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 MKSInternational, 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 (L2):

1 ft2 = 0.0929 m2
10.76 ft2 = 1 m2
Force: = mass acceleration (mL/t2):
1 dyne = 1 g cm/s2
(Force applied on a mass of 1 g, which gives an acceleration of 1 cm/s2)
1 Newton (N) = 1 kg m/s2
= (1000 g) (100 cm)/s2
1 N = 105 g cm / s2 = 105 dynes
Work/energy: = 1 kg m/s2
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/s2] [1 cm]
= 1 g cm2/s2
1 Joule = (1 N) (1 m)
= 105 g cm/s2 100 cm
= 107 g cm2/s2
1 Joule = 107 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.ft2. Find its equivalent in kg/s.m2
G (Mass velocity) = (200) lb/h.ft2
=
11 1 2
(200) m
(3600 s) (0.0929)
= 0.2712 kg/s.m2
1.2 Convert the heat transfer coefficient of value 100 Btu/h.ft2.F into W/m2 C
h (Heat transfer coefficient) = (100)
(0.0929 m2)

(1.8 C) [1 degree variation in Farh. scale is equivalent to 1.8 times the variation in celsius scale]

= 4.186 102 kcal/s.m2 C = 4.186 102 103 4.18 W/m2 C = 174.98 W/m2 C

1.3 The rate of heat loss per unit area is given by (0.5) [(DT)1.25/(D)0.25] Btu/h ft2 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. m2
using DT in C and D in m.
We know that,
9C + 32 = F15
1
9C + 32 = F25
2
Therefore,
1.8 [DC] = (DF)
qT()1.25
0.5()0.25A
q , Btu/h ft2 = 0.5 '(F)1.25A (ft)0.25
We know that,

1 Btu = 0.252 kcal

1 ft2 = 0.0929 m2
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 ft2 = (0.252 kcal)/h (0.0929 m2)

= 2.713 kcal/h m2 (c)
From (b) and (c) we get the expression for heat flux in units of kcal/h m2 with temperature difference
in Celsius and diameter in metre as:

Heat flux, kcal/h m2 =

(m)0.25
T 1.25
C)
' 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 m2 (0.2)
Also, from Eq. (d), heat flux = 2.101
(10)1.25 (0.06096)0.25
= 75.2 kcal/h m2
Both the values agree.

1.4 If Cp of SO2 is 10 cal/g mole K, what is the value in FPS units? The Cp 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/m3.
Basis: 500 lb of Iron = 500/2.2 = 227.27 kg
29.25 lit = 29.25 103 m
3
227.27 103 = 7770 kg/m3Density = 29.25

1.6 Etching operation follows the relation d = 16.2 16.2e0.021t, 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 e0.021t]
Let d be in mm and t be in min. (d = d 103 and t = t 60) Then, d = d 103 = 16.2 [1 e0.021t
60]

d = 0.0162 [1 e1.26t]
1.7 The density of fluid is given by r = 70.5 exp (8.27 107). Convert this equation to calculate the
density in kg/m3 with pressure in N/m2.

1000 kg/m3 = 62.43 lb/ft3

14.7 psi = 1.0133 105 N/m2
1 kg/m3 = 62.43 103 lb/ft3
Let, r be in kg/m3 and p be in N/m2.
Then, (r 62.43 103) = 70.5 exp (8.27 107 p 14.7/1.0133 105) r (kg/m3) = 1.129
103 exp [119.97 1012 p (N/m2)]

1.8 Vapour pressure of benzene in the range of 7.5 C to 104 C is given by log10 (p) = 6.9057
1211/(T + 220.8), where T is in C and p is in torr 1 torr = 133.3 N/m2. Convert it to SI units.

Let p be in N/m2and T be in K.
Then, log

p = 6.9057 1211
(T273) 220.8
1211log p log 133.3 = 6.90305
T 52.2
1211
log (p .) = 9.0305 T52.2
EXERCISES
1.1 Convert the following quantities:

(a) 42 ft2/h to cm2/s

(b) 25 psig to psia
(c) 100 Btu to hp-h
(d) 30 N/m2 to lbf/ft2
(e) 100 Btu/h ft2 F to cal/s cm2 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 Cp G0.8/D0.2

where h = Heat transfer coefficient in Btu/(h)(ft)2(F) D = Flow diameter, inches

G = Mass velocity, lb/(s)(ft)2
Cp = 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 Cp = 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 h2.5/g0.5] tan F

where q = Volumetric flow rate, ft3/s
h = Weir head, ft

g = Local acceleration due to gravity, ft/s2

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 k0.67 C0.5/(D0.2m0.47
p )

where G = Mass velocity of liquids, lb/ft2.s

k = Thermal conductivity, Btu/ft.h.F
Cp = 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) CaCO3 CaO + CO2 (2.1) [40 + 12 + 3 16] [40 + 16] + [12 + 32] 100 56 + 44
(ii) 3Fe + 4H2O Fe3O4 + 4H2 (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
CaCO3 reacts, 56 parts by weight of CaO and 44 parts by weight of CO2 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 CaCO3 gives 1 kmole of CaO and 1 kmole of CO2
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:
Na2CO3 + Ca(OH)2 CaCO3 + 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:

2Cr2O3 + 3CS2 2Cr2S3 + 3CO2

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 ft3at NTP.
1 kmole of any gaseous substance occupies 22.414 m3 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 + O2 CO2 i.e. 12 kg of carbon will burn with 32 kg of oxygen to form 44 kg of CO2.

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.

WA, WB = Weight of components A and B respectively. MA, MB = Molecular weight of components A
and B respectively,

if they are compounds.

AA, AB = Atomic weight of components A and B respectively, if they are elements.
V = Volume of the system.
VA and VB= 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.

WAMAMole fraction of A = WA WB MA MB 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. WA Atomic fraction of
A
=

AA WA WB AA AB

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
60F 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
145Degrees 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 = 141.5 131.5G
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 400G
WORKED EXAMPLES 2.1 Convert 5000 ppm into weight %.
5000 100= 0.5%106
2.2 The strength of H3PO4 was found to be 35% P2O5. 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 Cl2 = 25kmoles of Cl22 35.46
25 22.414= 7.9 m3Volume =
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 (C3H8) is 44
1 g mole of any gas occupies 22.414 litres at NTP
500 litres of propane at NTP = 500 = 22.31 g moles22.414

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 H2 = 50 kmoles of hydrogen
volume occupied by 50 kmoles of hydrogen 50 22.414

= 1120.7 m3 (b) 100 lb of H2 50 lb moles of hydrogen

Volume occupied by 50 lb moles of hydrogen 50 359 = 17950 ft3

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 C10H8 128 Benzene C6H6 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 CH4 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 C7H5N

2.9 An analysis of a glass sample yields the following data. Find the mole %.
Na2O : 7.8%, MgO : 7.0%, ZnO : 9.7%, Al2O3: 2.0%, B2O3 : 8.5% and rest SiO2.
Basis: 100 g of glass sample

Component Weight, g Molecular weight g mole mole %

Na2O 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
Al2O3 2.0 102.0 0.0196 1.194
B2O3 8.5 69.6 0.1221 7.439
SiO2 65.0 60.1 1.0815 65.857

Total 100.0 1.6419 100.0

2.10 A gaseous mixture analyzing CH4: 10%, C2H6: 30% and rest H2 at 15 C and 1.5 atm is flowing
through an equipment at the rate of 2.5 m3/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

CH4 10 16 160 13.56

C2H6 30 30 900 76.27
H2 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 m3/min
Moles of the gas = 3.555 = 0.156 kmole22.414
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 kg0.25
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 N2 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 N2 in the flue gases. If the remaining gases are CO2 and O2 calculate their composition
also.
Basis: 100 g moles of flue gas
Component g mole I Engineer II Engineer

N2x 28x 14x CO2y 44y 44y O2z 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 Na2CO3 by weight. Express the composition in mole
percent.
Basis: 100 g of solution

Component grams Molecular g mole Composition in weight mole % Na2CO3 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) (355.84) (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 H2
\ For producing 100 kg of H2 (by stoichiometry)

100 t167.52Iron (Fe) required = 8

= 2094 kg
Similarly, for getting 100 kg of H2 the amount of steam (H2O) required is
= 100 t 72= 900 kg8
The total weight of reactants is
2094 kg Fe and 900 kg H2O = 2994 kg
The weight of Fe 231.52 2094 = 2894 kg3O4 formed is = 167.52

\ The total weight of products is (100 kg H2 + 2894 kg Fe3O4) = 2994 kg

The total weight of reactants is (2094 kg Fe + 900 kg H2O) = 2994 kg

Method 2 (Based on moles)

100 kg of H2
4 kmoles H2 comes from

50 kmoles of H2 comes from Weight of 37.5 katoms Fe

50 kmoles H2 from

Weight of 50 kmoles H2O Moles of Fe3O4 formed is

Weight of Fe3O4 formed is

Total weight of reactants Total weight of products = 50 kmoles

= 3 katoms of Fe (by stoichiometry)

50

t= 37.5 katoms Fe4

= (37.5 55.84) = 2094 kg of iron

=
50 kmoles of water4t

= (50 18) = 900 kg H2O

=37.5kmoles3
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

Ca3(PO4)2 + 2H2SO4 CaH4(PO4)2 + 2CaSO4

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 SO2 is produced by the reaction between copper and sulphuric acid. How much Cu must be used
to get 10 kg of SO2?
Cu +2H SO
24

CuSO +SO +2H O

422
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? 2KClO3 2KCl + 3O2
(2 122.46) (2 74.46) (6 16) 244.92 148.92 96

2HgO 2Hg + O2
(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 O2
0.1698 g O2 is obtained from (244.92 0.1698)/96 = 0.4332 g of KClO3.

2.18 Ammonium phosphomolybdate is made up of the radicals NH3, H2O, P2O5 and MoO3. What is %
composition of the molecule with respect to these radicals?

