= 26,714 g = 26.714 kg
56
7.47 The available nitrogen content in a urea sample is 45%. Find the actual urea content in the
sample.
CO(NH
2
)
2
= Molecular weight 60
Therefore, N
28
= 0.4666
2
in urea is =
60

Purity of sample = 0.45
100
= 96.43%
0.4666
7.48 Carbon tetrachloride is made as follows:
CS
+ 3Cl

CCl + S Cl

22 422
212.76 153.84
The product gases are found to contain CCl
4
33.3%; S
2
Cl
2
33.3%; CS
2
1.4% and Cl
2
32%. Calculate
the following:
(a) the percentage of the excess reactants used.
(b) the percentage conversion.
(c) kg of CCl
4
produced per 100 kg Cl
2
converted.
Basis: 100 kmoles of product gas
(a) CS
2
reacted = 33.3 kmoles
CS
2
remaining = 1.4 kmoles
CS
2
taken = 34.7 kmoles
% excess reactant, CS
2
= 1.4
100
= 4.2%
33.3
CS
2
is the limiting reactant and Cl
2
is the excess reactant. (based on the kmole left in the product)
Cl
2
required (theoretical) = 34.7 3 = 104.1 kmoles (100% conversion) Cl
2
reacted = 99.9 kmoles
But Cl
2
unreacted = 32.0 kmoles
\ Cl
2
taken = 99.9 + 32.0 =131.9 kmoles
% excess reactant = 32.0
100
= 30.73%
104.1
(b) % Conversion:
CS
2
= 33.3
100
= 95.97%
34.7

100
= 75.74%\ Cl
2
= 99.9
131.9
(c) Cl
2
reacted = 99.9 kmoles = 7084.91 kg
212.76 kg Cl
2
gives 153.84 kg CCl
4

7087.91
= 5122.87 kg CCl
4
\7084.91 kg Cl
2
gives 153.84
212.76

CCl
4
produced/100 kg Cl
2
reacted = 5122.87
100
= 72.31 kg
7084.91
7.49 Limestone is a mixture of calcium and magnesium carbonates and inert. Lime made by calcining
the limestone by heating until the CO
2
is driven off. When 100 kg of limestone is calcined 44 kg of
CO
2
is obtained. If the limestone contains 10% inert, calculate the following:
(a) Compute the analysis of limestone. 10 kg of above limestone is mixed with 2 kg of coke and is
burnt with 100% excess air. The calcination is complete.
(b) Calculate the composition of gases leaving the kiln. Analysis of coke C : 76%, ash : 21% and
moisture : 3%
Basis: 100 kg of limestone containing 10 kg inert.
(a) Let the limestone contain x kg of CaCO
3
and y kg of MgCO
3
\ x + y = 90 (1)
CaCO

CaO + CO
32
100 56 44
MgCO

MgO + CO
32
84.3 40.3 44
CO
2
balance gives, 0.44x + 0.52y = 44.0 (2) Eq. (1) 0.44 gives, 0.44x + 0.44y = 39.6 (3) Eq. (2)
Eq. (3) 0.08y = 4.4
\ y = 55 kg MgCO
3
; x = 35 kg CaCO
3
(b)
CaCO + C + O

CaO + 2CO 32 2
100 12 32 56 88
MgCO
+ C + O

MgO + 2CO 32 2 84.3 12 32 40.3 88
10 kg of limestone = 5.5 kg MgCO
3
; 3.5 kg CaCO
3
; and 1 kg inert
2 kg Coke = 1.52 kg Carbon; 0.06 kg moisture.
Gases leaving kiln CO
2
, O
2
, N
2
and H
2
O
CO
2
From CaCO
3
= 3.5
88
= 3.08 kg
100

From MgCO
88
= 5.74 kg
3
= 5.5
84.3

Total CO
2
= 8.82 kg =
8.82
= 0.2 kmole
44
O
2
Carbon present = 1.52 kg = 0.1266 k atom
O
2
supplied (100% excess) = (0.1266 2) = 0.2532 kmole
N
79
= 0.9525 kmole
2
entering = 0.2532
21

H
2
O (3%) = 0.06 kg =
0.06
= 0.00333 kmole
18
Total CO
2
in gases leaving
= CO
2
from limestone + CO
2
from Carbon (Coke) = 0.2 kmole + 0.1266 kmole
= 0.3266 kmole
Composition of gases leaving:
Gas kmole mole %
CO
2
0.3266 23.18
O
2
(Excess) 0.1266 8.99
N
2
0.9525 67.60
H
2
O 0.0033 0.23
Total 1.4090 100.00
7.50 A chemical manufacturer produces ethylene oxide (EO) by burning ethylene gas with air in the
presence of catalyst. If the conditions are carefully controlled, a substantial fraction of the ethylene
converted to ethylene oxide, some unconverted, some completely oxidized to form CO
2
and H
2
O.
Formation of CO
2
is negligible. After the gases leave, they are passed through an absorber in which
the ethylene oxide is removed. A typical orsat analysis of the gases leaving the absorber is CO
2
:
9.6%, O
2
: 3%, C
2
H
4
: 6.4% and N
2
: 81%. Of the ethylene entering the reactor, what percent is
converted to oxide?
CO
2
,O
2
,
C
2
H
4
Reactor
N
2
Exit Gases
ReactorAir EO,
CO
2
,O
2
, C
2
H
4
,N
2H2O
Reaction (1): 2C
2
H
4
+ O
2
2C
2
H
4
O
Reaction (2): C
2
H
4
+ 3O
2
2CO
2
+ 2H
2
O
Basis: 100 g moles of exit gas
6.4 g moles of C
2
H
4
unreacted.
9.6 g moles of CO
2
4.8 mole of C
2
H
4
converted to CO
2
81 g moles of N
2
(81 21/79) = 21.53 g
moles of O
2
supplied. O
2
consumed = oxygen supplied oxygen remaining
= (21.53 3) = 18.53 g moles
O
2
consumed by Reaction (2) = (4.8 3) = 14.4 g moles Therefore, O
2
consumed by Reaction (1) =
18.53 14.4 = 4.13 g moles \ C
2
H
4
converted to C
2
H
4
O = 8.26 g moles
C
2
H
4
supplied = C
2
H
4
remaining + C
2
H
4
consumed by Reaction (1)
+ C
2
H
4
consumed by Reaction (2) = 6.4 + 8.26 + 4.8 = 19.46 g moles
C
2
H
4
converted to C
2
H
4
O = 8.26
100
= 42.4%
19.46
7.51 A spent dye sample obtained from a soap-making unit contains 9.6% glycerol and 10.3% salt. It
is concentrated at a rate of 5,000 kg/h in a double effect evaporator until the solution contains 80%
glycerol and 6% salt. Assume that 4.5% glycerol is lost by entrainment. Find:
(a) the amount of salt crystallized out in the salt box of the evaporator and
(b) the evaporation taken place in the system.
Basis: One hour
Glycerol = 5,000
9.6
= 480 kg
100
Salt = 5,000 0.103 = 515 kg Water = 4,005 kg
Entrained Vapour
5,000 kg/hr Evaporator Solution
Salt
Final solution: Loss of glycerol = 480 0.045 = 21.6 kg Glycerol remaining = (480 21.6) = 458.4
kg

458.4
= 573 kg\ Solution leaving =
0.8
Salt in it = 573 0.06 = 34.38 kg
Water in this leaving solution = (573 458.4 34.38) = 80.22 kg Salt crystallized = (515 34.38) =
480.62 kg
Vapours leaving = Water in vapour + Glycerol in vapour
= (4,005 80.22) + 21.6 = 3,946.38 kg Check: Vapour + solution + salt = (3,946.38 + 573 + 480.62)
= 5,000 kg = Feed
7.52 Coal with 90% purity and rest ash is burnt with 25% excess air. Find the analysis of the flue
gases.
Basis: 100 g of coal:
carbon present is 90 g = 7.5 g atoms
C + O
2
CO
2
O
2
needed for the above reaction is 7.5 g moles
O
2
supplied: 7.5 1.25 = 9.375 g moles (25% excess)
N
2
from air:
9.375 79
= 35.27 g moles
21
O
2
remaining 9.375 7.5 = 1.875 g moles
Exit gases CO
2
O
2
N
2
Total g mole 7.5 1.875 35.27 44.645 mole % 16.8 4.2 79.0 100.0
7.53 Determine the weight of water removed while drying 1,000 kg of wet substance from 35% to
5%.
Basis: 1,000 kg of wet material.
Dry material is the Tie element.
Moisture present is 1,000 0.35 = 350 kg
Dry material is 1,000 350 = 650 kg
Dry material appears as 95% in the exit.
Therefore the total weight of material leaving is
650
= 684.21 kg
0.95
So water removed during the drying is 1,000 684.21 = 315.79 kg
7.54 A mixture containing 47.5% of acetic acid is being separated by extraction in a counter current
multistage unit. The operating temperature is 24 C and the solvent used is iso-propyl ether. Using the
solvent in the ratio of 1.3 kg/kg of feed, the final extract composition on a solvent free basis is found
to be 82% of acid. The raffinate is found to contain 14% of acid on solvent free basis. Find the
percentage of acid unextracted?
Acetic acid
Solvent
Extract E Isopropyl ether
Extraction unit
Raffinate R
Basis: 1 kg of feed contains 0.475 kg of acid and 0.525 kg of water Solvent used = 1.3 kg
Let E kg and R kg be the weight of extract and raffinate Acid balance: 0.475 = 0.82E + 0.14R
Water balance: 0.525 = 0.18E + 0.86R
Solving the above, we have, E = 0.493 kg and R = 0.507 kg
0.507
= 14.94%.\ Acid unextracted:
0.475
7.55 A plant makes liquid carbon-dioxide by treating Dolomite with commercial sulphuric acid. The
ore analyzes CaCO
3
: 68%, MgCO
3
: 30% and rest silica. Acid used is 94% pure. Find: (a) CO
2
produced
(b) acid required per tonne of the ore and
(c) the composition of the solid left behind.
Basis: 1 tonne of the ore
Weight of CaCO
3
: 680 kg, MgCO
3
: 300 kg and SiO
2
: 20 kg The reactions taking place are:
Reaction (i):
CaCO + H SO

CaSO + CO + H O
324 4 2 2

100 98 136 44 18
Reaction (ii):
MgCO + H SO

MgSO + CO + H O 324 4 2 2 84.3 98 120.3 44 18

(a) CO
2
produced by
Reaction (i):
680 44
= 299.2 kg
100

Reaction (ii):
300 44
= 156.6 kg
84.3
Total weight of CO
2
produced = 299.2 + 156.6 = 455.8 kg (b) H
2
SO
4
required during
Reaction (i):
680 98
= 666.4 kg
100

Reaction (ii):
300 98
= 348.8 kg
84.3
Total weight of H
2
SO
4
required = 1,015.2 kg
1,015.2
Commercial acid required =

= 1,080 kg

(c) The solid residue contains CaSO

4
, MgSO
4
and SiO
2
CaSO
4
formed:
136
= 924.8 kg

MgSO
4
formed:
120.3
= 428.1 kg

Silica remaining from the ore = 20 kg

Composition of the solid left behind
CaSO
4
: 67.36%, MgSO
4
: 31.18% and SiO
2
: 1.46.%
7.56 A fuel gas contains 70% methane, 20% ethane and 10% oxygen. The fuel-air mixture contains
200% excess O
2
before combustion. 10% of the hydrocarbon remains unburnt. Of the total carbon
burnt 90% forms CO
2
and the rest forms CO. Calculate the composition of the flue gas on dry and wet
basis.
Basis: 100 g moles of the fuel gas
The reactions taking place are:
CH
4
+ 2O
2
CO
2
+ 2H
2
O
CH
4
+ 1.5O
2
CO + 2H
2
O
C
2
H
6
+ 3.5O
2
2CO
2
+ 3H
2
O
C
2
H
6
+ 2.5O
2
2CO + 3H
2
O
Oxygen required for complete combustion = (70 2) + (20 3.5) 10 = 200 g moles
Oxygen supplied: 200 3 = 600 mole (200% excess) Nitrogen entering from air = (600 79/21) =
2,257 g moles Methane burnt: (70 0.9) = 63 mole, unburnt = 7 g moles Ethane burnt: (20 0.9) = 18
mole, unburnt = 2 g moles CO
2
formed: (63 0.9) + (18 0.9 2) = 89.1 g moles CO formed: (63
0.1) + (18 0.1 2) = 9.9 g moles O
2
used: (63 0.9 2) + (63 0.1 1.5) + (18 0.9 3.5)
+ (18 0.1 2.5) = 184.1 moles H
2
O formed: (63 0.9 2) + (63 0.1 2) + (18 0.9 3) + (18 0.1
3) = 180 g moles
Component Weight, g mole gases
CH
4
7.0
C
2
H
6
2.0
CO
2
89.1
CO 9.9
O
2
415.9
N
2
2,257.0
Total (dry) 2,780.9
H
2
O 180.0
Total (wet) 2,960.9
Composition %
Wet basis Dry basis
0.236 0.252
0.067 0.072
3.010 3.204
0.334 0.356
14.049 14.959
76.224 81.157
100.00
6.080
100.000
7.57 In a catalytic incinerator a liquid having a composition of 88% carbon and 12% hydrogen is
vaporized and burnt with dry air to a flue gas of the following composition on a dry basis. CO
2
:
13.4%, O
2
: 3.6% and N
2
: 83%. Find:
(a) How many kmole of dry flue gas are produced per 100 kg of the liquid feed and
(b) What was the % excess air?
Basis: 100 kg of feed. C : 88 kg = 7.334 katoms
H
2
: 12 kg = 6 kmoles
The reactions are:
C + O
2
CO
2
H
2
+ 0.5O
2
H
2
O
CO
2
produced will be 7.334 kmoles and it appears as 13.4% of exit gases.

7.334
Thus the exit gas moles is

= 54.73 kmoles

Water present in the exit gases =
12
= 6 kmoles
2
Dry flue gas leaving is = 54.73 kmoles
Oxygen reacted: (7.334 + 3) = 10.334 kmoles
3.6
Percentage excess air:

100 = 34.84%

7.58 Aviation gasoline is isooctane C

8
H
18
. It is burned with 20% excess air and 30% of the carbon
forms CO and rest goes to carbon dioxide. What is the analysis of the exit gases (on dry basis)?
Basis: 1 kmole of the isooctane. The reactions that are taking place are:
C
8
H
18
+ 8.5O
2
8CO + 9H
2
O;
C
8
H
18
+ 12.5O
2
8CO
2
+ 9H
2
O.
Oxygen required for complete combustion is 12.5 kmoles Oxygen supplied is (12.5 1.2) = 15
kmoles
Nitrogen coming from air

79
= 56.43 kmoles

CO
2
formed by the reaction is (1 0.7 8) = 5.6 kmoles CO formed by the reaction is (1 0.3 8) =
2.4 kmoles Oxygen reacted: (1 0.7 12.5) + (1 0.3 8.5) = 11.3 kmoles Oxygen remaining is (15
11.3) = 3.7 kmoles
Gases CO
2
CO O
2
N
2
Total mole 5.6 2.4 3.7 56.43 68.13
mole % 8.22 3.52 5.43 82.83 100.0
7.59 Isothermal and isobaric absorption of SO
2
is carried out in a packed tower containing Raschig
rings. The gases enter the bottom of the tower with 14.8% of SO
2
. Water is distributed at the top of
the column at the rate of 1,000 litres per minute. The total volume of gas handled at 1 atm and 30 C
is 1,425 m
3
/h. The gases leaving the tower are found to contain 1% of SO
2
. Calculate the percentage
of SO
2
in the outlet water and express it in weight %. Basis: One hour.
Volume of the gases at standard conditions:

273
= 1283.9 m
3

1283.9
Amount of gases =

= 57.281 kmoles

SO
2
entering absorber: (57.281 0.148) = 8.4776 kmoles Inert gases are the tie element
Inert gases: (57.281 8.4776) = 48.8034 kmoles
If 99% is equal to 48.8034 kmoles then 1% is

48.8034

= 0.493 kmole

SO
2
absorbed in the tower: 8.4776 0.493 = 7.9846 kmoles = 511 kg
Amount of water flowing = 1,000 60 = 60,000 kg/h
Weight of the total liquid leaving the tower is 60,511 kg
Weight % of SO
2
=



100 = 0.84%.

7.60 A pure gaseous hydrocarbon is burnt with excess air. The Orsat analysis of the flue gas: CO
2
:
10.2%, CO : 1%, O
2
: 8.4% and rest nitrogen. What is the atomic ratio of H to C in the fuel? Find the
% excess oxygen supplied.
Basis: 100 kmoles of the flue gases.
N
2
in flue gas = 100 (10.2 + 1 + 8.4) = 80.4 kmoles Let the hydrocarbon be C
x
H
y
.
Let a kmole of it get oxidized to CO
2
and b kmole of it get oxidized to CO.
The reactions are:
C
x
H
y
+ (x + y/4)O
2
xCO
2
+ y/2H
2
O;
C
x
H
y
+ (x/2 + y/4)O
2
xCO + y/2H
2
O.
We also know that,
2C + O
2
2CO
i.e. 2 kmoles of CO requires 1 kmole of O
2
.
\ 1 kmole of CO requires 0.5 kmole of O
2
for conversion to CO
2
21
= 21.37 kmoles\ O
2
supplied =
79
O
2
reacted = (21.37 8.4) = 12.97 kmoles for forming CO and CO
2
For converting CO to CO
2
additional O
2
required is 0.5 kmoles \ O
2
excess = 8.4 0.5 kmoles
= 7.9 kmoles
i.e. O
2
required = 21.37 7.9
= 13.47 kmoles
7.9 t100
58.65% excess air =
13.47
Carbon balance = a + b = 11.2
CO
2
formed = ax = 10.2; CO formed: bx = 1
ax/bx = 10.2
Oxygen consumed; ax +

aybx by

= 12.97
42 4
Solving, we get x = 1 and y = 0.8
Hence, y is approximated to a full number 1
Molar ratio, H/C = y/x = 1;
The hydrocarbon will be C
2
H
2
, acetylene.
7.61 A feed of 100 kmoles/h containing 40 mole % A is to be distilled to yield a product containing
95 mole % A and a residue containing 90 mole % B. Estimate the flow rate of distillate and residue.
Making a total material balance,
F = D + W (1) Making a component balance,
F.X
f
= D.X
D
+ W.X
w
(2) Substituting,
F = 100 kmoles/h, X
f
= 0.4, X
D
= 0.95 and X
w
= 0.1
100 = D + W (3) 1000(0.4) = D(0.95) + W(0.1) (4) Solving (3) and (4), we get
D = 353 kmoles/h
W = 647 kmoles/h
7.62 One hundred kilograms of liquid mixture containing 30% A and 70% B is extracted with a
solvent mixture containing C and D. After thorough mixing and allowing the system to reach
equilibrium, two separate layers are observed. The composition of both the layers have been
analyzed and given below:
Layer Component
A B C D
Top 10 05 60 25
Bottom 20 60 05 15
Estimate (i) the weight of each layer, (ii) weight of solvent, and (iii) composition of C and D in
solvent.
Basis: 100 kg of feed
Solvent
Feed
Extractor
x
y
Let the weight of top layer be x, and the weight of bottom layer be y from the extractor.
Let the weight of solvent used be s
Total material balance gives
100 + s = x + y
(or)
s = [x + y] 100
Making component balance for A, we get
100(0.3) = x(0.1) + y(0.2)
30 = 0.1x + 0.2y
Similarly, making component balance for B, we get
100(0.7) = x(0.05) + y(0.6)
70 = (0.05)x + 0.6y
Solving, we get
x = 80 kg, and
y = 110 kg
Solvent used is
s = [x + y] 100
= 110 + 80 100 = 90 kg
Making a component balance for C and D
Weight of C = 80(0.6) + 110(0.05) = 48 + 5.5 = 53.5 kg Weight of D = 80(0.25) + 110(0.15) = 20 +
16.5 = 36.5 kg Since, the total weight of solvent is 90 kg
x
C
=
53.5
= 0.5945
90

x
D
=
36.5
= 0.4055
90
7.63 One hundred kg of a mixture containing 80% alcohol and 20% water is mixed with another
mixture containing 40% alcohol and 60% water. If it is desired to produce a mixture containing 50%
alcohol and 50% water, estimate the quantity of 40% alcohol and 60% water mixture needed.
Basis: 100 kg of feed mixture
Let the weight of 40% alcohol + 60% water mixture to be mixed be x kg Making a material balance
for alcohol:
100(0.8) + x(0.4) = (100 + x)(0.5)
i.e. 80 + 0.4x = 50 + 0.5x
Solving, x = 300 kg
Check: by making water balance
100(0.2) + x(0.6) = (100 + x)(0.5)
i.e. 0.1x = 30
Solving, x = 300 kg
7.64 A gas mixture has CO : 10%, CO
2
: 50%, O
2
: 5% and rest nitrogen by volume. It is desired to
have the nitrogen composition as 40% in the final mixture by mixing it with fresh air. Estimate the
gas/air ratio to be maintained to achieve the composition as 40% in the final air. Also, estimate the
composition of leaving air.
Basis: 1 kmole of incoming gas mixture
Since the composition of gas is given in volume %, it is to be taken as mole %.
Air is assumed to contain 79% N
2
and 21% O
2
by mole %. Let 1 kmole of gas be mixed with y kmole
of air to give final product containing 40 mole % N
2
in (1 + y) kmole of leaving air Making a material
balance for nitrogen
(1) (0.35) + y(0.79) = (1 + y) (0.4)
0.05 = 0.39y
Solving, y = 0.128 kmole
Gas to air ratio is 1/0.128 = 7.813
y kmole O
2
: 21% N
2
: 79%
1 kmole
CO = 10% (1 + y) kmole
CO
2
= 50% Mixer
N2 = 40%O2 = 5%
N
2
= 35%
Leaving stream:
Component Weight, kmoles mole % CO 0.1 8.86
CO
2
0.5 44.32
O
2
0.05 + 0.128 0.21 = 0.07688 6.82
N
2
0.35 + 0.128 0.79 = 0.45112 40.00
Total 1.128 100.00
Average molecular weight:
(0.0886) (28) + (0.4432) (40) + (0.0682) (32) + (0.4) (28) = 33.5912
7.65 A gas containing 5% SO
2
, 10% O
2
, and rest 85% N
2
enters a catalytic chamber where the
leaving gas contains only 0.5% SO
2
. Estimate the fractional conversion of SO
2
to SO
3
and also the
composition of gases leaving catalytic chamber.
Basis: 100 kmoles of gas entering the chamber
The reaction is
SO
2
+ O
2
SO
3
Let x be the kmoles of SO
2
reacted
So, unreacted SO
2
= 5 x
Then, SO
3
formed is x and the corresponding O
2
reacted is x/2 moles (by stoichiometry)
Balance O
2
=

10
x
2

Total amount of gas leaving = 85 + 10
x
+ x + [5 x]
2

x
= 100
2

Mole fraction of SO
2
in the leaving stream = 0.005 i.e.
5 -x
= 0.005 100
-
x
2
Solving, we get
x = 4.511
Fractional conversion of SO
2
to SO
3
=
4.511
100 = 90.22%
Gas analysis:
Component Weight, kmoles mole % SO
2
5 4.511 = 0.489 0.500
SO
3
4.511 4.615
O
2
10 4.511/2 = 7.744 7.923
N
2
85.000 86.962
Total 97.744 100.000
EXERCISES
7.1 The waste acid from a nitrating process contains 25% HNO
3
, 50% H
2
SO
4
and 25% water. This
acid is to be concentrated to 30% HNO
3
, 60% H
2
SO
4
by addition of 95.3% H
2
SO
4
and 90% HNO
3
.
Calculate the weight of acids needed to obtain 10,000 kg of desired acid.
7.2 The gas obtained from a furnace fired with a hydrocarbon fuel oil analyses
CO
2
: 10.2%, O
2
: 7.9%, N
2
: 81.9%.
Calculate: (a) percentage excess air, (b) C:H ratio in the fuel and (c) kg of air supplied per kg of fuel
burnt.
7.3 The flue gas from an industrial furnace has the following composition by volume. CO
2
: 11.73%,
CO: 0.2%, H
2
: 0.09% ,O
2
: 6.81% N
2
: 81.17%. Calculate the percentage excess air used, if the loss of
carbon in the clinker and the ash is 1% of the fuel used. The fuel gas has the following composition by
weight:
C: 74%, H
2
: 5%, O
2
: 5%, N
2
: 1%, H
2
O: 9% S: 1% and ash: 5%.
7.4 A fuel gas contains CO
2
: 2%, CO: 34%, H
2
: 41%, O
2
: 1%, C
2
H
4
: 7%, CH
4
: 11% and rest N
2
. It
is burnt with 25% excess air. Assuming complete combustion, estimate the composition of leaving
gases.
7.5 Limestone is burnt with coke having 85% carbon, producing a gas of 28% CO
2
, 5% O
2
, and rest
N
2
. Calculate the amount of lime produced per 100 kg of coke burnt and the amount of excess air.
7.6 Pure S is burnt in a furnace with 65% excess air. During combustion 90% of S is burnt to SO
2
and
rest to SO
3
. Estimate the composition of gases leaving.
7.7 In the manufacture of nitric acid, ammonia is reacted with air at 650 C and 7 bar. The
composition of the mixed vapour is nitrogen: 70%, oxygen: 18.8%, ammonia: 10% and rest water.
Find the average molecular weight, composition of leaving gases in weight % and the density of
gases.
7.8 Thirty kilograms of coal analyzing 80% carbon and 20% hydrogen are burnt with 600 kg of air
yielding a gas having an orsat analysis in which the ratio of CO
2
to CO is 3 : 2. What is the
percentage of excess air?
7.9 Pure sulphur is burnt in a burner at a rate of 1,000 kg/h. Fresh air is supplied at 30 C and 755
mm Hg. Gases from the burner contain 16.5% SO
2
and 3% O
2
and rest nitrogen on SO
3
free basis.
Gases leave the burner at 800 C and 760 mm Hg pressure. Calculate
(a) fraction of sulphur burnt to SO
3
(b) % excess air over the amount required to oxidize sulphur to SO
2
. 7.10 Butane is burnt with 80%
of the theoretical air. Calculate the analysis of the gases leaving assuming that all H
2
present is
converted to water.
7.11 Determine the combustion gas analysis when a medium fuel oil with 84.9% carbon, 11.4%
hydrogen, 3.2% sulphur, 0.4% oxygen and 0.1% ash by weight is burnt with 25% excess air. Assume
complete combustion.
7.12 A synthetic fuel oil is known to contain only H and C, gives on combustion an Orsat analysis of
CO
2
: 2%, O
2
: 2.8% and N
2
: 80.6%. Calculate the C:H ratio in the fuel.
7.13 A low grade pyrites containing 32% sulphur is mixed with 10 kg of pure sulphur per 100 kg of
pyrites so that the mixture will burn readily forming a burner gas that analyzes 13.4% SO
2
, 2.7% O
2
and 83.9% N
2
. No sulphur is left in the cinder. Calculate the % of sulphur fired that burnt to SO
3
.
7.14 A mixture containing 20 mole % butane, 35 mole % pentane and rest hexane, is to be separated
by fractional distillation into a distillate containing 95 mole % butane, 4 mole % pentane and rest
hexane and a bottom product. The distillate is expected to contain 90% of the butane in the feed.
Calculate the composition of the bottom product.
7.15 Gypsum (plaster of Paris: CaSO
4
2H
2
O) is produced by the reaction of calcium carbonate and
sulphuric acid. A certain limestone analyzes: CaCO
3
: 96.89%, MgCO
3
: 1.41% and inerts : 1.70%.
For 5 metric tonne of limestone reacted completely, determine:
(a) kg of anhydrous gypsum (CaSO
4
) produced.
(b) kg of sulphuric acid solution (98 weight %) required. (c) kg of carbon dioxide produced.
7.16 The synthesis of ammonia proceeds according to the following reaction N
2
+ 3H
2
2NH
3
In a given plant, 4,202 kg of nitrogen and 1,046 kg of hydrogen are fed to the synthesis reactor per
hour. Production of pure ammonia
from this reactor is 3,060 kg per hour.
(a) What is the limiting reactant?
(b) What is the percent excess reactant?
(c) What is the percent conversion obtained (based on the limiting
reactant)?
7.17 A triple effect evaporator is designed to reduce water from an incoming brine stream from 25
weight % to 3 weight %. If the evaporator unit is to produce 14,670 kg/h of NaCl (along with 3
weight % H
2
O), determine:
(a) the feed rate of brine in lb/h.
(b) the water removed from the brine in each evaporator.
7.18 A natural gas analyzes CH
4
: 80.0% and N
2
: 20.0%. It is burnt under a boiler and most of the
CO
2
is scrubbed out of the flue gas for the production of dry ice. The exit gas from the scrubber
analyzes CO
2
: 1.2%, O
2
: 4.9% and N
2
: 93.9%.
Calculate:
(a) percentage of the CO
2
absorbed.
(b) percent excess air used.
7.19 A synthetic gas generated from coal has the following composition: CO
2
: 7.2%, CO : 24.3%,
H
2
: 14.1%, CH
4
: 3.5% and N
2
: 50.9%. (a) Calculate the cubic metre of air necessary for complete
combustion per cubic metre of synthetic gas at the same conditions.
(b) If 38% excess air were used for combustion, what volume of flue gas at 400 C and 738 mm Hg
would be produced per cubic foot of synthetic gas at standard conditions?
(c) Calculate the flue gas analysis for (a) and (b).
7.20 The gas obtained by burning pure carbon in excess oxygen analyzes 75% CO
2
, 14% CO, and rest
O
2
in mole %.
(a) What is the percentage of excess oxygen used?
(b) What is the yield of CO
2
in kg per kg of carbon burnt?
7.21 A producer gas has the following composition by volume: CO: 23%, CO
2
: 4.3%, oxygen: 2.7%,
and nitrogen: 70% (a) Calculate the average molecular weight.
(b) Calculate the gas (in m
3
) at 30 C and 760 mm Hg pressure formed per kg of carbon burnt.
(c) Calculate the volume of air at 30 C and 760 mm Hg pressure per 100 m
3
of the gas at the same
conditions if the total oxygen present be 20% in excess of that theoretically required, and
(d) Calculate the composition of gases leaving for part (c) assuming complete combustion.
7.22 A sample of coke contains 80% C, 5.8% hydrogen, 8% oxygen, and 1.4% nitrogen. Rest is ash.
It is gasified and the gas produced has 5% CO
2
, 32% CO, 12% H
2
, and 51% N
2
.
(a) Estimate the volume at 25 C and 750 mm Hg of the gas formed
per 100 kg of coke gasified, and
(b) Calculate the volume of air used per unit volume of gas produced,
both measured under same conditions.
7.23 A coal containing 87.5% total carbon and 7% unoxidised hydrogen is burnt in air
(a) If 40% excess air is used than that of theoretically needed,
calculate the kg of air used per kg of coal burned. (b) Calculate the composition by weight of gases
leaving the furnace
assuming complete combustion.
7.24 In a lime manufacturing process, pure limestone is burnt with coke having 87% carbon,
producing a gas of 27% CO
2
, 3% O
2
, and rest N
2
. Calculate (a) the amount of lime produced to coke
burnt.
(b) the percentage of excess air, and
(c) the amount of stack gas obtained per tonne of lime produced. 7.25 A liquid hydrocarbon feed is
passed into a flash vaporizer where it is heated and separated into vapour and liquid streams. The
analysis of various streams in weight % is as follows:
Stream component Feed Vapour Liquid C
4
H
10
20 71.2 8.6 C
5
H
12
30 23.8 C
6
H
14
50 4.8
Estimate the flow rates of liquid and vapour stream for a feed rate of 100 kg/h. Also, evaluate the
composition of other two components in liquid phase.
7.26 The petrol used for petrol engine contains 84% carbon and 16%
hydrogen. The air supplied is 80% of that required theoretically for complete combustion. Assuming
that all the hydrogen is burnt and that carbon is partly burnt to CO and to CO
2
without any free carbon
remaining, find the volumetric analysis of the dry exhaust gas.
7.27 Producer gases are produced by burning coke with a restricted supply of air so that more CO is
produced than CO
2
. The producer is producing gas having CO:CO
2
mole ratio as 5:1 from a coke
containing 80% carbon and 20% ash. The solid residue after combustion carries with it 2% unburnt
carbon. Calculate: (a) moles of gas produced per 100 kg of coke burnt,
(b) moles of air supplied per 100 kg of coke burnt, and (c) percentage of carbon lost in the ash
7.28 A furnace uses coke containing 80% carbon and 0.5% hydrogen and the rest ash. The furnace
operates with 50% excess air. The ash contains 2% unburnt carbon. Of the carbon burnt 5% goes to
form CO. Calculate,
(a) the composition of the flue gas,
(b) the ash produced, and
(c) the carbon lost per 100 kg of coke burnt.
7.29 A petroleum refinery burns a gaseous mixture containing C
5
H
12
:7%
C
4
H
10
: 10%
C
3
H
8
: 16%
C
2
H
6
:9%
CH
4
: 55%
N
2
:3%
at rate of 200 m
3
/h measured at 4.5 bars and 30 C. Air flow rate is so adjusted that 15% excess air is
used and under these conditions the ratio of moles of CO
2
: moles of CO in the flue gas is 20:1.
Calculate
(a) m
3
/h of air being introduced at 1 atm and 30 C, and (b) the composition of the flue gas on dry
basis.
7.30 The off gas from a phosphate reduction furnace analyses P
4
:8%
CO : 89%
N
2
:3%
and is burnt with air under the conditions such that phosphorus is selectively oxidized. From the flue
gas analysis, the oxides of phosphorus precipitate on cooling and are separated from the remaining
gas. Analysis of the latter shows that:
CO
2
: 0.9%
CO : 22.5%
N
2
: 68%
O
2
: 8.6%
It may be assumed that oxidation of phosphorus is complete and phosphorus exists in the flue gas
partly as P
4
O
6
and partly as P
4
O
10
. Calculate what % of CO entering the burner is oxidized to CO
2
,
and what % of P
4
is oxidized to P
4
O
10
?
7.31 Determine the flue gas analysis, airfuel ratio by weight, and the volume of the combustion
products at 250 C, when the coal refuse of the following composition burns with 50% excess air:
Proximate analysis Moisture
Ash
Volatile matter
Fixed carbon
Ultimate analysis Carbon
Hydrogen
Nitrogen
Sulphur
Balance is oxygen
Air dried % 8
20
28.5
43.5
Air dried % 81.0
4.6
1.8
0.6
If the rate of burning of coal is 3 tonnes/h, what is the capacity of the air blower used? Assume
complete combustion.
7.32 Determine the flue gas analysis and the airfuel ratio by weight when a medium viscosity of
fueloil with 84.9% C, 11.4% H
2
, 3.2% S, 0.4% O
2
and 0.1% ash is burnt with 20% excess air.
Assume complete combustion.
7.33 A furnace burns producer gas with 10% excess air at a rate of 7200 Nm
3
/h and discharges flue
gases at 400 C and 760 mm Hg. Calculate the flue gas analysis, air requirement, and the volume of
flue gases per hour. The gas is supplied from the gas holder and its orsat analysis is as follows:
CO
2
:4%
CO : 29%
N
2
: 52.4%
H
2
: 12%
CH
4
: 2.6%
Normal temperature = 30 C. Assume complete combustion. 7.34 The following is the ultimate
analysis of a sample of petrol by weight:
C 85%
H
2
15%
Calculate the ratio of air to petrol consumption by weight if the volumetric analysis of the dry exhaust
gas is:
Composition Volume %
CO
2
11.5
O
2
0.9
CO 1.2
N
2
86
Also find the % excess air.
Recycle and Bypass 8
8.1 RECYCLE
In industries, sometimes a part of the main product stream or the intermediate product stream
comprising both reactants and products or the intermediate product is sent back along with feed to the
system or somewhere in the middle of the system. Such a stream is called Recycle stream. This is
done to improve the conversion whenever the conversion is low and to have energy economy in
operations. This also improves the performance of an equipment as in the case of absorption of
sulphur trioxide using sulphuric acid rather than water, as the solubility is low in pure water.
8.2 BYPASS
Bypassing of a fluid stream is dividing it into two streams, and is often used in industries to have a
closer control in operation. This is done if there is a sudden change in the property of a fluid stream
like excessive heating (or cooling) as it passes through a preheater (cooler) before entering another
unit. In such cases this conditioned stream is mixed with a portion stream at its original condition and
then used in the process. This is called bypassing operation.
8.3 PURGE
One of the major problems encountered during recycling is the gradual increase in the concentration
of inert or impurities in the system. A stage may reach when the concentration of these components
may cross permissible levels. By bleeding off a fraction of the recycle stream, this problem can be
overcome. This operation is known as purging. This is quite common in the synthesis of ammonia and
electrolytic refining of copper. The above (8.1, 8.2, and 8.3) definitions have been shown in Figure
8.1.
180
Bypass
Fresh
feed Mixing
Process Feed
unit
Gross product
Sepa
Net product
rator
Recycle Purge
Figure 8.1 A scheme indicating recycle, bypass and purge. WORKED EXAMPLES
8.1 A distillation column separates 10,000 kg/h of a 50% benzene and 50% toluene. The product
recovered from the top contains 95% benzene while the bottom product contains 96% toluene. The
stream entering the condenser from the top of the column is 8,000 kg/h. A portion of the product is
returned to the column as reflux and the remaining is withdrawn as top product. Find the ratio of the
amount refluxed to the product taken out.
8,000 kg/h
V
Condenser
Distillation
R
D
Benzene 95% B 10,000 kg/h F
column
50% B, 50% T
W
96% Toluene
Figure 8.2 Overall balance
F = D + W
or, 10,000 = D + W
Benzene balance gives,
5000 = 0.95D + 0.04W Solving, D = 5,050 kg/h W = 4,950 kg/h Balance around condenser gives,
V = D + R
or, 8,000 = 5,050 + R
\ R = 2,950 kg/h
Reflux ratio =
Refluxed quantityR
= 0.584
Actual product D
8.2 What is the flow rate in recycle stream in Figure 8.3 shown below?
Water W
300F
F Feed
10,000 kg/h
Evaporator 20% KNO
3
50% KNO3
0.6 kg KNO
3
/kg water (i.e. 0.6/1.6 = 0.375 KNO
3
solution) M
R
Crystallizer
100F
C
Crystal with 4% H
2
O
Figure 8.3
Basis: One hour. KNO
3
entering = 2,000 kg/h
2000
\
Crystal leaving crystallizer,
C
=