The formula of ammonium phosphomolybdate is

(NH4)3PO4 12MoO3 3H2O
First let us form the final product from the radicals:
3NH3 + 4.5H2O + 12MoO3 + P2O5 (NH4)3PO4 12MoO33H2O
(317 = 51) (4.518 = 81) (12144 = 1728) (142 = 71) 1931

% of NH3=51
100= 2.64
1931
% of H2O= 81 100= 4.191931
% of MoO3 = 1728 100= 89.491931
% of P2O5=71100= 3.681931
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 Na2SO4 10H2O
(142 + 180 = 322)

2NaClH SO Na SO + 2HCl
(2

58.46 =116.92)

+24 24
98 142 (236.46)

Thus, 142 g of Na2SO4 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 (Na2SO4 10H2O) obtained is 2500 322/142 = 5669 g

2.20 (a) How many grams of K2Cr2O7 are equivalent to 5 g KMnO4? (b) How many grams of KMnO4
are equivalent to 5 g K2Cr2O7? 2KMnO4 + 8H2SO4 + 10FeSO4 5Fe2(SO4)3 + K2SO4 + 2MnSO4
+ 8H2O
K2Cr2O7 + 7H2SO4 + 6FeSO4 3Fe2(SO4)3 + K2SO4 + (Cr2SO4)3 + 7H2O
2KMnO4 gives 5Fe2(SO4)3
(2 158 = 316) (5 400 = 2000)

K2Cr2O7 gives 3Fe2(SO4)3

(294) (3 400 = 1200)

1200 t 316= 189.6 g KMnO4\ 294 g K2Cr2O7 is equivalent to 2000

3 t189.6= 1.935 g KMnO \ 3 g K Cr O
4 2 2 7 294
Similarly, 5 g KMnO
4
5 t 294=7.75 g K2Cr2O7 189.6
Alternatively, 53t= 7.75 g K2Cr2O71.935
2.21 If 45 g of iron react with H2SO4, 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 (i)(2)
42

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

i.e. 1.611= 0.806 g mole2
0.806 g mole 0.806 22.414 = 18.06 litres
(b) Case II
2Fe3H SO Fe (SO ) + 3H
(111.7) + (ii)(6) 24 2 43 2

The moles of hydrogen formed by reaction (ii) is 45 6 = 2.418 g111.7

2.418 g H2 = 1.209 g moles of hydrogen 1.209 22.414 27.1 litres
2.22 A natural gas has the following composition by volume CH4 : 83.5%, C2H6: 12.5%, and N2: 4%.
Calculate the following:

(a) composition in mole % (b) composition in weight % (c) average molecular weight (AVMWT) (d)
density at standard condition (kg/m3) Basis: 100 kmoles of gas mixture
Component Molecular mole % Weight, kg Weight % weight

CH4 16 83.5 83.5 16 = 1336 1336 100/1823 = 73.29

C2H6 30 12.5 12.530 = 375 375 100/1823 = 20.57
N2 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 m3
(d) Density of gas at standard condition =
1823= 0.813 kg/m3 2241.4

2.23 Convert 54.75 g/litre of HCl into molarity.

Molarity = g moles/litre of solution
= 54.75 = 1.536.45

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 = 0.252918

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 = 0.62490

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

H2O 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 ft3 (since the density of water is 62.47 lb/ft3) We know that 1 ft3 = 7.48 gallons
Therefore, 1.28 ft3 = 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/ft3 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 ft3 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/m3 and 1000 kg/m3 respectively. Basis:
1 m3 of solution.

Compound Molecular Volume, Density, Weight, Number Weight mole weight m3 kg/m3 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 (NH2CONH2) is 60 and that of N2 is 28. Basis: 100 kg of sample

60 kg of urea has 28 kg of N2
100 kg of urea will have = 28 100 = 46.67 kg of N260

(Theoretically)
The given sample has 40% N2
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, NH4NO3 = 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% HNO3, 60% H2SO4 and 8.5% H2O. 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

C6H6 + HNO3 C6H5NO2 + H2O

Feed, C6H6 : 663/78 = 8.5 kmole
HNO3 : 31.5% of 1700 kg = 535.5 kg = 8.5 kmoles H2SO4 : 60 % of 1700 kg = 1020 kg = 10.408
kmoles H2O : 8.5 % of 1700 kg = 144.5 kg = 8.028 kmoles Reaction is 95% complete
Hence, HNO3 unreacted : 0.05 8.5 = 0.425 kmole C6H6 unreacted : 0.05 8.5 = 0.425 kmole
H2SO4 unreacted : 10.408 kmoles
H2O unreacted : 8.028 kmoles
H2O 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 %

HNO3 0.425 63 26.775 1.133

H2SO4 10.408 98 1020.000 43.165
H2O (8.075 + 8.028) = 16.103 18 289.850 12.266
Nitrobenzene 8.075 123 993.225 42.032
C6H6 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% Na2O by weight. Estimate the purity of flakes.

Reaction is as follows:
2NaOH Na2O + H2O
Amount of Na2O in pure flakes = 62 100/80 = 77.5% % Purity = 0.746/0.775 100 = 96.26%

2.34 Two kg of CaCO3 and MgCO3 was heated to a constant weight of 1.1 kg. Calculate the %
amount of CaCO3 and MgCO3 in reacting mixture.

Reaction is as follows:
CaCO3 CaO + CO2
(100) (56) (44)
MgCO3 MgO + CO2
(84) (40) (44)

Let, x be the amount of CaCO3.

Therefore, (2 x) be the weight of MgCO3
100 kg of CaCO3 gives 56 kg of CaO
Therefore, x kg of CaCO3 gives 56x = 0.56x kg of CaO.100
Similarly, 84 kg of MgCO3 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, %

CaCO3 1.761 88.05

MgCO3 0.239 11.95
Total 2.000 100.00

2.35 The composition of NPK fertilizer is expressed in terms of N2, P2O5 and K2O 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:

2NH3 N2 +3H2
(34) (28) (6)
2H3PO4 P2O5 +3H2O
(196) (142) (54)
2KCl + H2O K2O + 2HCl
(149) (18) (94) (73)
N2, K2O and P2O5 are each equivalent to 15 weight % = 150 kg each Ammonia reacted = 34
150= 182.14 kg
28
150
H = 207.04 kg3PO4 needed = 196 142
KCl needed = 149 150= 237.77 kg94
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 m3 (since density is 1000 kg/m3 due to specific gravity being unity)
Mass/volume = density
Assuming ideal behaviour

350 650= 1700 SB

rB = 1300 kg/m3
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/m3,
express the composition of A in weight %.

Basis: 1 m3 of solution
Volume of A in solution = 1 0.47 = 0.47 m3
Weight of A = 0.47 1250 = 587.5 kg
Volume of water = (1 0.47) = 0.53 m3
Therefore, the weight of water = 0.53 m3 1000 = 530 kg

Hence, weight % of A =
587.5= 52.57%
530 587.5

2.38 An aqueous solution contains 43 g of K2CO3 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 K2CO3 = 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 moles138
Molarity = g mole/volume of solution in lit = 0.312= 2.833M0.11

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%, O2: 1.3%, ethane: 25%, N2: 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 %

C2H4 30.6 28 856.8 22.00
C6H6 24.5 78 1911.0 49.07
O2 1.3 32 41.6 1.07
CH4 15.5 16 248.0 6.37
C2H6 25 30 750.0 19.26
N2 3.1 28 86.8 2.23

Total 3894.2 100.00

Density = Weight/Volume =
3894.2 22.414 = 1.737 kg/m3 = 1.737 g/l.
100

2.40 A compound has a composition of 9.76% Mg, 13.01% S, 26.01% O2 and 57.22% H2O 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
H2O 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 = MgSO4.7H2O 2.41 A substance on analysis gave
1.978 g of Ag, 0.293 g of S and 0.587 g of O2. Find the molecular formula of the compound.
Compound Weight, Atomic weight g or Molecular weight Number Converting to of moles whole
numbers dividing by 9.156 103

Ag 1.978 108
S 0.293 32
O2 0.587 16

Molecular formula = Ag2SO4

0.0183 2
9.156 103 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 CH4)(X) + (Molecular weight of C2H6) (1 X)

21.6 = 16 X + 30 (1 X)

Solving, we get X = 0.6

2.44 A mixture of FeO and Fe3O4 was heated in air and is found to gain 5% in mass. Find the
composition of initial mixture.
Reactions involved are:

2FeO + 0.5 O2 Fe2O3

2Fe3O4 + 0.5 O2 3 Fe2O3
Basis: 100 kg of feed mixture
Let X be the weight of FeO in the mixture
From 144 kg of FeO, Fe2O3 formed is 160 kg

Therefore, from
X
kg of FeO, Fe
2

O
3

formed is 160

X 144 From 232 kg of Fe3O4, Fe2O3 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.
160Xtt (480) 105
144 464
Solving, X, the weight of FeO = 20.25 kg
Fe3O4 = (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 CaCO3 will have 56% CaO
If the CaO is 54.5%, then % of CaCO3 in the sample is

54.5 100/50 = 97.32%

2.46 Express the composition of magnesite in mole %.

Compound Weight %
MgCO3 81
SiO2 14
H2O5

Compound Weight % Molecular weight moles mole % MgCO3 81 84 0.964 65.34

SiO2 14 60 0.233 15.82
H2O 5 18 0.278 18.83

2.47 The concentration of H3PO4 is expressed in terms of P2O5 content. If 35% P2O5 is reported, find
the composition of H3PO4 by weight. P2O5 + 3H2O 2H3PO4
(142) (54) (98)

i.e. 142 kg of P2O5 196 kg of H3PO4

Therefore, 35 kg of P2O5 35 196 = 48.3 H3PO4142

i.e. H3PO4 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 PbO2 according to the
reaction shown below:
PbS + O2 Pb + SO2 (1) PbS + 2O2 PbO2 + SO2 (2) Estimate (i) unreacted PbS, (ii) % excess
oxygen supplied, (iii) total SO2 formed, and (iv) the % conversion of PbS to Pb.

PbS + O2 Pb + SO2 (1)

(239.2) (32) (207.2) (64)
PbS + 2O2 PbO2 + SO2 (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 PbS207.2

239.2 kg of PbO2 comes from 239.2 kg of PbS

Therefore, 1 kg of PbO2 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
O2 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 PbO2, oxygen needed = 6

32= 0.927 kg
207.2

From Reaction 2:
239.2 kg of PbO2 requires 64 kg of oxygen
Therefore, to produce 1 kg of PbO2, 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 SO2 formed
If 207.2 kg of Pb is formed, SO2 formed is 64 kg
If 6 kg of Pb is formed, SO6 = 1.853 kg2 formed is 64 207.2
If 239.2 kg of PbO2 is formed, SO2 formed is 64 kg
If 1 kg of PbO64 = 0.268 kg2 is formed, SO2 formed is 239.2
Total SO2 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/m3 m3

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/m3Average density = Mass/Volume = 0.0504

Average molecular weight = Weight/Total moles = 40 = 47.50.842
(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?

As2O3 + 3C 3CO + 2As

2.3 Oxygen is prepared according to the following equation: 2KClO3 2KCl + 3O2. 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/m3. 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 C12H22O11, determine

(a) kg sugar/kg H2O

(b) kg solution/m3 solution
(c) g sugar/litre solution

2.11 The synthesis of ammonia proceeds according to the following reaction

N2 + 3H2 2NH3
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?
2Cr2O3 + 3CS2 2Cr2S3 + 3CO2

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 H3PO4. 2.15 Hydrogen gas in the
laboratory can be prepared by the reaction of sulphuric acid with zinc metal
H2SO4 (l) + Zn(s) ZnSO4(s) + H2 (g)

How many grams of sulphuric acid solution (97%) must act on an excess of zinc to produce 12.0 m3/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 H2SO4 CuSO4 + 2H2O + SO2.
Find how much copper and how much 94% sulphuric acid must be used to obtain 32 kg of SO2.

2.17 Aluminium sulphate is produced by reacting crushed bauxite ore with sulphuric acid as shown
below:
Al2O3 + 3 H2SO4 Al2 (SO4)3 + 3 H2O

Bauxite ore contains 55.4% by weight Al2O3, the reminder being impurities. The sulphuric acid
contains 77.7% H2SO4, the rest being water. To produce crude aluminium sulphate containing 1798
kg of pure Al2(SO4)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/cm2 1.01325 bar 359 ft
1 atm3/lb mole 22.414 m3/kmole 22.414 m3/kmole
491.69 273.16 K 273.16 K 0.73 atm ft
oR 3/lb mole oR 0.085 kgf m3/kmole K 0.083 Bar m3/kmole K
35

Pressure 1 atm = 1.033 kgf/cm2 = 1.01325 bar

1 atm = 14.67 psia = 105 N/m2 = 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 ft3/lb mole R
nT
R = 10.73 lbf ft3/in2 lb mole R

Avogadros Number: 6.023 1023 molecules per g mole

2.73 1026 molecules per lb mole
6.023 1026 molecules per kg mole

Different units are used to express pressure like atmosphere, mm of Hg, psia, kg/cm2, bar, N/m2, and
Pa. Similarly, volume is expressed in cm3, m3, litre, ft3 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 Rg

R psia in3 18.51

R psia ft3 10.73
R atmospheres ft3 0.73
KPa m3 8314
K atmospheres m3 0.08206
K atmospheres cm3 82.06
K cm Hg cm3 6239.79

Units of gas
constant

in3psia/lb mole R ft3psia/lb mole R

ft3atm/lb mole R
m3Pa/kmole K
m3atm/kmole K
cm3atm/g mole K (cm3cm Hg)g mole K

Rg = 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 pA pB pC P Number of moles nA nB nC n Pure component volume VA VB VC 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.
pA + pB + pC = P
where pA, pB, pC, 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
VA + VB + VC = V

VA, VB, VC, stand for pure component volume of components A, B, C,

Where ideal gas law is applicable;
n RT; p = Bn RT; pC = Cn RT(a) pA = A
B
VVV
Adding all the partial pressures of A, B and C, we have,
RT
P
=
p
A

+
p
B

+
p
C

(nA + nB + nC)
Dividing, pRT V nA ;A/P = V ()RT n ++n
A BC

pressure fraction = mole fraction.

(b) PVA = nART; PVB = nBRT; PVC = nCRT
Adding P(VA + VB + VC) = RT (nA + nB + nC) = nRT = PV
nRTP = N A VA
AV = Dividing,
()AB Cn RT
++
or, VA = NA 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 Cl2 = 15/71.0 = 0.2113 kmole

1.0293 = 5.643 m3Its 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 Cl2
6/71 = 0.0845 lb mole of chlorine Volume at standard condition = (0.0845 359) = 30.34 ft3
PV1Volume at given condition = 00
01

760 530
=

= 33.4 ft3
3.3 Calculate the weight of 200 cu.ft. of water vapour at 15.5 mm Hg and 23 C
Basis: 200 ft3 of gas at given condition
PV T0Volume at standard condition =11

15.5 273= 3.76 ft =
3

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 CO2 to a volume
of 20 ft3 at 30 oC.
Find the pressure of the gas stored (required)?
30 0.6818Basis:
30 lb CO2 =
= 0.6818 lb mole = 2.2046

= 0.3102 kmole Volume at standard condition = 0.3102 22.414 = 6.9528 m3 Volume at given
condition = 20 0.02832 = 0.5664 m3
PV T1Pressure at the given condition P1= 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 ft3 chamber may
be heated without exceeding 100 psi pressure. Basis: 10 lb of N2 = 10/28 = 0.357 lb mole
Volume at standard condition = 0.357 359 = 128.21 ft3
TV P1\ Temperature T1= 01V
=
27330100

= 435.4 K = 162.4 C

3.6 When heated to 100 C and 720 mm Hg, 17.2 g of N2O4 gas occupies a volume of 11,450 cc.
Assuming that the ideal gas law applies, calculate the percentage dissociation of N2O4 to NO2?

NO
24 2NO2
(92) (2 46)

N2O4 present initially = 17.2/92 = 0.187 g mole;

Let x g mole of N2O4 dissociate,
then, 2x g moles of NO2 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 0Volume at standard condition = 11
01

720 273
= 11450
373
= 7939.2 cc
Therefore, no. of g moles remaining = 7939.2 = 0.35422,414\ (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.
CO2: 13.1%, O2: 7.7% and N2: 79.2% Basis: 1 g mole of the gas
Component Volume % = Molecular g mole Weight, g mole % weight

CO2 13.1 44 0.131 0.131 44 = 5.764

O2 7.7 32 0.077 0.077 32 = 2.464
N2 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/ft3 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 ft3 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 H2; (b) mole fraction and mole % H2; (c) pressure fraction of H2 (d) partial volume of
H2; (e) volume fraction and volume % of H2; (f) weight of H2; (g) weight fraction and weight % of
H2; (h) average molecular weight; (i) density of gas mixture; (j) density at standard condition

Also, show that volume % = pressure % = mole %

Basis: 1000 ft3 of gas mixture
(a) Partial pressure of hydrogen = 0.26 atm V = 1000 ft3, T = 710 R Volume of H
2

at standard condition = 1000

0.26 492
1.00 710 = 180.169 ft3

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 = 0.1383.648
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 1.89 492

3

(e) Volume fraction of hydrogen = 138 = 0.1381000

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 = 0.6931.89
Mole fraction of hydrogen = 0.26 = 0.1381.89
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 ft3 at NTP condition
Number of moles = 1309.7= 3.648 lb moles 3.648 35.5359
= 129.55 lb.
129.55
\
Density at given condition =
= 0.12955 lb/ft3

( j) Density at standard condition:

Volume at standard condition = 1000

1.89 492

= 1309.7 ft3
129.55
= 0.09892 lb/ft3\ 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 CxH

y
y
y
O2 xCO2 + H2O4 CxHy + x

y xyMoles: 1 x
4 2
Total moles of reactants = 1xy4
yTotal moles of products = x Reactants (1xy/4) 600 6 Products
++===
(xy/2) 700 7
7
y
7+7
x
+

= 6x + 3y
(7
x
6
x
)+
7y
= 7

x 5y = 74
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 = 32x = 1; 4 5
5y = 9; y = 36x = 2;
45
x = 3; 5y = 10; y = 40 = 84 5
5y = 11 y = 44x = 4
45

The value of y is to be an integer.

Hence, the hydrocarbon is C3H8 : (Propane)
The combustion reaction is C3H8 + 5O2 3CO2 + 4H2O

3.12 Combustion gases having the following molal composition are passed into an evaporator at 200
C and 743 mm Hg (N2: 79.2%, O2 : 7.2%, CO2: 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 N2: 48.3%, O2: 4.4% and
H2O : 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.

(N2, O2, CO2) Evaporator (N2, O2, CO2) + H2O

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 358Volume 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-enteringt
3972.31
3.13 How many g moles of nitrogen will occupy 1000 m3 at 112 103 N/m2 and 400 K
PV = nRT, where R = 8.314 J/g mole K = 8.314 (Pa) (m3)/g mole K PV
=
112
10 3

n = 1000= 33,678 g molesRT 8.314 400

Alternatively ,
P1 = 1.01325 105 N/m2
T1 = 273 K

since

PVPV T= T
11 22 12

V
1

(at NTP) =
112
103
tt1000 273=
754.4 m3 400 1.01325 t105
t
1000 g moles of gas occupies 22.414 m3 at NTP,
Hence, 754.4 m
3

contains

1000 = 33,658 g moles of nitrogen

(Error is due to the fact that T1 is taken as 273 K and not as 273.16 K on taking T1 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 litres760 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 Cl2
is 59 mm Hg and the remainder being inert gas. The gas leaves at 80 F and 743 mm Hg with Cl2
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 Cl2 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
Volumeof inert gas leaving = 100 742.5 297
(a) Volume of gas leaving = 92.5 litres (743 mm Hg)
Volumes of Cl2 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 Cl2 entering

= 100
59 273
= 7.14 litres760 297
Volume at standard condition of Cl2 leaving
= 92.5 0.5 273
= 0.055 litre760 299.7
Volume at standard condition of Cl2 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. 4NH3 + 5O2 6H2O + 4NO. The gases from this process are passed into towers where
they are cooled and the oxidation is completed according to the reactions:

2NO + O2 2NO2
3NO2 + H2O 2HNO3 + 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 + 1.5O2 + H2O 2HNO3, calculate the following:

(a) The volume of air to be used per 100 litres of NH3 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 NH3, assuming 90% of the nitric oxide entering the tower
is oxidized to acid.
NH
3 Catalyzer
Air
Exit gas Absorber
HNO3

Basis: 1 g mole of NH3 overall reaction is NH3 + 2O2 HNO3 + H2O O2 required is 2 g moles
But O2 supplied is 2 1.2 = 2.4 g moles

i.e. air supplied is

2.4 = 11.42 g moles
0.21
Thus, N2 = 9.02 g moles.
(a) Volume of air = 11.42 22.414 293 760
= 276.4 litres273 755
Volume of NH3 = 1 293 760 = 24.2 litres 22.414 273 755
Volume of air/100 litres of NH3 = 276.4 100= 1142.2 litres24.2
(b)

Component g mole mole % = volume % NH3 1.00 8.0

O2 2.40 19.3 N2 9.02 72.7 Total 12.42 100.0

(c) Gases leaving catalyzer are nitrogen, oxygen, ammonia, nitric oxide and water:
N2 (all that enters) = 9.02 g moles

NH3 (85% conversion) = (1 0.85) = 0.15 g mole

O5 = 1.06 g moles2 consumed = 4

O2 leaving = (2.4 1.06) = 1.34 g moles
NO formed = 0.85 g mole

H6 = 1.275 g moles2O formed =

Component N2 O2 NH3 NO H2O 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 NH3 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
HNO3 produced = 0.765 g mole = (0.765 63) = 48 g For 100 litres of NH3 weight of HNO3
produced

=
48 100= 199 g24.2

3.17 1000 kg/h of an organic ester C19H36O2 is hydrogenated to C19H38O2

in a process. The company purchases its H2 in cylinders of 1 m3
capacity. The pressure in cylinder is initially 10 kg/cm2 (abs.) and drops to 2 kg/cm2 (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

C19H36O2 + H2 C19H38O2
296 2 298
296 kg of ester reacts with 2 kg of H2
168000 kg of ester reacts with
2 168000= 1135 kg of hydrogen
296
1 kmole of any gas occupies 22.414 m3 at NTP
101
H initially present in the cylinder (10 m3) = (1) = 0.45 kmole (by reducing to
2
NTP condition)
12
H
2

after use =

= 0.09 kmole
\ H2 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
ft3 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 ft3 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 ft3Toluene entering =

Weight =
348.8
860

273 92 = 74 lb.
At exit, air is saturated with toluene.
90
Toluene leaving = 740

= 90 ft3

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 ft3 of entering air?
Basis: 1000 ft3 of entering air.
Moles of air entering =
1000 492 = 1.43 lb moles
359 960
Moles of water in it = 50 = 0.094 lb mole760
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:

CO2: 9.5%, CO : 0.2%, O2: 9.6% and N2: 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/m3 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 %

CO2 44 9.5 (9.5 44) = 418.0 13.978

CO 28 0.2 (0.2 28) = 5.6 0.187
O2 32 9.6 (9.6 32) = 307.2 10.273
N2 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 3
= 0.416 m
0.5
= 1.202 kg/m3(c) Density =

(d) Specific gravity = density of gas/density of air = 1.202 = 0.9251.3003.21 A producer gas has the
following composition CO2: 4.4%, CO : 23%, O2: 2.6% and N2: 70%. Calculate the following:
(a) volume of air at 25 C and 750 mm Hg required for the

combustion of 100 m3 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 m3 of
gas burnt.
Basis: 100 kmoles of producer gas.