= 2,080 kg/h

Overall balance F = C + W
since F = 10,000 kg/h
C = 2,080 kg/h
\ W = 7,920 kg/h
Crystallizer balance gives, M = C + R = (2,080 + R)
KNO
3
Balance gives 0.5M = 0.96C + 0.375R
Thus R = 7,680 kg/h
8.3 Metallic silver may be obtained from sulphide ores by roasting to sulphates and leaching with
water and subsequently precipitating silver with copper. In the Figure 8.4 shown below, the material
leaving the second separator was found to contain 90% silver and 10% copper. What percentage
excess copper was used? If the reaction goes to 75% completion based on the limiting agent Ag
2
SO
4
,
what is the recycle stream in kg/tonne of product?
Cu
CuSO
4
F
Reactor
S
1
S
2
90% Ag; 10% Cu
Ag
2
SO
4
Recycle R Ag
2
SO
4
Figure 8.4

Ag SO

24
+ Cu 2Ag + CuSO
4

312 63.5 (2 107.9) 159.5
Basis: 1 tonne of product = 1000 kg product
(i.e.) 900 kg silver; 100 kg of copper
Ag
900 t312
= 1300 kg
2
SO
4
needed =
t2107.9

CuSO
4
formed =
1,300 t159.5
= 665 kg
312

Cu needed =
1, 300 t63.5
= 265 kg (for forming CuSO
4
)
312
Total copper supplied = 265 + 100 = 365 kg
% Excess copper used = 100
100
= 37.7%
265
We know the reaction is 75% complete. 25% of the limiting reactant (Ag
2
SO
4
) was unconverted
which goes in the recycle steam.
Ag
2
SO
4
balance: F = R + 1,300 or, F = 1,733.3 kg
0.25F = R
or, 0.25 (R + 1,300) = R \ R = 433 kg
8.4 In the diagram shown in Figure 8.5, what fraction of dry air leaving is recycled?
x g dry air A
H
1
= 0.0152 g B of wv/g
0.099 g H
2
O/g
dry solid
CD
H
2
= 0.0525 g 52.5 g dry air (e)
of wv/g DA
Drier 1.562 g H
2
O/g dry solid
Figure 8.5
Basis: 1 g of dry solid. Let x g of dry air be recycled. Water removed by drying = (1.562 0.099) =
1.463 g Water removed/g of dry air = 0.0525 0.0152 = 0.0373 g
Dry air needed =
1.463
= 39.22 g\
0.0373
Dry air passing through drier (e) = 52.5 g (between B and C) \ Dry air recycled (x) = 52.5 39.22 =
13.28 g

x 13.28
= 0.253\ Fraction recycled = e
52.5
8.5 What is recycle, feed and waste for the system shown in Figure 8.6? Basis: 100 units of feed.
Material balance for A at = 20 + x = (100 + x)0.4
Solving, x = 33.3 units.
A
w
waste
40% A
20% A;
Feed Product P 80%
B
A 5% and B 95% Recycle A only
x
Figure 8.6

Recycle 33.3
= 0.333Feed 100
Material balance for A at = (100 + 33.3)0.4 = A
w
+ 33.3 + 0.05P Overall balance: 100 = A
w
+ P
Solving: A
w
= 15.81 units Product, P = 84.19 units
8.6 Methanol is produced by the reaction of CO with H
2
according to the equation CO + 2H
2

CH
3
OH. Only 15% of the CO entering the reactor is converted to methanol. The methanol product is
condensed and separated from the unreacted gases, which are recycled. The feed to the reactor
contains 2 kmoles of H
2
for every kmoles of CO. The fresh feed enters at 35 C and 300 atm. To
produce 6,600 kg/h of methanol calculate:
(a) Volume of fresh feed gas, and
(b) The recycle ratio.
35 C 300 atm
Reactor CH3OH
CO, 2H
2
6,600 kg/h
Unreacted CO, H
2
Figure 8.7 Basis: One hour of operation
Methanol produced =
6,600
= 206.25 kmoles
32
CO + 2H
2
CH
3
OH
15% conversion of CO entering gives 206.25 kmoles of methanol
206.25
= 1,375 kmoles\ CO entering the reactor =
0.15
and H
2
entering the reactor = 1,375 2 = 2,750 kmoles Total amount of CO and H
2
= 4,125 kmoles
CO unconverted (goes into recycle)
= CO entering CO converted = (1,375 206.25) = 1,168.75 kmoles
H
2
unconverted (goes into recycle) = (2,750 0.85) = 2,337.50 kmoles \ Total moles of feed
unconverted = 3,506.25 kmoles
Fresh CO needed = 206.25 kmoles
Fresh H
2
needed = 412.50 kmoles
Total moles of fresh feed = 618.75 kmoles\
(a) Volume of feed gas = 618.75

22.414

308 1
273

300

= 52.16 m
3
(b) Amount of gas leaving reactor = (3,506.25 + 206.25) = 3,712.50 kmoles
Amount of gas recycled = 3,506.25 kmoles
3,506.25
\
Recycle ratio =

= 0.944 (mole ratio)

By weight 1,168.75 kmoles of CO = 32,725 kg;

2,337.5 kmoles of H
2
= 4,675 kg
Recycle stream of CO and H
2
= 32,725 + 4675 = 37,400 kg Products leaving reactor = (37,400 +
6,600) = 44,000 kg
37,400
\
Recycle ratio =

= 0.85 (weight ratio)

8.7 Limestone containing 95% of CaCO

3
and 5% SiO
2
is being calcined. Heat for the reaction is
supplied from a furnace burning coke. The hot flue gases analyze 5% CO
2
. The kiln gas contains
8.65% CO
2.
In order to conserve some of the sensible heat a portion of the kiln gas is continuously
recycled and mixed with fresh hot flue gas. After mixing the gas entering the kiln analyzes 7% CO
2
(a) Find the kg of CaO produced/kg of coke burnt
(b) Find the recycle ratio, (i.e.) moles of gas recycled per mole of gas leaving the kiln.
Limestone
K Kiln
P
X R
Air
F Burner
Coke
Figure 8.8
Basis: 12 kg of coke
represent F kmole of flue gas (5% CO
2
) K, kmole of kiln gas (8.65% CO
2
)
R, kmole of gas recycled (8.65% CO
2
) P, kmole of product gas (8.65% CO
2
) X, kmole of gas entering
the kiln (7% CO
2
)
X
R
F
Figure 8.9
X = F + R (overall balance) (a) 0.07X = 0.05F + 0.0865 R (CO
2
balance) (b)
CaCO

CaO + CO

32
100 56 44
Assuming complete combustion
0.05F = 1 kmole CO
2
\ F = 20 kmoles
(
Q
1 kmole of CO
2
comes from 12 kg of Carbon)
C + O
2
CO
2
Solving (a) and (b), we have R = 24.2 kmoles; X = 44.2 kmoles Let m kmole of CO
2
be added in kiln
from the calcinations of limestone \ K = 44.2 + m
Making CO
2
balance, (0.07 X) + m = K 0.0865
or, 44.2 0.07 + m = (44.2 + m)(0.0865)
\ m = 0.8 kmole
\ K = 44.2 + 0.8 = 45.0 kmoles
CaO formed = (0.8 56) = 44.8 kg
(a) CaO formed/kg of coke burnt =
44.8
= 3.73
12

(b) recycle ratio (mole) =
R
=
24.2
= 0.538
K 45
8.8 Sea water is desalinated by reverse osmosis using the scheme shown in Figure 8.10D stream has
500 ppm salt = 0.05%
Find
(a) rate of B
(b) rate of D
(c) recycle R
R, Recycle
1,000 kg/h A
B, Waste 5.25% salt Reverse osmosis cell
3.1 salt % 4%
sea water
Desalinated water D, 0.05% salt
Figure 8.10
Basis: One hour
Overall balance, 1,000 = B + D
Salt balance = (1,000 3.1) = 5.25B + 0.050 Solving, B = 586.5 kg; D = 413.5 kg
R = 5.25%
Overall balance (At entry to cell), 1,000 + R = A
Salt balance, 1,000 0.031 + R 0.0525 = A 0.04
Solving, A = 1,720 kg and R = 720 kg
8.9 In the feed preparation section of an ammonia plant, hydrogen is produced by a combination of
steam-reforming/partial oxidation process. Enough air is used in partial oxidation to give a 3:1 H
2
-N
2
molar ratio in the feed to the ammonia unit. The H
2
-N
2
mixture is heated to reaction temperature and
fed to a fixed bed reactor where 20% conversion of reactants to NH
3
is obtained per pass. The
products from the reactor are cooled and NH
3
is removed by condensation. The unreacted H
2
-N
2
mixture is recycled and mixed with fresh feed. On the basis of 100 kmoles per hour of fresh feed
determine the NH
3
produced and recycle rate.
Fresh
feed
Reactor NH
3
Figure 8.11 Basis: 100 kmoles of feed
Given that H
2
: N
2
= 3 : 1
hydrogen: 75 kmoles and nitrogen: 25 kmoles N
2
+ 3H
2
2NH
3
Overall balance gives:
Feed NH
3
NH
3
formed = 50 kmoles
One mole of N
2
gives 2 moles of NH
3
Reactor balance gives:
3x, H2
Reactor NH
3
, N
2
and H
2x, N2
Let 3 x kmole of H
2
and x kmole of N
2
enter the reactor Since 20% conversion takes place,
NH
3
formed = x 0.2 2 = 0.4x = 50 kmoles \ x = 125 kmoles of N
2
; and 3x = 375 kmoles of H
2
Unreacted N
2
= 100 kmoles, and H
2
= 300 kmoles Ans.: NH
3
produced = 50 kmoles
Recycle = 400 kmoles
8.10 Find S, A, R and B from Figure 8.12 shown below, if 1 kg of grease/ 100 m
2
area is present and
the degreased surface per day is 10
5
m
2
.
Greased metal Solvent S
0% grease
G
Cleaned
metal
B
15% Grease solvent Separator A
Degreasing
40% grease 1% grease R
with
Solvent Recycle
solvent
Figure 8.12
Grease removed/day = 1,00,000/100 = 1,000 kg (i) Overall balance gives:
G 100%
40% Grease S Process A
100%
60% Solvent S + G = A (overall) (1) G = 0.4A = 1000 (grease balance) (2)
Solving Eqs. (1) and (2) A = 2,500 kg; S = 1,500 kg; G = 1,000 kg.
Degreasing
B (15%)
S (100%
free from
R-1% (recycle)
grease)
(ii) B = S + G + R (3)
B = 1,500 + 1,000 + R (overall) (4) 0.15B = 0 + 1,000 + 0.01R (grease balance) (5) Solving, (4) and
(5), B = 6,964.29 kg; R = 4,464.29 kg Check B = A + R; 6,964.29 = 2500 + 4,464.29
(0.15 6,964.29) = 1,000 + (0.01 4,464.29)
1,044.6435 = 1,044.6429
8.11 A solution containing 10% NaCl, 3% KCl and water is fed to the process shown in Figure 8.13
at the rate of 18,400 kg/h. The compositions of the streams are as follows: Evaporator product P
NaCl : 16.8%, KCl : 21.6% and water. Recycle product RNaCl : 18.9% and water. Calculate the
flow rates in kg/h and compute the composition of feed to the evaporator (F)
R
Fresh
feed
F
W
Evaporator Crystallizer P
NaCl only KCl only
Figure 8.13
Basis: One hour Water in feed = 18,400 0.87 = 16,008 kg/h KCl in feed = 18,400 0.03 = 552 kg/h
NaCl in feed = 18,400 0.1 = 1,840 kg/h Overall balance: water vapour
Feed,
F
Process KCl
NaCl
Balance around crystallizer: Overall balance: P = R + 552 NaCl balance: 0.168P = 0.189R
P Crystallizer R
KCl
Solving, R = 4,416 kg and P = 4,968 kg Balance around evaporator:
W
F Evaporator P
NaCl
F = W + NaCl + P
F = 16,008 + 1,840 + 4,968
= 22,816 kg/h
Feed to evaporator = recycle + fresh feed = 18,400 + 4,416 = 22,816 kg/h
Recycle, R
Fresh feed Feed to evaporator, F, m (Conc. of NaCl) n (Conc. of KCl)
Making a balance for NaCl, we have
18,400 0.1 + 0.189 4,416 = m 22,816
Solving, m = 11.72%
Similarly, for KCl, we have 18,400 0.03 = n 22,816 or, n = 2.42%
Check:
Making water balance, 18,400 0.87 + 4,416 0.811
= 22,816 (100 11.72 2.42) 19,589.6 kg = 19,589.6 kg
8.12 Ethylene oxide is produced by catalytic oxidation of ethylene and oxygen. The total feed to the
catalytic bed of the reactor contains 10:1 volume ratio of oxygen to ethylene and the conversion per
pass is 23%. Ethylene oxide is removed from the products completely and the unreacted ethylene is
recycled. The oxygen for the reaction is supplied from air. Calculate: (a) inlet and outlet composition
of the streams and (b) moles of fresh oxygen required for recycle gases.
Reaction: C
2
H
4
+ 0.5O
2
C
2
H
4
O.
Separator
Ethylene Reactor
GasesAir
Figure 8.14
Basis: 1 kmole of ethylene.
Oxygen supplied: 10 kmoles
Nitrogen entering: 10
79
= 37.62 kmoles
21
C
2
H
4
reacted: 1 0.23 = 0.23 kmole
C
2
H
4
O formed: 0.23 kmole
Oxygen reacted =
0.23
= 0.115 kmole
2
Oxygen remaining = 10 0.115 = 9.885 kmoles (a)
Inlet gases mole mole % C
2
H
4
1.0 2.056
O
2
10.0 20.560
N
2
37.62 77.384
Total 48.62 100.000
Ethylene recycled = (1 0.23) = 0.77 mole
(b) Moles recycled/mole of feed =
0.77
= 0.0159
48.62
oxygen required = 0.115 mole
(c)
Outlet gases mole mole % C
2
H
4
O 0.230 0.48
O
2
9.885 20.71
N
2
37.620 78.81
Total 47.735 100.000
8.13 In the diagram shown in Figure 8.15 find E, P, A and B. Also, find the composition of A.
The compositions are: F = 20% C
2
, 40% C
3
, 40% C
4
,
E = 95% C
2
, 4% C
3
, 1% C
4
,
P = 99% C
3
, 1% C
4
,
B = 8.4% C
3,
91.6% C
4
.
Basis: 100 kg of feed
E
P
A Feed, F
I Unit II Unit
B
Figure 8.15
Let us assume that the compositions given are in weight %. Overall balance: feed = 100 = E + P + B.
C
2
balance: 20 = 0.95E. So, the value of E = 20/0.95 = 21.053 kg C
3
balance: 40 = (0.04 21.053) +
0.99P + 0.0084B
C
4
balance: 40 = (0.01 21.053) + 0.01P + 0.916B
Solving the above, we find P = 35.9006 kg and B = 43.0464 kg
Since we know that F = E + A, we substitute the values of F and E, and observe, 100 = 21.053 + A.
Solving A is found to be 78.947 kg Composition of A:
C
3
balance: (0.99 35.9006) + (0.084 43.0464) = 39.1575 Weight % = 49.6. C
4
balance: (0.01
35.9006) + (0.916 43.0464) = 39.7895 Weight % = 50.4.
8.14 A contact sulphuric acid plant produces 98% acid. A gas containing 8% SO
3
(rest inert) enters a
SO
3
absorption tower at the rate of 28 kmoles/h 98.5% of SO
3
is absorbed in this tower by 97.3%
acid introduced at the top and 95.9% acid is used as the make up acid. Compute tonne/day of
(a) make up acid required
(b) acid fed at the top of the tower and
(c) acid produced.
Basis: In one day, gas entering = 28 24 = 672 kmoles SO
3
entering = 672 0.08 = 53.76 kmoles
= 53.76 80 = 4,301 kg
SO
H O
+H SO

32 24
80 18 98
SO
3
absorbed = 4,301 0.985 = 4,236.3 kg
Acid formed = 4,236.3
98
= 5,189.5 kg
80

Water reacted = 4,236.3
18
= 953.17 kg
80

97.3% SO
3
Exit r
Absorption
y 95.9%
tower
SO
3
in 28 kmoles/h
z x
98% (Acid)
Figure 8.16
Let us label x, y, z and r as shown.
Overall balance gives: z = (r + 4,236.3)
Acid balance gives, 0.98z = (0.973r + 5,189.5)
Solving the above, we get r = 1,48,271.5 kg;
z = 1,52,507.7 kg (overall)
Another balance of stream gives, z + y = x + r
Acid balance in this stream gives: 0.98z + 0.959y = 0.98x + 0.973r or, (0.98 1,52,507.7) + 0.959y =
0.98x + (0.973 1,48,271.5) Solving the above, we get x = 53,661.5 kg; y = 49,425.05 kg Check:
H
2
O balance, 0.021r 953.17 = (0.02 z)
or, (0.027 1,48,271.5) 953.17 = (0.02 1,52,507.7) 4,003.33 953.17 = 3,050.16.
EXERCISES
8.1 NO is produced by burning gaseous NH
3
with 20% excess O
2
: 4NH
3
+ 5O
2
4NO + 6H
2
O
The reaction is 70 percent complete. The NO is separated from the unreacted NH
3
, and the latter
recycled. Compute (a) moles of NO formed per 100 moles of NH
3
fed, and (b) moles of NH
3
recycled per mole of NO formed.
8.2 In a particular drier, 100 kg of a wet polymer containing 1.4 kg water/kg of dry polymer is dried
to 0.25 kg of water per kg of dry polymer per hour. 5,000 kg of dry air is passed into the drier. The
air leaving the drier is having a humidity of 0.0045 kg of water vapour per kg of dry air and fresh air
supplied at a humidity of 0.011 kg of water vapour per kg of dry air. Calculate the mass rate of fresh
air supplied and fraction of air recycled per hour.
Energy Balance 9
9.1 DEFINITIONS
The following definitions are frequently used since the study of energy balance concerns conversion
of our resources into energy effectively and utilize the same properly. In order to understand the basic
principles pertaining to the generation, transformation and uses of energy, the following terms need to
be discussed first.
9.1.1 Standard State
A substance at any temperature is said to be in its standard state when its activity is equal to one. The
activity may be looked upon as a thermodynamically corrected pressure or concentration. For pure
solids, liquids and gases the standard state corresponds to the substances at one atmosphere pressure.
For real gases, the pressure in the standard state is not 1 atmosphere but the difference from unity is
not large. In the case of dissolved substances the standard state is the concentration in each instance at
which the activity is unity. The enthalpies of substances in standard states are designated by the
symbol H, while the DH of a reaction where all reactants and products are at unit activity is
represented by DH.
9.1.2 Heat of Formation
The thermal change involved in the formation of 1 mole of a substance from the elements is called the
heat of formation of a substance. The standard heat of formation is the heat of formation when all the
substances involved in the reaction are each at unit activity. The enthalpies of all elements in their
standard states at 298 K are zero.
196
9.1.3 Heat of Combustion
It is the heat liberated per mole of substance burned. The standard heat of combustion is that
resulting from the combustion of a substance, in the state that is normal at 298 K and atmospheric
pressure, with the combustion beginning and ending at 298 K.
9.1.4 The Heat of Reaction
Heat of reaction from enthalpy data
It is defined as the enthalpy of products minus the enthalpy of reactants. The standard heat of reaction
for the reaction,
aA + bB cC + dD
is given by
D
H = [cDH

+ dDH

] [aDH
, A
+ bDH

]
r
r, C r, D
r
r, B
where DH
, i
is the standard heat of formation of i
th
component. By convention,
negative sign indicates that heat is given out and denotes exothermic reaction
positive sign indicates that heat is absorbed, i.e. endothermic reaction
Heat of reaction from heats of combustion data
For reactions involving organic compounds, it is more convenient to calculate the standard heat of
reaction directly from the standard heats of combustion instead of standard heats of reaction. The
standard heat of reaction under such circumstances is the standard heat of combustion of the reactants
minus the standard heat of combustion of products.
i.e. [DHreaction = SDHc, (reactants) SDHc, products]25C
9.1.5 Heat of Mixing
When two solutions are mixed, the heat evolved or absorbed during the mixing process is known as
heat of mixing.
9.2 HESSS LAW
If a reaction proceeds in several steps, the heat of the overall reaction will be the algebraic sum of
the heats of the various stages, and this sum in turn will be identical with the heat, the reaction would
evolve or absorb if it were to proceed in a single step.
9.3 KOPPS RULE
The heat capacity of a solid compound is approximately equal to the sum of the heat capacities of the
constituent elements. As per Kopps rule, the following atomic heat capacities are assigned to the
elements at 20 C:
Carbon: 1.8; Hydrogen: 2.3; Boron: 2.7; Silicon: 3.8; Oxygen: 4.0; Fluorine: 5.; Phosphorus: 5.4 and
all others: 6.2. Since the heat capacities of solids increase with temperature, it is clear that these
values do not apply over a wide range of temperature.
9.4 ADIABATIC REACTION TEMPERATURE
Adiabatic reaction temperature is the temperature attained by reaction products, if the reaction
proceeds without loss or gain of heat and if all the products of the reaction remain together in a single
mass or stream of materials.
9.5 THEORETICAL FLAME TEMPERATURE The temperature attained when a fuel is burnt in
air or oxygen without loss or gain of heat is called the Theoretical flame temperature.
WORKED EXAMPLES
9.1 Calculate the enthalpy of sublimation of Iodine from the following reactions and data
(a) H
2
(g) + I
2
(s) 2HI(g) DH = 57.9 kJ
(b) H
2
(g) + I
2
(g) 2HI(g) DH = 9.2 kJ
The desired reaction is I
2
(s) I
2
(g)
Solution: (a) (b) = DH = 67.1 kJ
9.2 Find the enthalpy of formation of liquid ethanol from the following
data:
DH, Heats of reaction, kJ (1) C
2
H
5
OH (l) + 3O
2
(g) 2CO
2
(g) + 3H
2
O(l) 1367.8 (2) C
(graphite) + O
2
(g) CO
2
(g) 393.5 (3) H
2
(g) + O
2
(g) H
2
O(l) 285.8 Solution: [2 (2) (1)
+ (3 (3))] = 2C + 3H
2
+ O
2
C
2
H
5
OH. The enthalpy of formation of ethanol = 276.6 kJ
9.3 200 kg of Cadmium at 27 C is to be melted. (The melting point is 320.9 C). The heat supply is
from a system, which supplies 210 kcal/ kg, at steady state. Find the quantity of heat to be supplied by
the system.
Atomic weight of Cadmium = 112.4, C
p
= (6 + 0.005T) kcal/kmole C and T in C.
Latent heat of fusion = 2050 kcal/kmole
Basis: 200 kg of Cadmium 1.78 katoms

2
Sensible heat = 1.78t t = 3885.5 kcal

Latent heat of fusion = 1.78 2050 = 3649.0 kcal

Total heat to be supplied = 7534.5 kcal
Quantity of steam to be supplied =
7534.5
= 35.88 kg
210
9.4 An evaporator is to be fed with 10,000 kg/h of a solution having 1% solids. The feed is at 38 C.
It is to be concentrated to 2% solids. Steam at 108 C is used. Find the weight of vapour formed and
the weight of steam used. Enthalpies of feed are 38.1 kcal/kg, product solution is 100.8 kcal/kg, steam
is 540 kcal/kg and that of the vapour is 644 kcal/kg.
Basis: One hour.
Feed = 10,000 kg/h
Vapour formed is 5000 kg/h
Thick liquor is 5000 kg/h
Enthalpy of feed = 10,000 38.1 = 38.1 10
4
kcal
Enthalpy of the thick liquor = 100.8 5,000 = 5,04,000 kcal. Enthalpy of the vapour = 644 5,000 =
32,20,000 kcal. Heat supplied by steam = M
s
l
s
= M
s
540 kcal.
Heat balance:
Heat input by steam + heat in, by feed
= Heat out, in vapour + Heat out, thick liquor or, [M
s
.(540) + 38.1 10
4
] = (32,20,000 + 5,04,000)
\ M
s
(540) = 33,43,000.
Thus the weight of steam required, M
s
= 6,190.75 kg/hr.
9.5 Calculate the standard heat of reaction:
CaC
2
+ 2H
2
O Ca(OH)
2
+ C
2
H
2
DH
f
cal/mole 15,000 68,317.4 2,35,800 54,194
Solution:
DH
rxn
= (2,35,800) + (54,194) (15,000) (2 68,317.4) The standard heat of reaction is
29,971.2 cal/mole
9.6 How much heat must be added to raise the temperature of 1 kg of a 20% caustic solution from 7
C to 87 C? Take datum temperature as 0 C.
Data:
Specific heat at 7 C = 3.56 and at 87 C = 3.76 kJ/kg K
Solution: Q = (m.C
p
.t)
1
(mC
p
t)
2
= 1 [(3.76 87) (3.56 7)] = 302.2 kJ
9.7 How many Joules are needed to heat 60 kg of sulphur trioxide from 273.16 K to 373.16 K?
C
pSO3
= 34.33 + 42.86 10
3
T 13.21 10
6
T
2
J/mole K Solution:
Number of moles of the trioxide =
60
= 0.75 kmole
80
At 373.16 K,
Q = nC
pSO3
dt
At 273.16 K
Q = [{34.33 (373.16 273.16)} + {(42.86 10
3
/2)(373.16
2
273.16
2
)}
+ {(13.21 10
6
/3)(373.16
3
273.16
3
)}] Q = 3,509.25 kJ/kmole.
9.8 Using the following data of heats of combustion in cal/g mole, calculate the following:
(a) Heats of combustion of benzene to water
(b) Heat of vaporization of benzene cal/g mole
(i) C
6
H
6
(l) to CO
2
(g) and H
2
O (l) = 7,80,980
(ii) C
6
H
6
(g) to CO
2
(g) and H
2
O (g) = 7,59,520
(iii) H
2
(g) to H
2
O (l) = 68,317
(iv) H
2
(g) to H
2
O (g) = 59,798
(v) Graphite to CO
2
(g) = 94,052
Desired reactions:
(a) C
6
H
6
(l) + 7.5O
2
6CO
2
(g) + 3H
2
O (l)
(b) C
6
H
6
(l) C
6
H
6
(g)
(a) Equation (i) itself gives value, DH
c
= 7,80,980 cal/g mole. (ii) C
6
H
6
(g) + 7.5O
2
6CO
2
(g) +
3H
2
O (g)
(iii) H
2
(g) + O
2
H
2
O (l)
(iv) H
2
(g) + O
2
H
2
O (g)
(v) C + O
2
CO
2
(g)
We can obtain the reaction (b) from the reaction (i) to (v) using
suitable multiplication factor for each step and adding or subtracting the equations as shown below:
i.e. Steps for equation. (b) = (i) + 3(iv) (ii) 3(iii) l = 8,097 cal/g mole
9.9 Find the heat of formation of ZnSO
4
from its elements and from these
data:
kcal/mole
(i) ZnS Zn + S 44
(ii) 2ZnS + 3O
2
2ZnO + 2SO
2
221.88
(iii) 2SO
2
+ O
2
2SO
3
46.88
(iv) ZnSO
4
ZnO + SO
3
55.1
Desired equation: Zn + S + 2O
2
ZnSO
4
kcal/mole
Steps: [(ii) + (iii) 2(i) 2(iv)] = 233.48 kcal/mole.
9.10 Steam that is used to heat a batch reaction vessel enters the steam chest, which is segregated
from the reactants, at 250 C, is saturated and completely condensed. The reaction absorbs 1000
Btu/lb of charge in the reactor. Heat loss from the steam chest to the surroundings is 5000 Btu/h. The
reactants are placed in the vessel at 70 F. At the end of the reaction, the materials are at 212 F. If
the charge contains 325 lb of material and the products and reactants have an average C
p
of 0.78
Btu/1b F, how many lb of steam are needed per lb of charge. The charge remains for an hour in the
vessel.
Basis: One hour: Datum 70 F Btu
Reaction absorbs heat = 1000 325 = 3,25,000
Heat loss to surroundings = 5,000
Heat in products: 325 0.78 (212 70) = 36,000
\ Q = total heat = 3,66,000
From steam tables at 482 F(250 C) l
s
= 734.9 Btu/lb we have, Q = m
s
l
s
= (m
s
) (734.9)
= 3,66,000 Btu
\ m
s
= 498.2 lb/h
lb of steam/lb of charge =
498.2
= 1.533
325
9.11 Pure ethylene is heated from 30 C to 250 C at a constant pressure. Calculate the heat added per
kmole
C
p
= 2.83 + 28.601 10
3
T 87.26 10
7
T
2
where
C
p
is in kcal/kmole K and T in K

T2
DH = n CdT
p
T
1
= 303 K, T
2
= 523 K

T1
n = 1 kmole
Or, DH = [2.83 {T
2
T
1
} + (28.601 10
3
/2) {T
2
T
2
}
2 1
{87.26

10
7
/3}{T
3
T
3
2 1
}] Heat added = 2,886.11 kcal
9.12 Calculate the amount of heat given off when 1 m
3
of air at standard conditions cools from 500 C
to 100 C at constant pressure. C
p
air = 6.386 + 1.762 10
3
T 0.2656 10
6
T
2
, where C
p
is in
kcal/kmole K and T in K.