CO = 23 kmoles
O2 needed = 23/2 = 11.5 kmole; O2 in feed = 2.6 kmoles O2 actually needed = (11.5 2.6) = 8.9
kmoles

Air supplied =
8.9 1.25= 52.98 kmoles
0.21
O2 supplied = 52.98 0.21 = 11.125 kmoles
N2 in air = 52.98 0.79 = 41.85 kmoles
298 760Volume of feed = 100 22.414
273 750
= 2479.28 m 3

Volume of air = 52.98

22.414

298 760 = 1313.43 m3

(a) Volume of air/100 m
3 of feed = 1313.43100= 52.98 m3 2479.28
(b) (assuming complete combustion)

CO2 leaving the burner = (4.4 + 23) = 27.400 kmoles O2 leaving = (8.9 0.25) = 2.225 kmoles N2
leaving = (70 + 41.85) = 111.850 kmoles

141.475 kmoles
Composition of gases leaving (volume % = mole %): CO2: 19.37%, O2: 1.57% and N2 : 79.06%
Volume of gases leaving = 141.475

22.414

623 760
273 750 = 7332.92 m3

Volume of gases leaving/100 m

3 of feed = 7332.92 100= 295.76 m3 2479.28

3.22 Natural gas has the following composition: CH4: 94.1%, C2H6:3% and N2: 2.9%. This gas is
piped from the well at 80F and 80 psi. Calculate the following.
(a) Partial pressure of N2
(b) Pure component volume of N2 per 100 ft3 of the gas (c) Density
Basis: 100 ft3 of the natural gas

(a) Partial pressure of N2 =

80 2.9= 2.32 psia.
100
(b) Pure component volume of N2 = 0.029 100 = 2.9 ft3
(c) Volume of gas at NTP = 100

80 492 = 497 ft3 14.67 540

No. of moles of gas = 497 = 1.38 lb moles.359

Component mole % lb mole Weight, lb

CH4 94.1 1.38 0.941 = 1.298 (1.298 16) = 20.777

C2H6 3.0 1.38 0.03 = 0.042 (0.042 30) = 1.260
N2 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/ft3Density of gas =

23.157
= 0.0466 lb/ft3Density at standard condition =

3.23 Compare pressures given by the ideal gas and van der Waals equation for 1 mole of CO2
occupying a volume of (381 106) m3 at 40 C
RT = 6.831 106 N/m2(a) Ideal gas law P =
nV
where, R = 8.314 N.m/g mole K (J/g mole K); T = 313 K; V = 381 106 m3
(b) van der Waals equation
P
a
(V b) = nRT
a = 0.3646; b = 4.28 105 rest same as above
RTa
P
=

V
tP = 65 62381
= 5.2 106 N/m2

3.24 It is desired to market O2 in small cylinders having volumes of 0.5 ft3 and exactly containing 1 lb
of gas at 120 F. What is the pressure? Basis: 1 lb of O2 = 1/32 = 0.031 lb mole; R = 0.73 ft3 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? P1 = 35 + 14.67 = 49.67 psia; P2 = 50 + 14.67 = 64.67 psia. T1 = 460
R; V1 = V2; n1 = n2; T2 = ?
PV P V
11
22

T
()( ) ( )460);600R
TT P2 49.6712 1

\ Temperature = 140 F
3.26 Calculate densities of C2H6 and air at NTP.
At NTP 1 g mole occupies 22,414 cc.

Density of C
2H6 =

130=1.3 103 g/cc22414

Density of air = 128.84= 1.29 103 g/cc22414

3.27 Acetylene gas is produced according to the reaction

CaC2 + 2H2O C2H2 + Ca(OH)2

Calculate the number of hours of service that can be got from 1 lb of carbide in lamp burning 2 ft3 of
gas/hour at 75 F and 743 mm Hg.
Basis: 1 lb of CaC
1 = 0.0156 lb mole. =
2 64
CaC2 + 2H2O C2H2 + Ca(OH)2
64 36 26 74
Volume of acetylene got = 0.0156

359

535 760 = 6.24 ft3 492 743

6.24
Time of burning =

= 3.12 h.
A similar problem has been solved in MKS system also: Data: 1 kg CaC2; 25 C; 740 mm Hg; for a
lamp burning gas 40 litres h.
Basis: 1 kg CaC2 = 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: Cl2 : 67%, Br2: 28%, O2: 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 %

Cl2 71 67 (67/71) = 0.945 74.0

Br2 160 28 (28/160) = 0.175 13.7
O2 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/litre25.13
Specific gravity of gas mixture = 3.12 = 2.71.15

3.29 A mixture of NH3 and air at 730 mm Hg and 30 C contains 5.1 NH3 by volume. This gas is
passed at a rate of 100 ft3/min. through an absorption tower in which NH3 is removed. The gases
leave the tower at 725 mm Hg and 20 C having 0.05% NH3 by volume. Calculate:

(a) the rate of flow of gases leaving the tower and

(b) weight of NH3 absorbed.
Basis: 100 ft3 of entering gases.
Volume of NH3 = 5.1 ft3 and of air = 94.9 ft3 (730 mm Hg, 30 C)

730 293 = 92.4 ft3Volume of air at exit condition = 94.9 725 303
92.4 ft3 of air 99.95% of exit gas.
92.4
(a)
\
Volume of exit gas =
= 92.447 ft3
/min.
Volume of NH3 in exit = 0.047 ft3
Volume of exit NH
3

at inlet condition = 0.047

725 303

= 0.0482 ft3
(b) Volume of NH3 absorbed = (5.1 0.0482) = 5.0518 ft3
Volume of NH
3

absorbed at NTP = 5.0518

730 273

= 4.372 ft3
Moles of NH3 = 4.372= 0.012 lb mole = 0.207020 lb359

3
3.30 1000 ft3 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 ft3 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 ft3(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 303Volume of air leaving at inlet condition = 938 = 570 ft3

Volume of water vapour condensed = 1000 570 = 430 ft3

43022273
(b) Water condensed =

18 = 0.562 lb

3.31 A producer gas has the following composition by volume CO : 23%, CO2: 4.4%, O2 : 2.6% and
N2 : 70%
(a) Calculate the ft3 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 ft3 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 ft3 gas burnt.
Basis: 100 lb moles of gas
i.e. carbon in the feed = 23 + 4.4 = 27.4 atoms
530 760 = 39,200 ft3(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 ft3
/lb.
23
(b) O
2

required for the combustion of CO =


= 11.5 lb moles

O2 available in feed = 2.6 lb moles

Theoretical O2 required = (11.5 2.6) = 8.9 lb moles
O2 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 ft3

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

359

530 760 = 39,200 ft3

Volume of air/100 ft
3 of feed = 19930 100 39200
(c) CO2 leaving = (23 + 4.4)
O2 remaining = (10.68 8.9)
= 50.85 ft3

= 27.40 lb moles = 1.78 lb moles N2 leaving (from air) = (50.85 10.68) = 40.17 lb moles N2
entering along with feed

N2 Total
Total
Composition of CO2 Volume % 19.66 = 70.00 lb moles = 110.17 lb moles = 139.35 lb moles

O2 N2
1.28 79.06
(d) Volume of gases leaving
= 139.35

359

760
1060
= 1,09,218 ft3


1,09,218100= 278.6 ft3Volume of gases/100 ft3 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
ft3/min.

Basis: 100 lb of coke.

C + O2 CO2
C : 89.1 lb. Ash : 10.9 lb.
Carbon burnt = 89.1 0.9 = 80.19 lb
Carbon burnt to CO2 = 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
O2 supplied = 89.1 1.3 = 308.88 lb =
= 9.65 lb moles
100
Air supplied = 9.65

= 45.96 lb moles
N2 in air = (45.96 9.65) = 36.31 lb moles
6.48
0.2
O
2

required =

= 6.58 lb moles
Excess O2 leaving = (9.65 6.58) = 3.07 lb moles
(a)

Component lb mole mole % CO2 6.48 14.07

CO 0.20 0.43
O2 3.07 6.67
N2 36.31 78.83
Total 46.06 100.00

(b) Volume of flue gases = 46.06

359

760
1010

= 34,722 ft3

Hence, for 200 lb/h of coke charge, volume of flue gases is = (34,722 2) = 69,444 ft3/h
i.e. Volumetric flow rate of flue gases = 1157.4 ft3/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 NO2. Of the NO2
formed, 66% will be associated to N2O4 at 26 C. The gases are then passed into water washed
absorption towers where nitric acid is formed.

3NO2 + H2O 2HNO3 + 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 NO2 and N2O4 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 HNO3 of the combined nitrogen in the furnace gases is 85% complete.

H2O
Air ArcNO CoolerNO2 ChamberN2O4 Abs. N ,O 2% 26 C,Col. 750 mm
2 2
HNO3
Basis: 100 g moles of air contain N2: 79 g moles and O2: 21 g moles. (a) Reaction in arc furnace is
given as
N2 + O2 2NO
which means x mole of N2 react to give 2x mole of NO. Total moles of gas leaving = (79 x) + (21
x) + 2x = 100 (by stoichiometry) N2 O2 NO when x = 1, we have, N2 O2 NO

78 20 2
2x% NO = 2 = 100

\x=1
(b) Reaction in cooler NO + O2 NO2
2 g moles of NO gives 2 g moles of NO2
O2 remaining = (20 1) = 19 g moles
Reaction in chamber is 2NO2 N2O4
66% of NO2 remains as N2O4
Moles of NO2 associated to N2O4 = (2 0.66) = 1.32 \ N2O4 formed = 0.66 g mole
NO2 remaining = 2 1.32 = 0.68 g mole
NO2 N2O4 O2 N2 Total
Total moles: 0.68 + 0.66 + 19 + 78 = 98.34
Partial pressure of NO2 = 0.68 750= 5.188 mm Hg.98.34

Partial pressure of N 0.66 750= 5.030 mm Hg.2O4 = 98.34

(c) Combined N2: in NO2 0.68 g mole

in N2O4 (0.66 2) = 1.32 g moles/2 g moles
Thus, 3NO2 + H2O 2HNO3 + NO
Total moles of gas in 1000 litres of entering gas
PV= RT

750
1000
=

760
= 40.25 g moles
Moles of NO2 = (40.25) (0.68) = 0.278 g mole98.34
3 moles of NO2 yields 2 moles of HNO3.
2
\
0.278 kmole of NO
2

yields 0.278


0.85 = 0.158 kmole of HNO3

(85% conversion)
\ Weight of HNO3 formed = 0.158 63 = 9.95 g.

3.34 The gas leaving a gasoline stabilizer has the following analysis by volume C3H8: 8%, CH4:
78%, C2H6: 10% and C4H10:4%

This gas leaving at 90 oF and 16 psia at the rate of 70,000 ft3/h is fed to gas reforming plant where the
following reaction takes place.