1 m
3
=
1
= 0.0446 kmole
22.414

173

Q = 0.0446
C dT
= 0.0446 [6.386 600 + (1.762 10
3
/2)(173
2
773
2
)
p

773

(0.2656
6
/3) (173
3
773
3
)] 10
Q = 191.345 kcal,
Hence, heat is given off
9.13 Air being compressed from 2 atm and 460 C (enthalpy 210.5 Btu/lb) to 10 atm and 500 R
(enthalpy 219 Btu/lb). The exit velocity of air is 200 ft/s. What is the horse power required for the
compressor if the load is 200 lb of air/hour?
Basis: One hour.
(W
s
= shaft work, Btu/lb v: velocity, ft/s)
W
s
= (219 210.5) = 8.5 Btu/lb.
22
'v (200) = 0.8 Btu/lb tt 778)

Horse power needed = (8.5 + 0.8)
200
= 0.73 HP
2545
[1 Btu = 778 ft. lbf; 1 HP = 2545 Btu/h]
9.14 Find the heat of reaction at 1200 K. C
2
H
6
C
2
H
4
+ H
2
'H
f,C H26
84,720 kJ/kmole
'H
f,C H24
52,280 kJ/kmole
DH
rxn
,
298 K
: 52,280 (84,720) = 1,37,000 kJ
DH
rxn
= DH
rxn
nC
pReactants
(1200 298) + nC
pProducts
(1200 298)
= (1,37,000) [1 100 (1200 298)] + [{(1 78.7) + (1 29.7)}(1200 298)]
= 1,37,000 90,200 + 97,776.8
= 1,44,576.8 kJ/kmole (Heat to be supplied)
9.15 Calculate the heat input to raise the temperature of 132 kg of CO
2
from 100C to 1000C.
Perform the calculation in the following ways. (a) by integrating the expression for C
p
and (b) by
using mean heat capacity value C
p
in kcal/kmole K.
C
p
= 6.85 + 8.533 10
3
T 2.475 10
6
T
2
, kcal/kmole K Basis: 132 kg of CO
2
132/44 = 3
kmoles

T
2
(a) DH = n CdT
p
= 3 [6.85 900 + (8.533 10
3
/2)(1273
2
373
2
)

T1
(2.475
6
/3)(1273
3
373
3
)] 10
DH = 3[10,826.29] = 32,478.87 kcal
C
p
values at 1273 K and 373 K are:
C
p
at 1273 K = 13.702 kcal/kmole K
and C
p
at 373 K = 9.6884 kcal/kmole K
C
pav
= 11.6952 kcal/kmole K
DH = m C
pav
dT
= 3 11.6952 (1273 373)
= 31,577.04 kcal
9.16 SO
2
gas is oxidized in 100% excess air with 70% conversion to SO
3
. The gases enter the
converter at 400 C and leave at 450 C. How many kcals are absorbed in the heat exchanger of the
converter per kmole of SO
2
sent?
Basis: 1 kmole SO
2
.
SO
2
+ O
2
SO
3
O
2
sent = 0.5 2 = 1. SO
3
formed = 0.7 kmole N
2
in air = 1 79/21 = 3.76 kmole.
SO
2
remaining = 0.3 kmole
SO
3
SO
2
O
2
N
2
Total gases leaving kmoles 0.7 0.3 0.65 3.76 5.41 C
p
mean, cal/g mole C 15.5 11.0
7.5 7.1
H
rxn
= 23, 490 cal/g mole (given)D
DH
rxn
= 23,490 0.7 = 16,443 kcal
Datum: 0C
Heat in Heat out
SO
2
= 1 11 400 = 4,400 kcal SO
2
= 0.3 11 450 = 1,485.00 kcal O
2
= 1 7.5 400= 3,000 kcal O
2
= 0.65 7.5 450 = 2,193.75 kcal
N
2
= 3.76 7.1 400 = 10,676 kcal N
2
= 3.76 7.1 450 = 12,013.20 kcal
SO
3
= 0.7 15.5 450 = 4,882.50 kcal Total = 18,076 kcal Total = + 20,574.45 kcal DH
rxn
16,443 kcal \ Heat in 34,519.00 kcal
Hence, heat absorbed in heat exchanger = 13,944.5 kcal
9.17 From the following data compute the enthalpy change of formation for NH
3
at 480 C.
D H
f
at 25C for NH
3
= 10.96 kcal/kmole
C
p
N
2
= 6.76 + (6.06 10
4
T) + (13 10
8
T
2
)
C
p
H
2
= 6.85 + (2.8 10
5
T) + (22 10
8
T
2
)
C
p
NH
3
= 6.703 + (0.0063T) where T is in K,
Reaction: N
2
+3H
2
2NH
3
D H
f
/kmole 0 0 10.96
Basis: 1 mole of N
2
(Feed at 273 K)
DH
rxn
298 K: (2 10.96) = 21.92 kcal.
Find DC
p
= 2NH
3
(N
2
+ 3H
2
)
Da = (2 6.703) [7.76 + (3 6.85)] = 13.9
Db = (2 0.0063) [6.06 10
4
+ (3 2.8 10
5
)] = 0.0119 Dg = (2 0) (13 10
8
+ 3 22 10
8
)
= 7.9 10
7
D
H
o
=
D
H
rxn

Da
T

'
T2
'
T3

0.0119
t
298
2
7.9
10
73
D
H
o
= 21.92 (13.9

298)
2

t t
298
3
DH
o
= 3,598.87 kcal
480 C = 753 K
H
rxn, 480C
= DH
o
+ DaT +
'
T
2
+
'
T
3
D

0.0119
= 3,598.87 + (13.9

753) +

(753)2


7.9 107
(753)
3
+ t

\DH
rxn 480C
= 3,606.56 kcal/kmole
9.18 Calculate the calorific value of a blast furnace gas analyzing 25% CO, 12.5% CO
2
and 62.57%
N
2
.
(a) C + O
2
CO
2
; DH
rxn:
94 kcal
(b) C + O
2
CO; DH
rxn:
26 kcal
Also, calculate the theoretical flame temperature for the combustion of this gas assuming theoretical
amount of air is used, the combustion reaction is complete and reactants enter at 25 C.
C
p
= a + bT + cT
2
, cal/kmole K
where a, b and c are all dimensional constants and available in literature
3
c 10
5
Gas a b 10
CO
2
10.55 2.16 2.04 N
2
6.66 1.02
C CO
CO
2
CO II Combustion
2
I Combustion
O2 N2Air N2
Basis: 100 g moles of inlet gas
CO entering 25 g moles, CO
2
exit = 25 + 12.5 = 37.5 g moles

79
= 109.52 g moles
2
needed 12.5 g moles, N
2
= tO

CO + O
2
CO
2
Reaction (a) (b) gives
DH
rxn
= 94 + 26 = 68 kcal/kmole
Calorific value: Heat given out = 68 25 = 1,700 kcal Exit gases carry this heat away.
This gas temperature is called Theoretical flame temperature which is calculated as follows:
17 10
5
cal = 37.5 [{10.55 (T 298)} + 2.16 10
3
(T
2
298
2
)/2
2.04 10
5
(T
3
298
3
)/3] + 109.52[6.66 (T 298) + 1.02 10
3
(T
2
298
2
)/2] Solving the above
equation we have T = 2721.085K 2721 K = 2448 C.
9.19 An inventor thinks he has developed a new catalyst which can make the gas phase reaction CO
2
+ 4H
2
CH
4
+ 2H
2
O proceed to 100% conversion. Estimate the heat that must be provided or
removed if the reactants enter and products leave at 500 C (in effect, we have to calculate the heat of
reaction at 500 C).
DH
f
CO
2
CH
4
H
2
O kcal/kmole 94,052 17,889 57,798 at 298 K
\D H
rxn
= [17,889 (2 57,798)] [94,052]
= 39,433 kcal/kmole of CO
2
C
p
for CO
2
= 6.339 + 10.14 10
3
T 3.415 10
6
T
2
H
2
= 6.424 + 1.039 10
3
T 0.078 10
6
T
2
H
2
O = 6.97 + 3.464 10
3
T 0.483 10
6
T
2
CH
4
= 3.204 + 18.41 10
3
T 4.48 10
6
T
2
Da = [3.204 + (2 6.97) 6.339 (4 6.424)] = 14.891
Db = [18.41 + (2 3.464) 10.14 (4 1.039) = 11.047 10
3
= [4.48 (2 0.483) {3.415 (4 0.078)}] = 1.719 10
6
Dg
DC
p
= 14.891 + 11.047 10
3
T 1.719 10
6
T
2
We find DH
o
using data at 298 K
'
T
2

'
T
3
DH
o
= DH
rxn
DaT


= 39,433 (14.891

298)
11.047
10

3

2 tt2


3

1.716
10
6
tt 3
DH
o
= 39,433 + 4,430 491 + 15.16 = 35,479 kcal Next we find DH
rxn
at 500 C (or) 773
K:
'
T
3
DH
773
= DH
o
+ DaT +
'
T
2
+

= 35,479 + (14.891

773) +
11.047
10

32 tt 773
2
1.719

10
63
+
t t
773
3
= 43,943 kcal/kmole
\ 43,943 kcal of heat must be removed.
9.20 CO at 50 F is completely burnt at 2 atm pressures with 50% excess air, which is at 1000 F.
The products of combustion leave the combustion chamber at 800 F. Calculate the heat evolved from
the combustion chamber in terms of Btu/lb of CO entering.
Basis: 1 lb mole of CO = 28 lb, O
2
needed = 0.5 lb mole CO + O
2
CO
2
O
2
supplied = 0.5 1.5 = 0.75 lb mole (50% excess)
Air supplied = 3.57 lb mole and N
2
= 2.82 lb moles
DH
rxn
= 1,21,745 Btu/lb mole
Q = DH
rxn
+ DH
products
DH
reactants
O
2
remaining = 0.25 lb mole
CO
2
: 1 lb mole, N
2
: 2.82 lb moles
Datum: 32F
Data: DH (Btu/lb mole)
Temperature , F CO Air O
2
N
2
CO
2
50 125.2
77 313.3 312.7 315.1 312.2 392.2 800 5,690 5,443 8,026 1000 6,984
DHproducts = DH800F DH77F
= 1(8,026 392.2) + 2.82(5,443 312.2) + 0.25(5,690 315.1) = 23,446 Btu/lb mole
DH reactants: (DH
1000F
DH
77F
)
air
+ (DH
50F
DH
77F
)
CO
= 3.57 (6,984 312.7) + 1(125.2
313.3)
= 23,612 Btu/lb mole
Q = 1,21,745 + 23,446 23,628 = 1,21,927 Btu/lb mole Heat evolved by combustion =
1,21,927/28
= 4,354.5 Btu/lb of CO 9.21 Pure CO is mixed with 100% excess air and completely burnt at constant
pressure. The reactants are originally at 200 F. Determine the heat added or removed, if the product
temperatures are 200 F, 500 F, 1000 F, 1500 F, 2000 F and 3000 F.
Basis: 1 lb mole of CO
CO + O
2
CO
2
O
2
supplied = 1 lb mole, N
2
= 3.76 lb moles
Exit: CO
2
: 1 lb mole, O
2
: 0.5 lb mole, N
2
: 3.76 lb moles
Assuming a base temperature of 25
o
C, (77
o
F) and using mean heat capacities,
D H = Hp H
R;
Q = DH
DH = SnC
ppr
(77 200) + DH
rxn77 F
+ SnC
pR
(t 77)
Reactants: DH
rxn
= 1,21,745 Btu/lb mole
Gas n C
p
nC
p
CO 1 6.95 6.95
CO 1 6.95 6.95
O
2
1 7.10 7.10
N
2
3.76 6.95 26.13
Total 40.18
\SnC
ppr
(77 200) = (40.18 123) = 4,942 Btu DH = 4,942 1,21,745 + SnC
pR
(t 77)
200 F 500 F 1000 F 1500 F 2000 F 3000 F n C
p
nC
p
C
p
nC
p
C
p
nC
p
C
p
nC
p
C
p
nC
p
C
p
nC
p
CO
2
1.0 9.15 9.15 9.9 9.9 10.85 10.85 11.5 11.5 12.05 12.05 12.75 12.75
O
2
0.5 7.10 3.55 7.25 3.63 7.15 3.88 7.8 3.9 8.0 4.0 8.3 4.15
N
2
3.76 6.95 26.13 7.0 26.32 7.15 26.88 7.35 27.64 7.55 28.39 7.88 29.42
S
nC
pR
38.83 39.85 41.51 43.04 44.44 46.32
SnC
p
(t77) 4,776 16,857 38,314 61,246 83,758 1,35,810
Q = DH 21,911 1,09,830 88,373 65,441 41,229 +9,123
9.22 Coal is burnt to a gas of the following composition: CO
2
: 9.2, CO : 1.5, O
2
: 7.3, N
2
: 82%. What
is the enthalpy difference for this gas between the bottom and the top of the stack if the temperature at
the bottom is 550 F and at the top is 200 F?
C
p
of N
2
= 6.895 + 0.7624 10
3
T 0.7 10
7
T
2
C
p
of O
2
= 7.104 + 0.7851 10
3
T 0.5528 10
7
T
2
C
p
of CO
2
= 8.448 + 5.757 10
3
T 21.59 10
7
T
2
+ 3 10
10
T
3
C
p
of CO = 6.865 + 0.8024
10
3
T 0.736 10
7
T
2
Basis: 1 lb mole of CO
2
:
Multiplying these equations by the respective mole fractions of each component and adding them
together, we have
for N
2
= 0.82 C
pN2
for O
2
= 0.073 C
pO2
for CO
2
= 0.092 C
pCO2
for CO = 0.015 C
pCO
C
pnet
= 7.049 + 1.2243 10
3
T 2.6164 10
7
T
2
+ 0.2815 10
10
T
3
200

Cp
net
dT
\DH =

550
= 7.049 (200 550) +
1.2243

10
3

t

(200
2
550
2
)
2

2.6164

107
(200
3
550
3
) + 0.2815
1010
t
3
t

4

(200
4
550
4
)
or, DH = 2,465 160.6 + 13.8 0.633 = 2,612 Btu 9.23 Calculate the theoretical flame
temperature for CO burnt at constant
pressure with 100% excess air? The reactants enter at 200 F. CO + O
2
CO
2
Basis: 1 g mole CO
Temperature of reactants: 200 F = 93.3 C
Gases entering: CO1, O
2
1, N
2
3.76 (all in moles)
Gases leaving: CO
2
1, O
2
0.5, N
2
3.76 (all in moles)
\DH
rxn
25 C = 67,636 cal.
Gas mole DTC
pm
DH = nC
pm
DT CO 1.0 (93.3 25) 6.981 476
Air 4.76 (93.3 25) 6.993 2,270
Total 2,746 cal
Next we have DH
product
= (DH
reactants
DH
rxn
)
= (2,746 + 67,636) = 70,382 cal Let us assume exit temperature as 1800 C, then DT = (1800
25) = 1775 C Gas mole DTC
pm
DH
CO
2
1.0 1775 12.94 23,000
O
2
0.5 1775 8.35 7,400
N
2
3.76 1775 7.92 52,900
This total of 83,300 cal is not matching with 70,382 cal, the value calculated.
Let the Theoretical flame temperature be 1500 C, then DT = 1475 C DH = (1 12.7 1475) + (0.5
8.31 1475) + (3.76 7.88 1475)
= 68,460 cal
Making linear interpolation for the theoretical flame temperature, we have,
Theoretical flame temperature
= 1500 +

70,382
68,460

(1800 1500)
83,300

= 1500 + 39 = 1539 C 2798 F
9.24 Calculate the theoretical flame temperature of a gas having 20% CO and 80% N
2
when burnt
with 150% excess air. Both air and gas being at 25 C.
Data: Heat of formation of CO
2
= 94,052 cal/g mole, CO = 26,412 cal/g mole at 25 C.
C
pm
: CO
2
: 12.1, O
2
: 7.9, N
2
: 7.55 cal/g mole K (from literature) Basis: 1 g mole CO, CO + 0.5O
2

CO
2
O
2
supplied = (0.5 2.5) = 1.25 g moles (150% excess)

80
N
2
in feed
= 1

= 4 g moles

N
2
in air
=
79
= 4.7 g moles
21
Exit gas: CO
2
: 1 g mole, O
2
: 0.75 g mole, N
2
: 8.7 g moles Q = SH
products
+ SH
rxn
SH
reactants
. (Datum
298 K)
SH
reactants
is zero, since air and gas are at 25 C.
DH
rxn
= DH
CO2
DH
CO
= 94,052 (26,412) = 67,640 cal/g mole.
Let the Theoretical Flame Temperature be T, K
67,640 = [1 12.1 (T 298)] + [8.7 7.55 (T 298)] + [0.75 7.9 (T 298)], 67,640 = 83.71 T
24,945.6
\ T = 1106.03 K 833.03 C
1106 K 833 C.
9.25 Find the theoretical flame temperature of a gas containing 30% CO and 70% N
2
when burnt with
100% excess air. The reactants enter at 298 K.
DH
f
CO
2
= 3,93,700 kJ/kmole; DH
f
CO = 1,10,600 kJ/kmole Mean molar specific heat, kJ/kmole
K at different temperatures is given below:
Temperature K CO
2
O
2
N
2
800 45.4 31.6 30.3
1000 47.6 32.3 30.6
1200 49.4 33.0 31.2
1400 50.8 33.6 31.8
1600 52.0 34.0 32.3
1800 53.2 34.4 32.7
Basis: 1 kmole of CO, Datum: 298 K
N
2
in feed = 70/30 = 2.34 kmoles
O
2
supplied = 0.5 2 = 1 kmole
N
2
from air = 3.76 kmoles
Exit gas consists of:
CO
2
: 1, O
2
: 0.5, N
2
: (3.76 + 2.34) = 6.1 kmoles
Let us consider the equation
Q = SHproducts + DHrxn SHreactants
where SH
reactants
= Zero at 298 K (
Q
Datum is 298 K)
\DH
rxn
= (3,93,700) (1,10,600) = 2,83,100 kJ/mole By iteration method:
Let the theoretical flame temperature be 1400 K:
DT = (1400 298) = 1102 K
DH
pr
= (1 50.8 1102) + (0.5 33.6 1102) + (6.1 31.8 1102)
= 2,88,261 kJ/kmole 2,83,100 kJ/kmole
Let the theoretical flame temperature be 1200 K
\DT (1200 298) = 902 K
DH
pr
= (1 49.4 902) + (0.5 33 902) + (6.1 31.2 902)
= 2,31,110 kJ/kmole 2,83,100 kJ/kmole
So theoretical flame temperature lies in between these two values (by interpolation )
\ Theoretical flame temperature
2,83,100
2,31,110
= 1,200 +


2,88,261 2,31,110
(1400 1200)

So, the temperature of the exit gases is 1382 K = 1109 C.