CnH2n+2 + nH2O nCO + (2n + 1)H2 (1) CO + H2O CO2 + H2 (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 H2 leaving (lb/h) and (d) composition of
gases leaving (weight %)

Basis: One hour = 70,000 ft3 of gas.

492 16 = 68,295 ft3Volume of gas at NTP = 70,000 550

68,295
Moles of gas =

= 190.24 lb moles

Components C3H8 CH4 C2H6 C4H10Total

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)
CH
38 + 3H O2 3CO + 7H2
44 54 84 14

CH
+HO
42 CO + 3H2
16 18 28 6
26 2 CH +2H O 2CO+5H2
30 3656 10

CH
410 + 4H O2 4CO + 9H2
58 72 112 18

Weight of water produced from C3H8 = (15.22 3 18) = 821.88 lb Weight of water produced from
CH4 = (148.39 1 18) = 2,671.02 lb Weight of water produced from C2H6 = (19.02 2 18) =
684.72 lb Weight of water produced from C4H10 = (7.61 4 18) = 547.92 lb

Total = 4,725.54 lb CO + H2O CO2 + H2

Total CO formed = (15.22 3) + 148.39 + (19.02 2) + (7.61 4) = 262.53 lb moles.

H2O 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, H2O, CO, CO2, H2

H2 = 1808.000 lb
C3H8 15.22 0.05 44 = 33.484 lb
CH4 148.39 0.05 16 = 118.712 lb
C2H6 19.0 0.05 30 = 28.530 lb
C4H10 7.61 0.05 58 = 22.069 lb
CO 249.4 0.1 28 = 698.320 lb
CO2 249.4 0.9 44 = 9876.240 lb
H2O 262.53 0.05 18 = 236.277 lb

(from Reaction 1) H2O [4,725.54 (224.46 18)] = 685.260 lb

(from Reaction 2) 13,506.892 lb
Component C3H8 CH4 C2H6 C4H10 CO CO2 H2OH2Total
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. CH4 : 68%, CO2: 30%
and NH3: 2%. 600 m3/h of this gas at 30 oC 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

CH4 16 68 68 16 = 1,088
CO2 44 30 30 44 = 1,320
NH3 17 2 2 17 = 34

Total 100 2,442

Average molecular weight =
2, 442= 24.42 (b) Volumetric flow rate at standard condition
100
= 600 2732 = 1081.2 m3/h3031
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/m3.1081.2
3.36 In the process of manufacturing Cl2, HCl gas is oxidized with air as follows:
4HCl + O2 2Cl2 + 2H2O

If the air used is 30% excess and oxidation is 80% complete, find the composition of dry gases
leaving.
Basis: 4 kmoles HCl gas.

O2 needed = 1 kmole
O2 supplied = 1.3 kmoles

79
N
2

entering
= 1.3

= 4.89 kmoles

O2 remaining = (1.3 0.8) = 0.5 kmole

HCl un-reacted = (4 0.2) = 0.8 kmole
Cl2 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
O2 0.50 6.42
N2 4.89 62.77
Cl2 1.60 20.54

Total 7.79 100.00

3.37 A mixture of NH3 and air at 730 mm Hg and 30 C contains 5.1% NH3. The gas is passed
through an absorption tower at the rate of 100 m3/h where NH3 is removed. The gases leave the tower
at 725 mm Hg and 20 C having 0.05% NH3. Calculate (a) the rate of flow of gas leaving the tower
and (b) weight of NH3 absorbed in kg/h.

0.05% NH3,

Abs. 20 C 100 m3/h, Tower 725 mm Hg 30 C,

730 mm Hg
5.1% NH3

Basis: One hour of operation

Moles of gas entering per hour =

100730 273
22.414303

= 3.86 kmoles
NH3 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% NH3 while leaving the absorber Therefore the total moles of
gases leaving the absorber is

=
3.663 = 3.665 kmoles0.9995

Hence, NH3 leaving the tower = 0.002 kmole.

(b) NH3 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 N2 has CO2: 4.62%, CO : 3.08%, O2:
8.91% and N2: 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 CH4 and C2H6.

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
CH4 CO2
C2H6 CO Reactions are:
Air

O2 CH4 + 2O2 CO2 + 2H2O N2 C2H6 + 31/2O2 2CO2 + 3H2O

(b) O2 supplied = 105.56 0.21 = 22.17 kmoles
O2 consumed = (22.17 8.91) = 13.26 kmoles

O2 needed for conversion of CO to CO2 = 3.08= 1.54 kmoles2

\ O2 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 CH4 be x kmole and C2H6 be y kmole Making a CO2 balance, x + 2y = (4.62 + 3.08) =
7.70 O2 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 %

CH4 5.3 81.54
C2H6 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 CO2 :
14%, CO : 1%, O2: 6.4% and the rest N2

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.
N2 = 100 (14 + 1 + 6.4) = 78.6 kmoles
From the foregoing, air supplied = 78.6/0.79 = 99.5 kmoles; O2 in air supplied is = 20.9 kmoles

Furnace Flue gas

Coke (F)
Ash (P)

O2 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 + O2 2CO
C + O2 CO2;

CO + O2 CO2
Carbon lost in ash: 10% = 51.43 0.1 = 5.143 kg (for 205.72 kg of coke fed)
O2 needed theoretically:
O2 supplied: 20.9 kmoles
O2 needed (theoretically):
Total Carbon fed = 205.72 0.9

= 185.148 kg
= 15.429 katoms
O2 needed for conversion of C to CO2 is 15.429 kmoles (by stoichiometry) Excess O2 = 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 kg205.72

\ 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 m3/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 m3 of inlet air = 1000 litres = 106 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 = 0.0326768
In the outgoing stream, moles of water/mole of wet air = 100 = 0.1316768

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 m3

3.41 Applying Ideal gas law find out the maximum temperature which 20 kg of CO2 enclosed in 20 m3
chamber may be heated to with pressure not exceeding 20 bar.

Basis: 20 kg of carbon dioxide =

20 = 0.454 kmole44

Volume at standard conditions: 0.454 22.414 = 10.19 m3P1 = 1 bar, V1 = 10.19 m3, T1 = 273 K P2 =
20 bar, V2 = 20 m3, T2 = ?

PVPV
2 2We know that 11

12

Thus T2 is found to be 10,716.3 K = 10,433.3 C

3.42 A telescopic gas holder contains 1000 m3 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 m3 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 m3.
293760
20902.79

Amount of water = 725= 1.111 kmole = 20 kg of water22.414

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 m3 of mixture of N2, CO2 and H2 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 CO2 = 3 2 = 0.75 atm
Partial pressure of H2 = 1 2 = 0.25 atm
8
T
v 1Number of moles of N = p TP
2 22.414
=
1

100 273 1 = 2.88 kmoles

v 1Number of moles CO = p TP
2 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 % %

N2 2.88 28 80.676 45.531 0.500

CO2 2.16 44 95.080 53.66 0.375
H2 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-C4H10 : 50
n-C5H12 : 30
n-C6H14 : 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 m3 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 m3. 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: CH4 : 80%, C2H6 : 15% and N2
: 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 m3/h.
The internal pipe diameter is 50 mm. Express the concentration in kmole/m3, 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 CO2 enclosed in 20 m3 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 514 102 m3 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%
CO2 : 15%
H2O : 12%
O2 :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 m3 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 CH4 : 94%, C2H6 : 3% and N2: 3% is piped from the well at 298 K and 3
atm pressure. Find (a) partial pressure of N2, (b) volume of N2 per 100 m3 of gas and (c) density of
the gas.

3.16 A gas flowing at 1000 litres/s has the following composition: CH4: 10%, C2H6: 30% and H2:
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 m3 of gas

(c) Density of mixture
(d) Average molecular weight of mixture

3.19 Acetylene gas is produced according to the reaction

CaC2 + 2 H2O C2H2 + 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 m3 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/m3.

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, VG :

volume of gas and VL : 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 RT2
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 p0 and p and T0
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
pA = p pW

\ p = pA + pW
Total pressure = vapour pressure of component + vapour pressure of water
pp W
pA
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
T0 = 273 K, T1 = 293 K, T2 = 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 1log 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 2.31g mole of water Vapour pressure of water 225
gC H66 2.31 78 10.01gwater 18
g water 0.1g benzene

4.3 It is decided to purify myristic acid (C13H27COOH) 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 H2O = 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 = 4.3 105 kmoles = 0.0098 kgMole of water

Moles of water = 1 kmole = 18 kg
Weight of steam
18
1840 kgkg 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 kgkg 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 (C6H6)
Toluene (C7H8)
Xylene (C8H10)

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 NaNO3 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.

pA = xA PA; pB = xBPB; (xA + xB) = 1

where PA, PB are vapour pressures of hexane (A) and heptane (B) respectively.
pA = yAP; pB = yBP; (yA + yB) = 1
pA + pB = P; xB = (1 xA)
(xAPA) + (1 xA)PB = P
xA(PA PB) = (P PB)
xA 760 + (1 xA)295 = 760
At 69 C, (Boiling point of hexane)

xA(760 295) = (760 295); \ xA = 1

y
760 = 1 =
A 760

At 70 C xA(780 302) = (760 302); \ xA = 0.96

pA = (0.96 780) = 748.8; \ yA = 748.8/760 = 0.985 At 75 C xA(915 348) = (760 348); \ xA =
0.73
pA = (0.73 915) = 668; \ yA = 668/760 = 0.880 At 80 C xA(1060 426) = (760 426); \ xA = 0.53
pA = (0.53 1060) = 562; \ yA = 562/760 = 0.740 At 85 C xA(1225 498) = (760 498); \ xA = 0.36
pA = (0.36 1225) = 441; \ yA = 441/760 = 0.58 At 90 C xA(1405 588) = (760 588); \ xA = 0.21
pA = (0.21 1405) = 295; \ yA = 295/760 = 0.39 At 95 C xA(1577 675) = (760 675); \ xA =
0.0945 pA = (0.0945 1577) = 149; \ yA = 149/760 = 0.196 At 99.2 C Boiling point of heptane
xA(1765 760) = (760 760); \ xA = 0 = yA 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; pA = xAPA = (0.158 1520) = 240;

yA =
240 = 0.316
760
% Error =
Actual value
Calculated value

100
0.553 - 0.316
=

100 = 42.8%
4.9 Methane burns to form CO2 and water. If 1 lb mole is burnt with 10% excess pure O2 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 O2 in exit (c) Weight of water removed.

Basis : 1 lb mole of methane.

CH4 + 2O2 CO2 + 2H2O
O2 supplied = 2 1.1 = 2.2 lb moles
Gases leaving after drying: CO2 : 1.0 lb mole; O2 : 0.2 lb mole.

530 760(a) Volume of dry exit gas = 1.2 359 492 750
= 470.26 ft3
(b) Partial pressure of O2 in exit = 0.2 750= 125 mm Hg1.2

(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%, O2 : 4% and N2 : 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 m3 of original mixture? The vapour pressure of benzene at 21.1 C is 75 mm Hg.