9.26 The analysis of 15,000 lit of a gas mixture at standard condition is as follows: SO
2
: 10%, O
2
:
12% and N
2
: 78%. How much heat must be added to this gas to change its temperature from 30 C to
425 C?
The C
pm
values are in cal/g mole C
Gas SO
2
O
2
N
2
C
pm 30 C
10 6.96 6.80 C
pm 425 C
11 7.32 7.12
The amount of gas mixture = 15,000 litres

15,000
22.414
= 669.2 g moles
we can then write the amount of each component
SO
2
: 669.2 0.1 = 66.92 g moles
O
2
: 669.2 0.12 = 80.30 g moles
N
2
: 669.2 0.78 = 521.98 g moles
669.20 g moles
Reference temperature: 0 C
\ Q = 66.92 [(11 425) (10 30)] + 80.3 [(7.32 425) (6.96 30)]
+ 521.98 [(7.12 425) (6.8 30)] = 19,98,849.22 cal 9.27 Estimate the theoretical flame
temperature of a gas containing 20% CO and 80% N
2
when burnt with 100% excess air. Both air and
gas are initially at 25 C.
C
p
CO
2
= 6.339 + 10.14 10
3
T 3.415 10
6
T
2
C
p
O
2
= 6.117 + 3.167 10
3
T 1.005 10
6
T
2
C
p
N
2
= 6.457 + 1.389 10
3
T 0.069 10
6
T
2
The values of C
p
are in kcal/kmole K and temperature is in K DH
rxn
25 C = 67,636 kcal
Basis: 1 kmole of CO; N
2
= 4 kmoles
Air supplied: O
2
: 1 kmole, N
2 from air
: 3.76 kmoles
Exit gas: CO
2
: 1, O
2
: 0.5, N
2
: 7.76 kmoles
Datum 25 C = 298 K
DH
rxn
= DH products + 67,636 = [1 C
pCO2
(T 298)] + [0.5 C
pO2
(T 298)]
+ [7.76 C
pN2
(T 298)]
22
67,636 = 6.339(
T
298) + 10.14

10
3 T 298
2

33 T 298
3.415 10
6 T 298

3
+ 6.117
2

22
T
33
+ 3.167

10

3 T 298
1.005 10
6 298
4 6 T

22
+ 7.76

6.457

(
T
298) + 7.76

1.389

10
3 298
2 T

33
7.76

0.069

10
6 298
3
Solving for theoretical flame temperature = T = 1216 K = 943 C
9.28 Dry methane and dry air at 298 K and 1 bar pressure are burnt with 100% excess air. The
standard heat of reaction is 802 kJ/g mole of methane. Determine the final temperature attained by
the gaseous products if combustion is adiabatic and 20% of heat produced is lost to the surroundings.
Data: C
pm
values (J/g mole K) for the components are: O
2
: 31.9, N
2
: 32.15, H
2
O : 40.19, CO
2
:
51.79.
Basis: 1 g mole of methane.
Datum: 298 K
CH
4
+ 2O
2
CO
2
+ 2H
2
O
\ Oxygen supplied = 2 2 = 4 g moles
N
2
entering = 4
79
= 15.05 g moles
21
Gases leaving are: CO
2
: 1, H
2
O : 2, O
2
: 2, and N
2
: 15.05 g moles. Heat given out = 802 kJ
Heat loss = (802 0.2) = 160.4 kJ
\ Q = Heat in exit gases = (802 160.4) = 641.6 kJ
Q = [1 51.79 (T 298)] + [2 40.19 (T 298)] + [2 31.9 (T 298)] + [15.05 32.15 (T
298)] = [679.8275 (T 298)] = 641.6 10
3
J.
\ T = 1242 K = 969 C.
9.29 An iron pyrite ore contains 85% FeS
2
and 15% gangue. It is roasted with 200% excess air to get
SO
2
. The reaction is given. All the gangue plus Fe
2
O
3
end up in the solid waste produced which
analyzes 4% FeS
2
. Determine the standard heat of reaction in kJ/kg of ore roasted and the analysis of
the solid waste. Heat of formation data is in kJ/g mole.
4FeS
2
+ 11O
2
2Fe
2
O
3
+8SO
2
Weights 479.4 352 319.4 512
Heats of formation 177.9 0 88.2 296.9 (kJ/g mole)
Basis: 1 kg of ore containing FeS
2
= 0.85 kg and gangue = 0.15 kg Let x kg of FeS
2
be in the solid
waste,

319.4

then, FeS
2
reacted: (0.85 x) kg; Fe
2
O
3
formed (0.85 x)
= 0.666(0.85 x)
x = 0.04{(0.15) + 0.666(0.85 x) + x};
Solving the above, we find x = 0.029 kg
Solid waste = (0.15) + (0.029) + [0.666 (0.85 0.029)] = 0.725786 kg A summary of the
composition of the solid waste is given:
Solid waste kg Weight %
Gangue 0.150 20.66
FeS
2
0.029 3.99
Fe
2
O
3
0.547 75.35
Total 0.726 100.00
FeS
2
reacted = (0.85 0.029) = 0.821 kg = 6.85 10
3
kmole\
Fe
2
O
3
formed = 0.547 kg = 3.424 10
3
kmole
SO
2
formed =

512
= 1.068 kg = 0.016688 kmole
479.4

Heat of reaction = [(0.016688 296.9) + (3.424 10
3
822.3)
(6.85 10
3
177.9)]
= 6.55 kJ
9.30 For the following reaction, estimate the heat of reaction at 298 K. A + B C + D
Compound DH
f
(kcal/g mole)
A 269.8
B 195.2
C 337.3
D 29.05
DH at 25 C = SDH
f, Products
SDH
f, reactants
= [337.3 29.05] [269.8 195.2]
= 98.65 kcal
9.31 Estimate the standard heat of reaction DH
298
for the reaction. A + B C
Standard heats of combustion are:
DH
c, 298
for A = 328000 cal/g
DH
c, 298
for B = 212000 cal/g
DH
c, 298
for C = 542000 cal/g
DH
c, 298
= SDH
c
, reactants SDH
c
, products
= [328000 212000] [542000]
= 2000 cal
9.32 Calculate the heat of formation of CHCl
3
from the following data:
CHCl
3
+
1
O
2
+ H
2
O CO
2
+ 3HCl, DH = 509.93 kJ (1)
2
H
2
+
1
O
2
H
2
O; DH = 296 kJ (2)
2
C + O
2
CO
2
; DH = 393.78 kJ (3)
1
H
2
+
1
Cl
2
HCl; DH = 167.5 kJ (4)
2 2
CO
2
+ 3HCl
1
O
2
+ H
2
O; DH = 509.93 kJ CHCl
3
+
2

H
2
+
1
O
2
H
2
O; DH = 296 kJ
2
C + O
2
CO
2
; DH = 393.78 kJ
Eq. (4) 3 + Eq. (3)/2, gives
3
H
2
+ Cl
2
+
1
C +
1
O
2
3HCl +
1
CO
22 2 2 2
9.33 Standard heat of reaction accompanying any chemical change is equal to the algebraic sum of the
standard heat of formation of the products minus the algebraic sum. Calculate the standard heat of
reaction, DH
f, 298
for the reaction
2FeS
2
+ 1.5O
2
Fe
2
O
3
+ 4SO
2
The standard heats of formation are:
FeS
2
= 42,520 cal/g mole
Fe
2
O
3
= 1,96,500 cal/g mole
SO
2
= 70,960 cal/g mole
From the reaction,
DH
r, 298
= DH
Fe2O3
+ 4 [DH
SO2
] 2[DH
FeS2
]
= 19,6500 + 4[70,960] 2[42,520]
= 39,5300 cal
9.34 The heat of reaction at 300 K and 1 atm pressure for the reaction A + 3B C is 30,000 cal/mole
A converted.
C
p
data is as follows:
A = 0.4 + 0.1 T (T in K)
B = 10
C = 30
Calculate the heat of reaction at 600 K and 1 atm
A + 3B C
600
H
600
= DH
300
+ 'C
p
.dTD

300
600

= 30,000 + [{30
3 10 + 0.4}
0.1T] dT

300
= 30,000 + 0.4
T
0.1
T
2
2
= 30,000 + 0.4[600 300] [0.05 (600
2
300
2
)] = 43,380 cal/g mole of A
9.35 Calculate the theoretical flame temperature of a gas containing 20% CO and 80% N
2
when burnt
with 150% excess air, with both air and gas being at 25 C.
D H
f
C
pm
CO
2
= 393.137 kJ/g mole CO
2
= 50.16 kJ/kg K CO = 110.402 kJ/g mole O
2
= 33.02 kJ/ kmole H
2
=
31.56 kJ/kmole K
Basis: 100 g moles of feed
CO = 20 g moles
CO +
1
O
2
CO
22

O
2
needed =
1
20 = 10 g moles
2
O
2
supplied = 2.5 10 = 25 g moles
N
2
supplied = 25 79/21 = 94.05 g moles Gases leaving
CO
2
= 20 g moles
O
2
= 25 10 = 15 g moles
N
2
= 94.05 + 80 = 174.05 g moles
Atmospheric temperature = 25 C
Heat in reactants + DH
R
= Heat in products Standard heat of reaction,
D H
f

products
DH
f

reactants
= 393.137 [110.402 +
1
0]
2
= 282.835 kJ/g mole
Heat of reactants is zero (Reference temperature)
Heat produced when 20 g moles of CO is burnt
= 282.835 20 = 5654.700 kJ
Heat in outgoing gas,
{20 [50.16] + 15 [33.02] + 174.05 [31.56]} (T 25) = 5654700 Solving, T = 834 C
EXERCISES
9.1 Determine the theoretical flame temperature that can be attained by the combustion of methane
with 20% excess air. Air and methane enter at 298 K and a pressure of 1 atm. The reaction is
complete.
DH
r
= 1,91,760 cal/g mole
Mean heat capacities (cal/g mole K)
Component Temperature 2000 C 1800 C CO
2
13.1 12.95 H
2
O 10.4 10.25 O
2
8.4 8.3 N
2
8.0 7.9
9.2 Determine the heat of reaction at 720 K and 1 atm for the reaction
SO
2
+ 0.5O
2
SO
3
Mean molar specific heats of
SO
2
: 51.5 kJ/kmole K
O
2
: 45.67 kJ/kmole K
SO
3
: 30.98 kJ/kmole K
Standard heat of formation for
SO
2
: 2,97,000 kJ/kmole
SO
3
: 3,95,000 kJ/kmole
9.3 Calculate the enthalpy change in J/kmole that takes place in raising the temperature of 1 kmole of
the gas mixture of 80 mole %. Methane and rest ethane from 323 K to 873 K
Heat capacity equation, C
p
= R (A + BT + CT
2
) cal/g mole where, R is Gas constant, T is temperature
in K. A, B and C are constants and C
p
is the heat capacity at constant pressure.
Component Value of constant in C
p
equation AB 10
3
C 10
6
CH
4
1.702 9.081 2.164 C
2
H
6
1.131
19.225 5.561
9.4 Chlorine is produced by the reaction
4HCl(g) + O
2
(g) 2H
2
O(g) + 2Cl
2
(g)
The feed stream to the reactor consists of 67 mole % HCl, 30 mole %
O
2
and 3 mole % N
2.
If the conversion of HCl is 75% and the process is isothermal, how much heat is
transferred per mole of entering gas mixture.
Data:
(a) Standard heat of formation at 25 C, J/g mole
HCl(g) : 92,307 J/g mole
H
2
O(g) : 2,41,818 J/g mole
(b) Mean heat capacities: (cal/g mole K)
HCl(g) : 7.06
O
2
(g) : 8.54
H
2
O : 7.52
Cl
2
(g) : 8.61
N
2
(g) : 7.16
9.5 Calculate the number of joules required to calcine completely 100 kg of limestone containing
80% CaCO
3
, 11% MgCO
3
and 9% water. The lime is withdrawn at 900 C and the gases leave at
200 C. The lime stone is charged at 25 C.
Data: Standard heat of formation at 25 C and 1 atm, cal/g mole CaCO
3
: 2,88,450 cal/g mole
MgCO
3
: 2,66,000 cal/g mole
CaO : 1,51,900 cal/g mole
MgO : 1,43,840 cal/g mole
CO
2
: 94,050 cal/g mole
Mean molal heat capacity, cal/g mole K
H
2
O : 8.2
CO
2
: 10.5
CaCO
3
: 25.0
MgCO
3
: 23.0
CaO : 14.0
MgO : 10.0
9.6 In the reaction
4FeS
2
(s) + 11O
2
(g) 2Fe
2
O
3
(s) + 8SO
2
(g) the conversion from FeS
2
to Fe
2
O
3
is only 80%
complete. If the standard heat of formation for the above is calculated to be
197.7 kcal/g mole, what DH
reaction
should be used in energy balance per kg of FeS
2
fed.
9.7 Calculate the theoretical flame temperature for CO burnt at constant pressure with 20% excess
air. The reactants enter at 366 K. CO + O
2
CO
2
The heat capacities are 29.23 for CO, 29.28 for air, 54.18 for CO
2,
34.5 for O
2
and 33.1 for N
2
in J/g
mole K. Standard heat of reaction:
283.13 kJ/g mole.
9.8 A gaseous mixture of 1000 m
3
containing 60% hydrogen and 40% ammonia is cooled from 773 K
to 313 K at 1 atm pressure. Calculate the heat removed. The C
p
values in kcal/kmole K, and T in K
are: for hydrogen C
p
= 6.9 0.2 10
3
T + 0.48 10
6
T
2
for ammonia C
p
= 6.08 + 8.81 10
3
T 1.5
10
6
T
2
9.9 Determine the theoretical flame temperature that can be obtained by the combustion of
methane with 25% excess air. Air and methane enter at 298 K and a pressure of 1 atm. The reaction is
complete. Standard heats of formation at 298 K in kJ/kmole are: Methane (g) = 74,520
Carbon dioxide (g) = 3,93,500
Water vapour (g) = 2,41,813
9.10 Calculate the amount of heat given off when 1 m
3
of air at standard condition cools from 600 C
to 100 C at constant pressure C
p
air = 6.386 + 1.762 10
3
T 0.2656 10
6
T
2
C
p
is in kcal/kmole K and T is in K.
9.11 CO is burnt under atmospheric pressure with dry air at 773 K with 20% excess air. The products
leave at 1223 K. Calculate the heat involved in the reaction chamber in kcal/kmole of CO burnt,
assuming complete combustion.
Data: DH
298 K
= 67,636 kcal
Mean specific heats are: 7.017 for CO, 7.225 for air, 11.92 for CO
2,
7.941 for O
2
and 7.507 for N
2
in
kcal/kmole K.
Problems on Unsteady
10
State Operations
The term unsteady state refers to chemical processes in which the operating conditions generally
fluctuate with time. Although unsteady-state processes are difficult to formulate, the general formula
used to represent the total amount of material and energy in the process is given as
Rate of input + Rate of generation = Rate of output + Rate of accumulation This is the guiding
principle in solving problems on the unsteady state operations.
WORKED EXAMPLES
10.1 A storage tank contains 10,000 kg of a solution containing 5% acetic acid by weight. A fresh
feed of 500 kg/min of pure water is entering the tank and dilutes the solution in the tank. The mixture
is stirred well and the product leaves the tank at a rate of 500 kg/min. At what instant of time the acid
concentration in the tank will drop to 1% acetic acid by weight? After one hour of operation, what
will be the concentration in the tank?
F
i
X
i
M, X
F
o
, X
o
= X
221
Here inlet flow rate, F
i
= 500 kg/min
Outlet flow rate, F
o
= 500 kg/min
Initial mass = 10,000 kg
The total mass M, at any time in the tank
= Initial mass + (Inflow rate Outflow rate)(time) = 10,000 + (500 500)t
= 10,000 kg
We know that,
rate of input + rate of generation = rate of output
+ rate of accumulation (1)
Here, rate of generation is zero.
Let X be the concentration of acid and M the mass of solution of acid at any time.
Hence, rate of accumulation = rate of input rate of output or,

d MX()
= F
i
X
i
F
o
X (2)
dt
dXdM
MX= F
i
X
i
F
o
X (3)
dtdt

Here,
dM
= 0 (Since inlet and outlet flow rates are the same)
dt

Therefore, M
dX
= F
i
X
i
F
o
X(4)
dt
dX
Now substituting values, 10,000

= 500 0.0 500X (5)

(i.e.)
dX
= 0.05X
dt

(i.e.)
dX
= 0.05dt
X
Integrating, we get

Xt
dX 0.05dt
X
o
Xt 0
X
ln

= 0.05(t 0)

= 0.05t (6) Therefore,
X
= e
0.05t
(7)
Xo
Time taken to reach a concentration of 1% is given by,
0.01
ln

= 0.05t

i.e. t = 32.19 minutes

(b) Substituting for t as 60 minutes in Eq. (7), we get
X = 0.05 e
0.05 (60)
= 0.00249 = 0.249%
i.e. after one hour of operation, the concentration in the tank will be 0.249%
10.2 A tank contains 10 kg of a salt solution at a concentration of 2% by weight. Fresh solution enters
the tank at a rate of 2 kg/min at a salt concentration of 3% by weight. The contents are stirred well
and the mixture leaves the tank at a rate of 1.5 kg/min.
(a) Express the salt concentration as a function of time and (b) At what instant of time the salt
concentration in the tank will reach 2.5% by weight?
Here inlet flow rate, F
i
= 2 kg/min
Outlet flow rate, F
o
= 1.5 kg/min
Initial mass = 10 kg
The total mass M, at any time in the tank
= Initial mass + (Inflow rate Outflow rate)(time) = 10 + (2 1.5)t
or, M = 10 + 0.5t
Differentiating, we get
dM
= 0.5
dt
We know that
rate of input + rate of generation
= rate of output + rate of accumulation (1) Here, rate of generation is zero.
Let X be the concentration of acid and M the mass of solution of acid at any time.
Hence, rate of accumulation = rate of input rate of output
i.e.
d MX()
= F
i
X
i
F
o
X (2)
dt
or, M
dX
+ X
dM
= F
i
X
i
F
o
X (3)
dt dt
Here,
dM
= 0.5
dt
Therefore, by substituting values, we get
(10 + 0.5t)
dX
+ 0.5X = 2 0.03 1.5X (4)
dt

(i.e.) (10 + 0.5t)
dX
= 0.06 2X
dt

or, dXdt (5)
0.06 2Xt

Integrating, we get
Xt
dt Xt
o

Xt 0
Xt
also,
0.5
dXdt

Xt
o
Xt0
ln
X
0.03

(20 t)
(6)
0.02 0.03

20

4
or,
X

0.03
20

(7)
0.01

t
204

\ X = 0.03 0.01

(8)
20t
Time taken to reach a concentration of 2.5% is given by substituting X = 0.025 in Eq. (7).
Hence, we have,
(20 +
t
)
4
= 20
4

0.01
0.03 X
Hence, t = 3.784 minutes
Aliter
We shall go back to Eq. (4), which is
(10 + 0.5t)
dX
+ 0.5X = 2 0.03 1.5X
dt
or,


20.06 (9)
dtt t


This equation is of the form
dy
+ Py = Q (10)
dx
Where, P and Q are either functions of x or constants
The solution for this differential equation is
ye
Pdx
= Qe
Pdx
dx + constant (11)
Using the same analogy we can solve Eq. (9) in the following manner 24
P = 10 0.5 20tt
and
0.06 0.12 Q tt
Substituting for P and Q in Eq. (11), we get

44

dtdt
X

t t

0.12ee
dt + constant (12)
20 t
X 4 exp[ln(20 + t)]
X(20 + t)
0.12

=

4 exp[ln(20 + t)] dt + constant

20t
0.12

4
=

[20 + t]
4
dt + constant
20t

or, X(20 + t)
4
= [0.12][20 + t]
3
dt + constant
X
(20 +
t
)
4
= 0.12
[20 t]4
4
+ constant (13)
X = 0.03 +
constant
(14)
(20 t)4
Initial conditions are:
t = 0, X = 0.02
Substituting in Eq. (14), we get, Constant = 0.01 (20)
4
= 1600 Equation (14) thus becomes,
X = 0.03
1600
and (15)
(20 t)4
204

X = 0.03 0.01

(16)
(20t)
Comparing Eq. (16) with Eq. (8) we find both are same and hence the time taken to reach a
concentration of 2.5% is 3.784 minutes
10.3 A tank contains 10 litre of a salt solution at a concentration of 2 g/litre Another salt solution
enters the tank at a rate of 1.5 litres/min at a salt concentration of 1 g/litre. The contents are stirred
well and the mixture leaves the tank at a rate of 1.0 litre/min.
Estimate (a) the time at which the concentration in the tank will be 1.6 g/litre and (b) the contents in
the tank will be 18 litres
Here, Inlet flow rate, F
i
= 1.5 litres/min at a salt concentration of 1 g/litres Outlet flow rate, F
o
= 1.0
litre/min
Initial volume = 10 litres.
The total volume V, at any time
= Initial volume + (Inflow rate Out flow rate) (time) = 10 + (1.5 1.0)t
or, V = 10 + 0.5t
Differentiating, we get
dV
= 0.5
dt
We know that,
rate of input + rate of generation
= rate of output + rate of accumulation (1) Here rate of generation is zero.
Let C be the concentration of salt and V the volume of solution at any time.
Hence, rate of accumulation = rate of input rate of output
i.e.
d VC()
= F
i
C
i
F
o
C (2)
dt
V
dC
+ C
dV
= F
i
C
i
F
o
C (3)
dt dt

Here,
dV
= 0.5
dt
Therefore, by substituting values,
(10 + 0.5t)
dC
+ 0.5C = 1.5 1.0 1.0C (4)
dt

i.e. (10 + 0.5t)
dC
= 1.5 1.5C = 1.5(1 C)
dt
dC

or, dt (5)
1.5(1
=-+
Ct
Integrating, we get

Ct

dt
1.5

Ct0.5 )
=0oCt
Ct

dt
=Ct)
Ct 20
o
==
ln
Ct

(6)
-

3
C - =
(7)120+


3
\ C = 1 +
+
(8)
Time taken to reach a concentration of 1.6 g/litres is given by substituting C = 1.6 in Eq. (8):
0.6 = +