Basis: 1000 m3 of original mixture

1000 750 273Moles 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 N2 from a cylinder is bubbled through acetone at 840 mm Hg and 323 K at the rate of 0.012
m3/h. The N2 saturated with acetone vapour, leaves at 760 mm Hg and 308 K at 0.023 m3/h. Find the
vapour pressure of acetone at 308 K.
0.012= 5 104 kmole/h 22.414
760 323Molar flow rate of N2 =
840


(N2 + CH3COCH3) = 0.023= 9.09 104 kmole/h1.013 308
22.414 1.013

Let y be the mole fraction of N2 in leaving stream.

Then, 9.09 104y = 5 104
Solving, we get y = 0.55
Thus, mole fraction of acetone = 0.45
(PT) (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 oC. Assuming all ethane is
removed, estimate the pressure and vapour phase composition components of the system at 30 oC.

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 oC 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 oC.
Vapour pressure of benzene is 1340 mm Hg at 80 oC

Vapour pressure toluene is 560 mm Hg at 80 oC

At equilibrium, partial pressure of benzene
= (Mole fraction, xB, of benzene) (1340)
= (Total pressure) (Mole fraction in vapour phase)
= PT (0.8)
i.e. (xB) (1340) = PT (0.8)
Similarly for toluene,
xT (560) = PT (0.2)
PT (0.8) + PT (0.2) = PT
We also know that, xB + xT = 1
4 (1 xB) (560) = 4 PT (0.2)
xB (1340) = PT (0.8)
4 (1 xB) 560 = xB(1340)
2240 1340xB 2240xB = 0
Solving, xB = 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 PT be partial pressure and total pressure respectively PPA = (PT) (yA) = xA PA
PPB = (PT)(yB) = xB PB
PT(yA + yB) = xA (PA) + (1 xA) PB = PP
PT = PPA + PPB
PT = (0.7)(70) + (0.3)(20)
= 49 + 6 = 55 mm Hg
Hence, yA= (0.7)(70)/55 = 0.89
yB = (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,
PTot = (xB) (PB) + (xT) (PT)
760 = (xB) (960) + (1 xB) 380
Solving,
xB = 0.655
xT = 0.345

Px
yB = BB 960 t0.655= 0.827PTot760
In the same way, yP Px 380t 0.345= 0.173T = TT760Tot

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
ybenzene = 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.
VPA, 760 811 882 957 1037 1123 1214 1310 1412 1530 1625 1756 mm Hg
VPB, 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: C2H6 : 2%, n-C3H8 : 40%, i-C4H10 : 7%, n-C4H10 :
47% and C5H12 : 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 C2H6
were removed.
Vapour pressure data (mm Hg):
C2H6 : 28500, n-C3H8 : 6525, i-C4H10 : 2250, n-C4H10 : 1560 and C5H12 : 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 (C6H6) (molecular weight: 78) : 1340 mm Hg; Toluene (C7H8)
(molecular weight: 92) : 560 mm Hg, xylene (C7H8) (molecular weight: 106) : 210 mm Hg.

4.9 The partial pressure of actetaldehyde in a solution containing 0.245 kg of CH3CHO in 20 kg of

water is 190 mm Hg at 93.5 C. Calculate the partial pressure of CH3CHO 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 (nv): 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)
mass of B
M pp M BvB
87

Relative humidity or relative saturation ( yr%): It is normally expressed in percentage. If pv is the

partial pressure under a given condition and ps is the vapour pressure at DBT of the mixture, then

Relative saturation = yr % =
pv 100 (5.3)
ps

Percentage saturation or percentage absolute humidity ( yP): It is defined as the percentage of the
ratio of humidity under given condition to the humidity under the saturated condition.
Percentage saturation = yP % =
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 CS is the heat required to raise the temperature of unit mass of gas and
its accompanying vapour by one degree centigrade at constant pressure.

CS = CAnv+ CB (5.5) where CA and CB 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 tG, with a humidity of nv, the enthalpy relative to the reference
state t0 is,

H = enthalpy of gas + enthalpy of vapour component.

= CB(tG t0) + nv[CA(tG tDP) + lDP + CA,L (tDP t0)] (5.6) where
lDP = Latent heat of vaporization at dew point.
CA,L = Specific heat of component A (vapour) in liquid phase. The above Eq. (5.6) will reduce to
Eq. (5.7) when tDPitself is taken as the reference temperature, t0
H = CB (tG t0) + nv[CA(tG t0) + l0]
= CS (tG t0) + nv l0 (5.7)

Humid volume: The humid volume vHof 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 m3/kg is
2731105 v MM 273 p

=+
nt(5.8)

where, p= total pressure N/m2

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 % = yr =
pv 100 where,
ps
pv = Partial pressure of vapour ps = Vapour pressure of pure liquid Percentage saturation = yp = nv
100ns

where,
nv = moles of vapour per mole of vapour free gas actually present ns = moles of vapour per mole of
vapour free gas at saturation. If p is the total pressure, then from Daltons law,
v, and ns = snv =
- -
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 105 N/m2
Molecular weight of air = 28.84
(i) nv(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
pAmolal humidity (0.0483) = pp
-A
pA0.0483 =1.0133 105
p A

5
20.69 =
1

where,
pA = 4.672 103 N/m2

pA = Partial pressure of water p = Total pressure

Vapour pressure of water (Steam Tables) at 50 C = 92.51 mm Hg = 12.332 103 N/m2
\
% R.H. = 4.672

103
12.332
103 =37.88%
(iv) Dew point = 31.5C
(v) Humid heat = CS = CB + CA 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 = CS (tG t0) + n l0 (Eq. 5.7)
l0 = 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 vH

(a) vH = (8315)

1(325) n
= (8315)


= 0.969 m3 mixture/kg of dry air

Alternatively,
(b) Specific volume of saturated air = 1.055 m3/kg of dry air

Specific volume of dry air = 0.91 m3/kg of dry air By interpolation vH = 0.91 + (1.055 0.91)(0.35)
= 0.961 m3/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/ft3 of mixture
(d) lb of vapour/lb of vapour free gas
(e) lb moles of vapour/lb mole of vapour free gas
(a) Basis: 1ft3 of gas mixture

Percentage of ethyl ether =

442 1= 0.593 ft3 = 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 ft3

43.9
\
lb of vapour/ft
3
=
= 0.112
(d) lb of vapour/lb of vapour free gas = 43.9 = 3.8511.4
(e) lb mole vapour/lb moles vapour free gas = 0.593 = 1.4570.407
5.3 A mixture of acetone vapour and nitrogen contains 14.8% acetone by volume. Calculate yr and yp
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 n
184.8

0.248= 0.329 = n
s 560.2 0.752

yp = nv 0.174= 52.9%ns 0.329

Always yr > yp
5.4 Moist air is found to contain 8.1 grains of water vapour per ft3 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 ft3 of water vapourair mixture

Amount of water =
8.1 = 1.16 103 lb 6.42 105 lb moles
7000
Pure component volume of water at 30 C
303
= 6.42

10
5 359 = 0.0256 ft3

0.0256
= 19.4 mm HgPartial pressure of water vapour = 760

Vapour pressure of water vapour = 19.4 = 130 mm Hg0.15
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 ft3 of entering gas. Vapour pressure of water at 70 F = 0.36 psi.
Basis: 1000 ft3 of entering gas 70 F and 14.3 psi
1000 14.3 492lb mole of gas mixture =


= 2.52 lb moles
y
p

= 0.5 =
nv
ns
where nv = 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 ft3 of gases entering.
(d) Calculate the volume of gases leaving the evaporator per 1000 ft3 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 N2 = 634 mm Hg
mole of acetone/mole of N2 =
116 = 0.183
634
Leaving gases: partial pressure of acetone = 185 mm Hg partial pressure N2 = 750 185 = 565 mm
Hg

mole of acetone/mole of N2 = 185 = 0.328565

Basis: for (b), (c) and (d): 1 lb mole of N2 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 ft3Volume of entering gas = 1.183 359
750 273
Weight of acetone evaporated = (0.145 58) = 8.4 lb
Acetone evaporated per 1000 ft3 = 8.41000= 17.6 lb477
(d) Total moles of gas leaving = (1 + 0.328) = 1.328 lb moles
760 303Volume of gases leaving = 1.328 359 = 526 ft3
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 ft3 of gas. (d) Calculate the final volume of
wet air leaving.
Data: Vapour pressure of H2O 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
14Initial 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 Hg14.7
9.2Final humidity =

-
= 0.0051 kmole of water vapour/kmole of dry air Basis: 1000 ft3 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 ft3Volume 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 oC 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=17.5s
where, partial pressure of H2O vapour = pv = 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, ps = pv = 9.2 mm Hg)
p
s

=
pp2000 9.2--
= 4.6 103 g mole of water vapour/g mole of dry air (iii) Basis: 1000 litres of original wet air
1000 750273g 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 4.6 103) 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 solidDrier 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 H2O

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 kmoles18
\ Total moles of wet air = 94.33 kmoles
301
Volume of wet air = 94.33

22.414

= 2331.17 m3

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 lb0.995

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 H2O = 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 ft3/h.

5.13 Air at 100 oF 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 ft3 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 H2O in entering air = 1.9325 0.2 = 0.3865 inches of Hg

Partial pressure of H2O in exit air = 0.8754 0.7

= 0.6128 inches of Hg
(lb mole H2O/lb mole dry air) in entering air

=
0.3865= 0.0132829.48 0.3865
(lb mole H2O/lb mole dry air) in outgoing air
= 0.6128= 0.0212329.48 0.618
lb mole H2O evaporated/lb mole of dry air = 0.00795
18
lb H
2

O/lb of dry air = 0.00795

3
= 5 10 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 ft3Volume 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 N2 followed by cooling and compression of

the final gas mixture. In the solvent recovery unit 50 lb of acetone are removed per hour. The N2 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 ft3 of incoming gas must be admitted per hour to

obtain the required rate of evaporation of the acetone? (b) How many ft3 of gases leave the unit per
hour?
N2, Acetone 100 F 750 mm Hg N2, Acetone
Drier
partial pressure of acetone 10 mm Hg 85F, 740 mm Hg 85% saturation

(Molecular weight of Acetone (CH3)2CO 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 in entering stream =
2 = 0.0135

p v287yp = 0.85 = 740 p287

where
yp (percentage saturation) = 85%
pv (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 N2 removes: (0.5385 0.0135)
= 0.525 lb mole of acetone
lb mole N2 needed/h = 0.862 = 1.642 lb mole0.525
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 ft3
(b) Total moles of exit gas = 1.642 1.5385 = 2.526 lb moles
545 760Volume of exit gases = 2.526 359

= 1031.6 ft3
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 m3 at 20C and 108 kPa when dry. What was
the relative humidity of the air?
Basis: 1000 m3 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
p98.6 = 0.114 kPav = Partial pressure of water =
ps = Vapour pressure of water = 15 mm Hg = 2 kPa
pv, y = 0.114 100 = 5.7%, Relative humidity, y =
r Q r ps

5.17 At 297 K and 1 bar, the mixture of N2 and C6H6 has a relative humidity of 60%. It is desired to
recover 90% C6H6 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/m2 and 12.2 kN/m2 respectively.

Relative humidity = 0.6 = Partial pressure/Vapour pressure

12.2
60 103
Partial pressure =
= 7.32 103 N/m2
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. 3 780.0217 610
=3 28PT 610

Therefore, PT, the total pressure = 7.642 105 N/m25.18 Humid air at 75 C, 1.1 bar and 30%
relative humidity is fed at a rate of 1000 m3/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 = 1.1 105 N/m2

1 atm = 760 mm Hg = 1.013 105 N/m2
Therefore, 1.1 bar = 825.36 mm Hg
Mole fraction of water vapour = (86.7/825.36) = 0.105 Volumetric flow rate = 1000 m3/h at 75 C
and 1.1 bar 1000 825 273 138 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 103 N/m2. 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 =
7.4 103 N/m2

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/7.4 103
Partial pressure = 5.18 103 N/m2

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
removedDry air needed = Water removed per kg of dry air
=0.0868 = 3.17 kg/s0.02738
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 m3 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 = 0.02973740Mole fraction of water vapour
in original air when cooled to 15 C
= 12.7 = 0.017740
Therefore, mole fraction of dry air = 0.983
Moles of wet air at 15 C = 37.976 = 38.63 kmoles0.983
Volume of dry air at new condition (assuming ideal behaviour)
=
38.63

760 288= 938.11 m3/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 m3 of water.

Weight of water evaporated = 0.1 1000 = 100 kg (since the density is 1000 kg/m3)
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 s0.001
= 100000= 27.7 h3600

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/h5

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/h0.009

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 = Gs (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 m3/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 m3/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 m3 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
m3/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 (CS2) by
volume. Calculate the relative saturation and percent saturation of the mixture at 20 C and 740 mm
Hg pressure. Vapour pressure of CS2 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 m3/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 m3/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 m3 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
m3/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
xF Crystallizer
Mother liquor, M kg/h xM
Crystal, C kg/h
xC
Feed rate of solution of concentration, xF : F kg/h Amount of water evaporated
(xE = 0 as salt in water evaporated will be zero) : E kg/h Amount of mother liquor of concentration
xM : M kg/h (Mother liquor will always be a saturated solution)
Weight of crystal formed of concentration, xC : C kg/h Total mass balance gives, F = C + M + E (6.1)
Component balance gives, FxF = CxC + MxM + ExE (6.2)

Since we normally know F, E, xF xM xEwe can find C and M by solving the Eqs. (6.1) and (6.2). xE
will always be zero as it is free from salt.
When we get anhydrous salt, xCis 1.0. Some times we get hydrated salt during crystallization process.
Under such circumstances xC 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 H2O

Solubility of NaCl at 65 C = 6.37 kg mole/1000 kg H2O 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
1000Water 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 kg1000

6.2 After a crystallization process, a solution of calcium chloride in water contains 62 kg CaCl2 per
100 kg of water. Calculate the weight of this solution necessary to dissolve 250 kg of CaCl2 6H2O at
25 C (solubility = 7.38 kg mole CaCl2/1000 kg H2O)

Basis: x kg of water is present in original solution

CaCl2 6H2O has the molecular weight = 111 + 108 = 219 250 kg of solution will have 126.7 kg of
CaCl2 and 123.3 kg of 6H2O Total CaCl2 entering the process = (0.62x + 126.7) kg (1) Water
entering the process = (x + 123.3) kg
Solubility of CaCl2 at saturated condition for 1000 kg water

= 7.38 kmoles = 819.18 kg

\ CaCl2 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
162129.03 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% NaNO3 by weight.
(a) Calculate the percentage saturation of this solution (b) Calculate the weight of NaNO3 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 NaNO3 at 40 C = 51.4% by weight.
Solubility of NaNO3 at 10 C = 44.5% by weight.
Basis: 1000 kg of original solution
(a) kg of NaNO3 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 NaNO3 crystallized out

NaNO3 balance = (1000 0.49) = (1000 a) (0.445) + a; Solving, a = 81 kg

81
(c) % Yield =

100 = 16.53%

6.4 A solution of K2Cr2O7 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 K2Cr2O7 crystals formed.
Solubility at 20 C = 0.39 kmole/1000 kg H2O

Basis: 1000 kg of original solution

K2Cr2O7 = 130 kg;
Water = 870 kg
Water present finally = (870 640) = 230 kg
0.39
294 = 26.4 kg K Cr O present then = 230
2 2 7
\ K2Cr2O7 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 H2O)

Basis: 1000 g of original solution

100
= 91 gNaNO3 present initially = 1000 Water present initially = 909 g
Water retained along with NaNO3 = 1000 91= 172.6 g6.2 85

\ Ice formed = Original water water retained along with NaNO3 = (909 172.6) = 736.4 g

6.6 1000 kg of a 30% aqueous solution of Na2CO3 is slowly cooled to 20 C. During cooling, 10%
water originally present evaporates. The crystal is Na2CO3 10H2O. If the solubility of anhydrous
Na2CO3 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 Na2CO3=
106 and that of Na2CO3 10H2O = 286 a + b = (1000 70) = 930 kg

106 21.5 = 300 kg2CO3 balance = abNa

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

700

100 = 630 kg

6.7 A batch of saturated Na2CO3 solution of 100 kg is to be prepared at
50 C. The solubility is 4.48 g mole/1000 g H2O 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 Na2CO3/1000 kg H2O i.e. 474.88 kg Na2CO3/1474.88 kg
solution.
100 474.88In 100 kg of solution, Na2CO3 present = 1474.88

= 32.2 kg
water present = (100 32.2) = 67.8 kg
Molecular weight of Na2CO3 H2O = 106 + 18 = 124 kg Molecular weight of Na2CO3 10H2O =
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 kg106
Discussion: In case (ii), water available in the salt is
32.2 180 = 54.68 kg106

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/hrCentrifuge6% solution Evaporator
AdheringWater
solution
+ Dry crystal crystalDrier 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 H2O = 0.3 kg salt/kg H2O

(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 benzeneTank
0.183 wt fr. of naphthalene0.57 wt. fr. of naphthalene
Basis: 1 mole of feed solution
Component mole Molecular Weight, kg Weight weight fraction

Naphthalene (C10H8) 0.12 128 15.4 0.183

Benzene (C6H6) 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 Na2SO4. 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 Na2SO4/100 g water

Molecular weight of Glaubers salt (Na2SO410H2O) = 142 + 180 = 322 Basis: 7,500 kg of aqueous
solution.
Na2SO4 present = 7500 0.296 = 2220 kg
H2O present = (7500 2220) = 5280 kg
H2O lost in evaporation = 5280 0.05 = 264 kg
H2O 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 O balance: 5016 = 180
2

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 oC

(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.
Na2SO4.10H2O crystallizes out. If the mother liquor (after crystallization) is found to contain 18.3%
Na2SO4, calculate the weight of the mother liquor.

10% water
6,400 kg 18.3% Na2SO4Crystallizer Mother liquor M
29.6%
Na2SO4 10H2O (142 + 180) = 322

Basis: 6,400 kg solution.

Weight of Na2SO4 = 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 Na2SO4 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.

Na2SO4.10H2O (142 + 180 = 322)
Na2SO4 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 FeSO4.5H2O crystals per hour. The feed
solution contains 38.9 parts FeSO4/100 parts water. The feed enters at 70 C and is cooled to 27 C.
The solubility at 27 C is 30.3 parts FeSO4/100 parts water. Determine the quantity of feed and water
lost as vapour.

6.3 10,000 kg of a 30% aqueous solution of Na2CO3 is slowly cooled to 20 C. During cooling, 3%
water originally present evaporates. The crystal is Na2CO3.10H2O. If the solubility of anhydrous
Na2CO3 at 20 C is 21.5 kg/100 kg of water, what is the weight of Na2CO3.10H2O formed?

6.4 1000 kg of a solution containing 25% of Na2CO3 by weight is slowly cooled to 20 C. During
cooling 15% water originally present evaporates. The crystal formed is Na2CO3.10H2O. If the
solubility of anhydrous Na2CO3 at 20 C is 21.5 kg/100 kg of water, what is the weight of
Na2CO3.10H2O crystals formed?

6.5 1500 kg of a solution containing 20% of Na2SO4 and 80% water by weight is subjected to
evaporative cooling and 20% of original water evaporates. Calculate the yield of Na2SO4.10H2O
crystals formed from solution, if the temperature of solution is reduced to 20 C. The solubility of
anhydrous Na2SO4 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% KNO3 solution to 50% KNO3. The concentrated
liquor is sent to a crystallizer where crystals of KNO3 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 KNO3/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% Na2SO4 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% Na2SO4

At 5 C : 5.75% Na2SO4
6.9 A solution of K2Cr2O7 in water contains 16% K2Cr2O7 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 K2Cr2O7
crystals is 80%, calculate the amount of water evaporated.

Solubility of K2Cr2O7 at 20 C = 0.39 k mole/1000 kg H2O 6.10 A saturated solution of MgSO4 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 MgSO4.7H2O crystallizes. Solubility data: At 80 C : 64.28 g MgSO4 per 100 g
water At 25 C : 40.88 g MgSO4 per 100 g water

6.11 Hypo crystals Na2S2O3 5H2O are to be produced at the rate of 2000 kg/h. A 60% Na2S2O3
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 = 105 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 P4 : 8%, CO : 89% and N2: 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 CO2: 0.9%, CO : 22.5%, N2 : 68.0% and O2: 8.6%. Assume oxidation of phosphorus is
complete and that it exists in the flue gas partly as P4O6 and partly as P4O10. Calculate:

(a) % of CO entering the furnace that is oxidized to CO2 and (b) % of P4 that is oxidized to P4O10
P4 + 3O2 P4O6
P4 + 5O2 P4O10
CO + O2 CO2

Exit gas
from phosphate
reduction furnaceBurner CO2, O2, Air CO, N2
Oxides of P

Basis: 100 g moles of exit gas from phosphate reduction furnace P4 is 8 g moles.
Let x g mole of P4 get converted to P4O10
\ (8 x) g mole of P4 gets converted to P4O6 Carbon is the tie element
89 g atoms of C 23.4% of final gas. (Total carbon in CO and CO2)

89 =380.342 g moles\ Total final gas moles = 0.234

(a) % CO oxidized to CO2 = (380.342 0.009/89) 100 = 3.852 g moles
(b) N2 in final gas = (380.342 0.68) = 258.632 g moles N2 from air = (258.632 3) = 255.632 g
moles
O21 = 67.953 g moles2 from air = 255.632 79

O2 for formation of P4O10 = 5x g mole

O2 for formation of P4O6 = 3(8 x) g mole
O2 for formation of CO2 = 380.342 0.009 0.5 = 1.712 g moles O2 leaving = 380.342 0.086 =
32.71 g moles
O2 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
\ P4 converted to P4O10 = (4.7654 100/8) = 60%
7.5 A tank of weak H2SO4 contains 12.43% acid. If 200 kg of 77.7% H2SO4 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 kg0.91

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% NH3, 25.4% N2 and the rest H2 is flowing in a pipe. To measure the flow
rate an ammonia rich gas containing 96%

NH3, 3% H2 and 1% N2 is sent at a rate of 100 cc/min. The concentration of NH3 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% NH3NH rich gas
3
(96%) 100 cc/min.