3
+
solving, t = 3.71 minutes.
(b) Final volume
= Initial volume + (volume flowing in volume flowing out)(time) or, 18 = 10 + (1.5 1.0)t
Therefore, time taken for the water in the tank to reach 18 litres is = 16 minutes.
EXERCISES
10.1 A tank contains 500 kg of a 10% salt solution. A stream containing salt at 20% concentration
enters the tank at 10 kg/h and the mixture leaves the tank after thorough mixing at a rate of 5 kg/h.
Obtain an expression for the salt concentration in the tank as a function of time and the salt
concentration in the tank after 3 hours.
10.2 A tank contains 1000 kg of a 10% salt solution. A stream containing salt at 20% concentration
enters the tank at 20 kg/min and the mixture leaves the tank after complete mixing at a rate of 10
kg/min. Obtain an expression for the salt concentration in the outlet as a function of time and the salt
concentration in the tank after 1 hour. What will be the time at which the salt concentration in the tank
will be 15%?
10.3 A tank contains 50 litres of a salt solution at a concentration of 2.5 g/litre. Another salt solution
enters the tank at a rate of 2.0 litres/min. at a salt concentration of 1 g/litre. The contents are stirred
well and the mixture leaves the tank at a rate of 2.5 litres/min.
Estimate (a) the time at which the concentration in the tank will be 1.25 g/litre and (b) the contents in
the tank will be 20 litres.
10.4 A tank contains 20 kg of a salt solution at a concentration of 4% by weight. Fresh solution enters
the tank at a rate of 2.5 kg/min at a salt concentration of 3% by weight. The contents are stirred well
and the mixture leaves the tank at a rate of 2.0 kg/min. (a) Express the salt concentration as a function
of time and (b) At what instant of time the salt concentration in the tank will reach 3.75% by weight?
10.5 A storage tank contains 5000 kg of a 1% sugar solution by weight. A fresh feed of 400 kg/min of
pure water is entering the tank and dilutes the solution in the tank. The mixture is stirred well and the
product leaves the tank at a rate of 400 kg/min. At what instant of time the sugar concentration in the
tank will drop to 1% sugar by weight? After one hour of operation, what will be the concentration in
the tank?
10.6 A 15% Na
2
SO
4
solution is fed at the rate of 12 kg/min into a mixer that initially holds 100 kg of
a 50 : 50 mixture of Na
2
SO
4
and water. The exit solution leaves at the rate of 9 kg/min. Assuming
uniform mixing, what is the concentration of Na
2
SO
4
in the mixer at the end of 10 minutes. Volume
change during mixing can be neglected.
10.7 A cylindrical tank of cross-sectional area A is filled with liquid up to a height H
o
. A hole of
diameter d at the bottom of the tank, which was plugged initially is opened to let the liquid drain
through it. Set up an unsteady state balance equation to calculate the time for the liquid level to fall to
a new height H
1
.
10.8 A solution is having solute A at a concentration C
Af
is fed continuously into a mixing vessel of
constant volume V, into which water is added continuously and diluted. The outlet concentration of
the solution is C
ao
. Write the unsteady state solute balance equation. Discuss about the solution of the
equation.
Tables
TABLE I Important Conversion Factors
Quantity
Length
To convert Multiply by from to
in ( ) m 0.0254 ft () m 0.3048 cm m 0.01 Angstrom () m 10
10
6
microns (m)m 10
Area in
2
m
2
6.452 10
4
ft
2
m
2
0.0929 cm
2
m
2
10
4
Volume ft
3
m
3
0.02832
cm
3
m
3
10
6
litre m
3
10
3
Gallons (UK) m
3
4.546 10
3
Gallons (US) m
3
3.285 10
3
Mass Pound (lb) kg 0.4536 Gram (g, gm) kg 10
3
Density
Force lb/ft
3
kg/m
3
16.019 g/litre kg/m
3
1.0 g/cm
3
kg/m
3
1000
lbf N 4.448
kgf N 9.807
Pa N 980.7
dyne N 10
5
TABLE I Important Conversion Factors (contd.)
(Contd.) 229
Quantity To convert Multiply by from to
Pressure lb
f
/ft
2
lb
f
/in
2
(psi) in Hg
in water
mm Hg
atm
torr
bar
kg
f
/cm
2
N/m
2
= Pa 47.88 N/m
2
= Pa 6895
N/m
2
= Pa 3386
N/m
2
= Pa 249.1 N/m
2
= Pa 133.3 N/m
2
= Pa 1.0133 10
5
N/m
2
= Pa 133.3 N/m
2
= Pa 10
5
N/m
2
= Pa 9.807 10
4
Heat or energy
Volumetric flow rate Btu
erg
cal
kcal
kW.h
ft
3
/s
ft
3
/h, ft
3
/h cm
3
/s
lit/h
J = N.m 1055 J = N.m 10
7
J = N.m 4.187 J = N.m 4187 J = N.m 3.6 10
6
m
3
/s 0.02832 m
3
/s 7.867 10
6
m
3
/s 10
6
3
/s 2.777 10
7
m
Mass flow rate (Mass flux)
lb/ft
2
.h
g/cm
2
s kg/m
2
s 1.356 10
3
kg/m
2
s 10
Molar flow rate (Molar flux)
Enthalpy lb mole/ft
2
.h g mole/cm
2
s
Btu/lb
cal/g = kcal/kg kmole/m
2
s 1.356 10
3
kmole g/m
2
s10
J/kg = N.m/kg 2326 J/kg = N.m/kg 4187
Heat capacity (Holds good for molal heat
capacity also)
Btu/lb. F
cal/g.C N.m/kg K = J/kg K 4187
N.m/kg K = J/kg K 4187
TABLE II Atomic Weights and Atomic Numbers of Elements
Element Symbol Atomic Number Atomic weight
Actinium Ac Aluminium Al Americium Am Antimony Sb Argon A Arsenic As Astatine At Barium Ba
Berkelium Bk Beryllium Be Bismuth Bi Boron B Bromine Br Cadmium Cd Calcium Ca Californium
Cf Carbon C Cerium Ce Cesium Cs Chlorine Cl Chromium Cr Cobalt Co Columbium Nb Copper Cu
Curium Cm Dysprosium Dy Erbium Er Europium Eu Fluorine F Francium Fr Gadolinium Gd Gallium
Ga Germanium Ge 89 217.00 13 26.98 95 243.00 51 121.76 18 39.94 33 74.91 85 210.00 56 137.36
97 245.00
4 9.01
83 209.00
5 10.82
35 79.92
48 112.41
20 40.08
98 246.00
6 12.01
58 140.13
55 132.91
17 35.46
24 52.01
27 58.94
41 92.91
29 63.54
96 243.00
66 162.46
68 167.20
63 152.00
9 19.00
87 223.00
64 156.90
31 69.72
32 72.60
Element Symbol Atomic Number Atomic weight
Gold Au Hafnium Hf Helium He Holmium Ho Hydrogen H Indium In Iodine I Iridium Ir Iron Fe
Krypton Kr Lanthanum La Lead Pb Lithium Li Lutetium Lu Magnesium Mg Manganese Mn Mercury
Hg Molybdenum Mo Neodymium Nd Neptunium Np Neon Ne Nickel Ni Niobium Nb Nitrogen N
Osmium Os Oxygen O Palladium Pd Phosphorus P Platinum Pt Plutonium Pu Polonium Po Potassium
K Praseodymium Pr 79 197.20 72 178.60
2 4.00
67 164.94
1 1.00
49 114.76
53 126.91
77 193.10
26 55.85
36 83.80
57 138.92
82 207.21
3 6.94
71 174.99
12 24.32
25 54.93
80 200.61
42 95.95
60 144.27
93 237.00
10 20.18
28 58.69
41 92.91
7 14.01
76 190.20
8 16.00
46 106.70
15 30.98
78 195.23
94 242.00
84 210.00
19 39.10
59 140.92
Element Symbol Atomic Number Atomic weight
Promethium Pm Protactinium Pa Radium Ra Radon Rn Rhenium Re Rhodium Rh Rubidium Rb
Ruthenium Ru Samarium Sm Scandium Sc Selenium Se Silicon Si Silver Ag Sodium Na Strontium Sr
Sulphur S Tantalum Ta Technetium Tc Tellurium Te Terbium Tb Thallium Tl Thorium Th Thulium
Tm Tin Sn Titanium Ti Tungsten W Uranium U Vanadium V Xenon Xe Ytterbium Yb Yttrium Y Zinc
Zn Zirconium Zr 61 145.00 91 231.00 88 226.05 86 222.00 75 186.31 45 102.91 37 85.48 44 101.70
62 150.43 21 44.96 34 78.96 14 28.09 47 107.88 11 23.00 38 87.63 16 32.07 73 180.88 43 99.00 52
127.61 65 159.20 81 204.39 90 232.12 69 169.40 50 118.70 22 47.90 74 183.92 92 238.07 23 50.95
54 131.30 70 173.04 39 88.92 30 65.38 40 91.22 TABLE III(a) Empirical Constants for Molal Heat
Capacities of Gases at
Constant Pressure
C
p
= a + bT + cT
2
, where T is in Kelvin; g-cal/(g-mole) (K) Temperature range 300 to 1500 K
Gas a b 10
3
c 10
6
H
2
6.946 0.196 0.4757
N
2
6.457 1.389 0.069
O
2
6.117 3.167 1.005
CO 6.350 1.811 0.2675
NO 6.440 2.069 0.4206
H
2
O 7.136 2.640 0.0459
CO
2
6.339 10.140 3.415
SO
2
6.945 10.010 3.794
SO
3
7.454 19.130 6.628
HCl 6.734 0.431 +0.3613
C
2
H
6
2.322 38.040 10.970
CH
4
3.204 18.410 4.480
C
2
H
4
3.019 28.210 8.537
Cl
2
7.653 2.221 0.8733
Air 6.386 1.762 0.2656
NH
3
(*) 5.920 8.963 1.764
* Gas
TABLE III(b) Molal Heat Capacities of Hydrocarbon Gases For 10 to 760
o
C, C
p
= a + bT + cT
2
o
C, C
p
= 7. 95 + mT
n
For 180 to 95
T in Rankine (
o
F + 460)
Compound a b
3
c 10
6
m n 10
Methane 3.42 9.91 1.28 6.4 10
12
4.00
Ethylene 2.71 16.20 2.80 8.13 10
11
3.85
Ethane 1.38 23.25 4.27 6.20 10
8
1.79
Propylene 1.97 27.69 5.25 2.57 10
3
1.26
Propane 0.41 35.95 6.97 3.97 10
3
1.25
n-Butane 2.25 45.40 8.83 0.93 10
2
1.19
i-Butane 2.30 45.78 8.89 0.93 10
2
1.19
Pentane 3.14 55.85 10.98 3.9 10
2
1.00
Answers to Exercises
CHAPTER 1
1.1 (a) 10.84 cm
2
/s
(b) 39.67 psia
(c) 0.03929 hp-hr
(d) 0.627 lb
f
/ft
2
(e) 0.01355 cal/s cm
2
C
(f) 1163 W/m K
1.2 10.93 [C
p
G
0.8
/D
0.2
]
1.3 4.55 * 10
3
[P/T
0.5
]
1.4 (0.09453) [h
2.5
/g
0.5
] tan F
1.5 As long as consistent units are used, the equation remains the same.
CHAPTER 2
2.1 500 g moles
2.2 0.5455 kg of carbon
2.3 (a) 3.572 g of O
2
(b) 12.77 g of KClO
3
2.4 (a) 2.8%
(b) 0.088
(c) 5.378 g moles/kg of water
2.5 Mole ratio: 0.0425
Mole %: Na
2
CO
3
: 4.1%
Water: 95.9%
2.6 Molality: 5.98 g moles/kg of solution
Molarity: 5.98 g moles/litre
Volume of solution: 0.0836 litre
Normality: 5.98
235
2.7 Weight %: 39.02% Volume %: 26% 2.8
Compound Weight % Volume % mole % NaCl 23.3 11 8.54 H
2
O 76.7 89 91.46 Total 100.00 100
100.00
Atomic %:
Na: 2.93%; Cl
2
: 2.93%; H
2
: 62.76%; and O
2
: 31.38% Molality: 5.185 g moles/kg of solution
2.9 AVMWT: 65.02
Chlorine: 54.98%
Bromine: 10.15%
Nitrogen: 34.87%
2.10 (a) 0.1455 kg sugar/kg water
(b) 1075 kg/m
3
solution
(c) 136.56 g sugar/litre
2.11 (a) Nitrogen
(b) 16.17% and
(c) 59.97%
2.12 0.945 g of Cr
2
S
3
2.13 9.3445 kg of AgNO
3
2.14 (a) Mole fraction of H
3
PO
4
: 0.02
Mole fraction of Water: 0.98
(b) 890.8 cc of solution
2.15 54,090 g
2.16 31.75 kg Cu, 104.26 kg of 94% H
2
SO
4
2.17 (a) H
2
SO
4
(b) 79.25%
(c) 89.625
2.18 NaCl:75%, KCl 25% and NaCl: 79.25%, KCl 20.75%
2.19 2094 kg iron and 900 kg water
2.20 (a) 26.94
(b) Methane: 24.94%, ethane: 14.47%, ethylene: 25.98%, propane: 9.79%, propylene: 14.03% n-
butane 10.76%
(c) 0.93
2.21 (a) Methane: 24.16% and carbon dioxide: 66.44% and nitrogen 9.4% (b) 29.8
(c) 1.33 kg/m
3
CHAPTER 3 3.1
Compound Weight fraction mole fraction mole %
Butane 0.5 0.5701 57.01
Pentane 0.3 0.2758 27.58
Hexane 0.2 0.1541 15.41
Total 1.0 1.0000 100.00
AVMWT: 66.138
3.2 70,748 g
3.3 37.63%
3.4 (a) and (b)
Component mole % Weight % Methane 80 68.45
Ethane 15 24.10
Nitrogen 5 7.45 Total 100 100.00
(c) AVMWT: 18.7
(d) Density: 0.0008 g/cc
3.5 AVMWT: 30.5; Density of gas: 1.36 g/litre
3.6 Methane: 0.008892 kmole/m
3
Ethane: 0.02231 kmole/m
3
Hydrogen: 0.01338 kmole/m
3
Velocity: 30,558 m/h
Density: 0.00405 g/cc
3.7 1.169 g/litre
3.8 0.567 litre
3.9 10,719.7 K 3.10 C
3
H
8
3.11 300.37 atm 3.12 (a) and (c)
Component Volume % mole fraction N
2
64.75 0.6475
CO
2
9.52 0.0952
H
2
O 18.62 0.1862
O
2
6.11 0.0611
CO 1.00 0.0100
Total 100.00 1.0000
(b) Average density: 0.792 kg/m
3
3.13 52.923 kg 3.14 Component Volume % = mole %
Chlorine 68.59
Bromine 12.67
Oxygen 18.74
Total 100.00
3.15 (a) Partial pressure: 0.09 atm
(b) 3 m
3
(c) 2.06 g/litre
3.16 (a), (b) and (c)
Component mole fraction Concentration, Partial pressure g mole/cc mm Hg
CH
4
0.1 1.058 10
5
200
C
2
H
6
0.3 3.173 10
5
600
H
2
0.6 6.347 10
5
1,200
(d) 1.058 10
4
g mole/cc
(e) 1,248 g/s
(f) AVMWT: 11.8
3.17 (a) Nitrogen,
(b) 7.5% hydrogen
(c) 19.76%
3.18 (a) 0.05 atm
(b) 5 m
3
(c) 0.707 g/litre
(d) 17.3
3.19 34.4 s
3.20 (a) Chlorine: 54.98%, bromine: 10.16% nitrogen: 34.85% (b) 65.05
(c) Density: 2.59 g/litre
3.21 (a) Nitrogen: 67.5%, oxygen: 15.74% water: 1.79%, ammonia: 14.97%
(b) 2.48 kg/m
3
3.22 10.45 litre
3.23 0.982 kg
CHAPTER 4
4.1 31,941 J/g mole
4.2 77.25 C
4.3
x 1.0 0.897 0.773 0.660 0.555 0.459 0.369 0.288 0.212 0.140 0.076 0.013 0
y 1.0 0.958 0.897 0.831 0.758 0678 0.590 0.496 0.393 0.281 0.162 0.030 0
x, y: Mole fraction of benzene in liquid and vapour phase respectively. 4.4 x
A
1.0 0.724 0.415 0.134
0.0
y
A
1.0 0.819 0.548 0.205 0.0 x, y: Mole fraction of A in liquid and vapour phase respectively. 4.5
0.1847 kg/kg of steam, 0.1385 kg/kg of steam
4.6 Total pressure: 2,044.79 mm Hg
Mole fraction of methanol in vapour phase: 0.5052 Mole fraction of ethanol in vapour phase: 0.4948
4.7 (a) Total pressure: 4087.9 mm Hg
C
2
H
6
: 0.139, n-C
3
H
8
: 0.639, i-C
4
H
10
: 0.039, n-C
4
H
10
: 0.179 and C
5
H
12
: 0.004
(b) 3589.87 mm Hg
4.8 Total pressure: 906.9 mm Hg
Component
Benzene Toluene Xylene
Liquid phase Vapour phase composition, x composition, y
0.500 0.739
0.377 0.233
0.123 0.028
4.9 Partial pressure: 102.6 mm Hg
4.10 (a) Ethyl acetate: 12.22 %, air: 87.78% (By volume) (b) Ethyl acetate: 29.8 %, air: 70.2% (By
weight)
CHAPTER 5
5.1 (a) RH% = 24.94%
(b) 0.01358 mole of toluene/mole of vapour free gas (c) 0.0433 kg toluene/kg of air
(d) % saturation: 23.93%
(e) Mole % = volume % = 1.34%
5.2 Humidity: 0.019 kg/kg
% saturation: 21%
Humid volume: 0.9394 m
3
/kg dry air
5.3 2961.6 m
3
/h
5.4 0.567 mole/mole
1.534 kg/kg
5.5 0.25 mole/mole
0.676 kg/kg
5.6 Humidity: 0.025 kg/kg
Dew point: 28.5 C
Humid volume: 0.907 m
3
/kg dry air
Adiabatic saturation temperature: 30 C
Humid heat: 1.0521 kJ/kg dry air
Enthalpy: 0.951 kJ/kg dry air
5.7 Cool to 18.5 C and then reheat it to 30 C Air needed initially 5114.03 m
3
/h
5.8 27.5 C and 0.019 kg/kg
5.9 (a) 96.5%, (b) 115.08 m
3
/h
5.10 (a) 0.0351 kmole/kmole
(b) 0.00857 kmole/kmole
(c) 1.830 kg of water
(d) 49.858 m
3
5.11 46.5 C; 0.0475 kg/kg dry air
5.12 (a) % RH: 29.6%
(b) Humid volume: 0.974 m
3
/kg dry air
5.13 (a) 3703.7 kg dry air/h
(b) 0.8586 and 0.9739 m
3
/kg dry air respectively (c) 18 and 28.5 C respectively
(d) 35C
5.14 (a) 0.008 kg/kg
(b) 12 C
(c) 2.81 kg of water
(d) 7,405.2 kJ
(e) 32.5 C
5.15 % Relative saturation: 57.5%
Percentage saturation: 44.59%
5.16 Humidity: 0.027 kg/kg
% saturation: 70%
5.17 Humid volume: 0.9205 m
3
/kg dry air
Enthalpy: 106.6 kJ/kg dry air
5.18 (a) 809.4 m
3
/min
(b) 74.04 kg
5.19 (a) 0.0259 kmole/kmole, 0.01616 kg/kg (b) 0.0677 kmole/kmole 0.00423 kg/kg (c) 13.48 kg of
water
5.20 (a) 29.45
(b) 781.24 mm
(c) 810.69 Hg
(d) 0.0377 mole/mole
5.21 5.7%
5.22 (a) 86%, (b) 1396.5 m
3
/h
CHAPTER 6
6.1 Mother liquor: 3,324.64 kg
6.2 Feed: 83,078.34 kg
6.3 Crystals: 6,636 kg
6.4 Crystals: 479.2 kg
6.5 Crystals: 342 kg and Mother liquor: 918 kg
6.6 Water evaporated: 7,916.67 kg and crystals: 2,083.33 kg
6.7 Water evaporated: 720 kg Mother liquor: 6589 kg and
crystals: 1,691 kg
6.8 87.4%
6.9 Water evaporated: 561 kg
6.10 Water evaporated: 82.35 kg; Mother liquor: 1,122.85 kg and Feed: 2,705.2 kg
6.11 2393.6 kg/h
CHAPTER 7
7.1 H
2
SO
4
: 5,310.86 kg, HNO
3
: 2,811.87 kg and Feed: 1,877.27 kg
7.2 (a) 56.96%; (b) 8.338; (c) 21.81 kg
7.3 50.62%
7.4 CO
2
: 11.41%, H
2
O: 14.4% O
2
: 3.53% and N
2
:70.66%
7.5 Excess air: 39.06%, 471.06 kg of lime/100 kg coke burnt
7.6 O
2
: 12.14%, N
2
: 79.34%, SO
2
: 7.67% and SO
3
: 0.85%
7.8 54.22% Excess air
7.10 CO
2
: 4.9%, CO: 9.1% H
2
O: 17.51% and N
2
: 68.49%
7.11 CO
2
: 11.183%, O
2
: 3.956%, SO
2
: 0.158%, N
2
: 75.693%, and H
2
O: 9.010%
7.14 Butane: 2.46%, Pentane: 42.25% and Hexane: 55.29%
7.15 (a) 6,600 kg, (b) 4,920 kg and (c) 2,165 kg
7.16 (a) Nitrogen; (b) 16.2% and (c) 60%
7.17 (a) 18,973.2 kg/hr and (b) 1,434.4 kg/h in each evaporator
7.19 (a) 1.25 m
3
(b) 6.41 m
3
(c) Component Condition (a) Condition (b)
CO
2
0.23 0.14
H
2
O 0.14 0.08
N
2
0.63 0.74
O
2
0.04
Total 1.00 1.00
7.20 (a) 4.49%
(b) 3.08
7.21 (a) 28.8
(b) 7.55 m
3
/kg carbon burnt
(c) 50.285 m
3
/100 m
3
(d) CO
2
: 19.66%, O
2
: 1.28%, N
2
: 79.06%
7.22 (a) 446.7 m
3
(b) 0.642
7.23 (a) 18
(b) CO
2
: 17.5%, O
2
: 6.3%, H
2
O: 3.5%, and N
2
: 72.7%
7.24 (a) 2.965
(b) 19.23%
(c) 5081 kg
7.25 Liquid : 81.789 kg/hr, vapour : 18.211 kg/hr, C
5
H
12
: 31.38, C
6
H
14
: 60.06
7.26 Air supplied =
12.24 kg
, air required theoretically for complete
kg of fuel
combustion = 15.3 kg, volumetric analysis = (mol. basis) N
2
= 82.8%
CO = 10.9%
CO
2
= 6.5%
7.27 (a) Moles of CO: 5.444 kmoles; moles of CO
2
: 1.089 kmoles (b) Moles of air supplied: 18.388
kmoles
(c) Percentage of carbon lost in the ash: 7.407%
7.28 (a) Composition of the flue gas (wt. basis): CO
2
= 273.0933 kg, CO = 9.1467 kg, N
2
=
1091.3911 kg, O
2
= 118.5901 kg, H
2
O = 4.5 kg,
(b) Ash produced = 21.1 kg
(c) Carbon lost per 100 kg of coke burnt = 7.58%
7.29 (a) Volume of air being introduced = 21729.54 m
3
/h
(b) Composition of flue gas on dry basis (mol. basis): CO
2
: 10.74%, CO: 0.5373%, N
2
: 85.487%,
O
2
: 3.2267%
7.30 (a) 3.846% (b) 70.3%
7.31 Airfuel ratio =12.59478, flue gas analysis:
Composition Weight % Volume % CO
2
17.7382 11.9749
O
2
7.2088 6.69
N
2
72.5086 76.92
H
2
O 2.4726 4.08
SO
2
0.7167 0.3326
Amount of air supplied = 37.78434 ton 7.32 Airfuel ratio by mass = 16.7165
Flue gas analysis:
Composition Weight (kg) CO
2
3.113
O
2
0.6408
N
2
12.8717
H
2
O 1.026
SO
2
0.064
Total = 17.7155 kg/kg of fuel
7.33 Air requirement = 432.433 kmoles, volume = 15416.56 Nm
3
/h
Flue gas analysis:
Composition Weight (kg) CO
2
16.63 O
2
1.2 H
2
O 8.032 N
2
74.14
7.34 Airfuel ratio = 17.51058, % excess air = 16.167%
CHAPTER 8
8.1 (a) 100 moles (b) 0.4286 mole of Ammonia/mole of NO formed
8.2 (a) 1,425.8 kg, (b) Recycle fraction: 0.7179
CHAPTER 9
9.1 1760 C
9.2 1,16,295.8 kJ/kmole
9.7 1,874 C
9.10 51.44 kcal
CHAPTER 10
10.1 C = 0.1 [100/(100 + t)]
2
+ 0.2
10.2 C = [10,000 + 400t + t
2
]/(100 + t)
10.3 (a) t = 100 100 [(C 1)/1.5]
0.25
, 36.1 minutes
(b) 60 minutes
10.4 (a) C = 0.01 [40/(t + 40)]
5
+ 0.03
(b) 2.369 minutes
10.5 28.78 minutes
10.6 0.2675 kg Na
2
SO
4
/kg of solution
Index
Adiabatic reaction temperature, 198 Gas constant, 35, 36 Antoine equation, 75
API scale, 12
Atomic numbers of elements, 231233 Hausbrand chart, 75
Atomic percent, 11 Heat, 196
Atomic weights of elements, 231233 Heat capacity of gases (empirical Average molecular weight,
38 constants), 234 Avogadros hypothesis, 9 Heat of
Avogadros number, 36 combustion, 197
formation (also standard), 196 mixing, 197
Baume gravity scale, 12 reaction, 197
Brix scale, 13 from combustion data, 197
Bypass, 180 from enthalpy data, 197 Humid heat, 88
Humid volume, 88
ClausiusClapeyron equation, 74 Humidity, 87
Composition of absolute, 87
liquid systems, 11 percentage absolute humidity, 88 mixtures, 10 relative, 88
solutions, 10 Hydrated salt, 111
Conservation of mass, 8
Conversion, 9
Conversion factors, 229230 Ideal gas law, 35
Crystal, 111
Crystallization, 111
Kopps rule, 198
Density, 12, 38
Dew point, 88 Law
Dry bulb temperature, 87 Amagats, 37
Daltons, 37
Hesss, 197
Energy balance, 196 Leducs, 37
Enthalpy, 88 Law of conservation of mass, 8
247 248
INDEX
Magma, 111
Mass balance, 122 Mass relations, 7 Mole fraction, 11 Mole percent, 11 Mother liquor, 111
Normal boiling point (NBP), 74 Normal temperature and pressure
(NTP), 9
Saturated vapour, 89 Saturation, 89
partial, 89
percentage, 89 relative, 89
Specific gravity, 12 Standard
condition, 35
state, 196
Steam distillation, 75
System, 3
isolated, 3
Partial pressure, 36
Percentage saturation, 88 Process, 3
Property, 3
extensive, 3
intensive, 3
Psychrometry, 87
Pure component volume, 36 Purge, 180
Table of
atomic numbers, 231233 atomic weights, 231233 conversion factors, 229230 molal heat
capacities, 234
Theoretical flame temperature, 198 Twaddell scale, 13
Rate of
accumulation, 221 generation, 221 input, 221
output, 221
Reactant, 9
excess, 9
limiting, 9
Reaction
endothermic, 197 exothermic, 197
Recycle, 180
Units and notations, 1
derived units, 2
Unsteady state operations, 221
Vapour pressure, 74 Volume percent, 10
Weight percent, 10
Wet bulb temperature, 87
Yield, 9