7.8 A lime stone analysis shows CaCO3: 94.52%, MgCO3: 4.16% and rest insoluble. (a) How many
kg of CaO could be obtained from 4 tonnes of limestone? (b) How many kg of CO2 are given off per
kg of limestone?
(a) Basis: 4 tonnes of limestone = 4,000 kg
CaCO3 = 0.9452 4000 = 3,780.8 kg
MgCO3 = 0.0416 4000 = 166.4 kg

CaCO3 CaO + CO2

100 56 44
MgCO3 MgO + CO2
84.3 40.3 44

CaO got =
3780.8 56= 2,117.3 kg
100
(b) Basis: 1 kg of limestone
CaCO3 = 0.9452 kg, MgCO3 = 0.0416 kg
44 44CO produced = 0.9452 +
2


= 0.4376 kg (by stoichiometry)

7.9 The gases from a sulphur burner have the following analysis: SO2: 9.86%, O2: 8.54%, N2: 81.6%.
After passage of gases through a catalytic converter, the analysis is 0.605% SO2; 4.5% O2; 94.895%
N2. What percentage of SO2 entering the converter has been oxidized to SO3?

Basis: 100 g moles of gas entering the converter

N2 is the tie element.
Exit stream =
81.6 = 86 g moles
0.94895

SO2 leaving = 86 0.00605 = 0.5203 g moles

SO2 converted to SO3
= SO2 entering SO2 leaving the converter
= (9.86 0.52) = 9.34 g moles

% SO2 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 H2SO4. 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 + 2HCl24 24
(2 58.4) 98142 (2 36.4)

2
36.4
(a) HCl formed = 1960

2 58.4= 1221.6 kg
(b) Na2SO4 formed = 1960 142= 2382.9 kg2

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 H2SO4 to recover Mg as MgSO4. The rock analysis indicates 20% Ca, 10% Mg and 5%
SiO2. After reaction the soluble material is filtered off and the solid are washed and discarded.
Analysis of the sludge cake shows 50% moisture, 2% SiO2; 0.5% Mg and 1% Al. What fraction of
Mg was extracted? Basis: 100 g of dolomite

SiO2 is the tie element

5 g SiO2 2% sludge cake
\ weight of sludge cake =
5 = 250 g
0.02
Mg in sludge cake = 250 0.5 = 1.25 g100
Mg extracted = (10 1.25) = 8.75 g
Fraction Mg extracted = 8.75= 0.87510

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 CO2 gas. When pure limestone is calcined, 44.8 g of CO2 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 CaCO3 and y g be the weight of MgCO3

CaCO3 CaO + CO2

100 56 44
MgCO3 MgO + CO2
84.3 40.3 44
Overall balance: x + y = 100 (since pure)
CO2 balance = 0.44x + 0.52y = 44.8
Solving, x = 90 g (CaCO3) and y = 10 g (MgCO3) 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.
xy
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%, H2: 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% CO2 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; H2: 0.152 kg = 0.076 kmole; Noncombustibles 0.008 kg
C+O

CO ; H +O
nn H O222 2 2
12 32 44 2 16 18

CO2 formed 0.07 kmole

H2O 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 kmole0.21

Exhaust gas contains CO2, N2 and O2
Excess air in exhaust = Total moles in exhaust stream (dry)

(N2 entering as per stoichiometry + CO2 formed) = 0.814 (0.4063 + 0.07)

= 0.814 0.4763 kmole
= 0.3377 kmole

We know what air contains

O2 = 0.071 kmole (21%) N2 = 0.2667 kmole (79%)
N2 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

CO2 0.0700 8.6

O2 0.0710 8.7
N2 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 CO2 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 C2H4 : 1.085%, CO2: 4.345%, O2: 13.055% and N2: 81.515% on dry basis.
The partial pressure (pp) of H2O 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% C2H4
Reactor

95% air Gases Ethylene, CO2, Absorber O2, N2

pp.H2O 15.4 mm Hg
Ethylene glycolwater
Reactions:
1.
2C H + O 24 2 Ethy lene

2C H O 24
Ethy lene oxide

2. C2H4 + 3O2 2CO2 + 2H2O

3. C H O+HO (CHOH)
24 2 2 2 Ethy lene gly col

Basis: 100 kmoles of feed gas.

C2H4: 5 kmoles; O2 : (95 0.21) = 20 kmoles; N2: 75 kmoles
N75 = 92 kmoles2 balance: Moles leaving the absorber = 0.81515

C2H4 : 92 0.01085 = 1 kmole

CO2 : 92 0.04345 = 4 kmoles
O2 : 92 0.13055 = 12 kmoles

H2O =
92 15.4= 1.94 kmoles
74515.4
C2H4 reacted : 5 1 = 4 kmoles
C2H4 converted to CO2 : 4 = 2 kmoles2

C2H4 converted to C2H4O : 4 2 = 2 kmoles

Water formed by reaction 2 = 4 mole CO2 kmole [oxygen sent] [used up oxygen] = 20 [1 + 6] =
13 kmoles

Moles of gases entering absorber: C2H4 : 1; CO2 : 4; C2H4O : 2; H2O:4; O2 : 12; N2:75
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 % (CH2OH)2 2.00 62 124.00 86.88
Ethylene glycol
(H2O) 1.04 18 18.72 13.12
Water
Total 3.04 142.72 100.00
7.19 The first step in the manufacture of H2SO4 from pyrites consists of burning pyrites in air. The
reactions taking place are:
FeS2 + 2.5O2 FeO + 2SO2 (1) 2FeS2 + 5.5O2 Fe2O3 + 4SO2 (2)

The flue gas analysis shows SO2: 10.2%; O2: 7.8%; N2: 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

SO2: 10.2%; O2: 7.8%; N2 : 82%
Let x kmole of FeS2 by reaction (1) and
y kmole of FeS2 by reaction (2) be reacted.

(a) O
21 = 21.8 kmoles (using nitrogen balance) fed = 82
2 79

O2 leaving = 7.8 kmoles; O2 used = 14 kmoles

SO2 balance = 2x + 2y = 10.2; \ x + y = 5.1 (a) O2 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
y5
(b) Total FeS2 reacted = 5.1 moles
O2 needed by Reaction (2) = 5.1 5.5= 14.025 moles2
Excess O2 supplied = 21.8 14.025 = 7.775 moles
7.775
% excess air =

100 = 55.4%

7.20 A producer gas contains CO2: 9.2%, C2H4: 0.4%, CO : 20.9%, H2: 15.6%, CH4: 1.9% and N2:
52%, when it is burnt, the products of combustion are found to contain CO2: 10.8%, CO : 0.4, O2 :
9.2%, N2: 79.6%. Calculate the following:

(a) m3 of air used per m3 of producer gas (b) % excess air

(c) % N2 that has come from producer gas. Basis: 100 g mole of producer gas

Component Weight, g mole C atom

CO2 9.2 9.2

C2H4 0.4 0.8
CO 20.9 20.9
H2 15.6 CH4 1.9 1.9
N2 52.0

Total 100.0 Reactions

C2H4 + 3O2 2CO2 + 2H2O CO + 0.5O2 CO2

H2 + 0.5O2 H2O
CH4 + 2O2 CO2 + 2H2O

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

N2 from air: N2 in exit = 293 0.796 = 233 g moles

N2 in feed = 52 g moles
N2 from air = 181 g moles

O
2

from air = 181

21 = 48; Total air = 229 g moles m3 of air/m3 79

feed = g mole of air/g mole of feed = 229 = 2.29100(b) O2 supplied = 48 g moles

needed = 23.25 g moles
Excess O2 supplied = (48 23.25) = 24.75 g moles

% excess air = 24.75 100 = 106.45%23.25

(c) Total N2 leaving = 233 g moles
% N100= 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:

CH3OH + 0.5O2 HCHO + H2O (1) HCHO + 0.5O2 HCOOH (2)

The product gases have the following composition. CH3OH : 8.6%; HCHO : 3.1%; HCOOH : 0.6%;
H2O : 3.7%; O2: 16%; N2: 68%. Find the following:
(a) the percentage conversion of CH3OH 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 CH3OH supplied = reacted by reaction (1) + unconverted at the end = (3.7 +
8.6) = 12.3 g moles
(a) % conversion of CH3OH 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; O2 = 18 g moles0.79
Moles of feed/moles of air = 12.3 = 0.14386.0
O2 needed for converting CH3OH to HCHO = 12.3= 6.152Excess O2 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%; FeS2: 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 Cu2O 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
2FeS2 + 5.5O2 Fe2O3 + 4SO2 (2) 2Cu O + C 2Cu + CO(3)142 12 126 28
Basis: 1 tonne of ore = 1000 kg
Ore Crushing andP 1
Roaster P 2 Cu, COFlotation

Inert (2/3) CuS : 100 : 16.67% FeS2 : 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 P1 \ P1 = 600 kg
CuS in P1 = 600 0.166 = 100 kg; FeS2 = 600 0.5 = 300 kg
(a) Cu2O got from CuS = 100 142 = 74.74 kg190
(b) Cu2O reacted = 74.74 0.95 = 71.0 kg
(c) Cu got from Cu 126 = 63 kg2O = 71 142

7.23 Pyrites is roasted in producing SO2. The gases leaving the roaster have a temperature of 500 C
with composition SO2: 9%, O2: 8.6% and N2: 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 FeS2 = 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 kmole2 = 75 kg = 120

SO2 produced = 0.625 8 = 1.25 kmoles4
SO2 = 1.25 kmoles 9% of exit gas.
1.25 = 13.89 kmoles\ Total exit gas in mole =
0.09
O2 in exit gas = 13.89 0.086 = 1.19 kmoles N2 in exit gas = 13.89 0.824 = 11.44 kmoles
O 11 = 1.72 kmoles2 consumed = 0.625 4
(a) % excess air = 1.19 100 = 69.2%1.72
(b) Air supplied = 1.19 1.72= 13.86 kmoles0.21
Volume of air supplied = 13.86 22.414 = 310.6 m3 at NTP.
773 = 881.5 m3(c) Volume of exit gas = 13.89 22.414
273

7.24 A fuel oil with the following composition C : 84%, H2: 13%, O2 : 1%, S : 1% and H2O : 1%; is
burnt and the flue gas obtained gives the following analysis: CO2 : 9.9%, CO : 1.6%, H2O : 10.75%,
SO2 : 0.05%, O2 : 3.7% and N2 : 74%. Calculate the % excess air used.

Basis: 100 g of oil

g g atoms O2 needed Reaction
C 84 7.00 7.00 C + O2 CO2
H2 13 6.50 3.25 H2 + O2 H2O
S 1 0.03 0.03 S + O2 SO2 10.28
O2 1 0.03 0.03
H2O 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
N2 in exit = (60.87 0.74) = 45.04 g moles
45.04
Air supplied =

= 57.02 g moles
\ O2 supplied = 11.98 g moles and
excess O2 = 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
SO3 and the remaining goes to SO2. S to SO3 is the desired reaction

(a) What is the analysis of resulting gases?

(b) The gases from the burner are passed through a converter where

SO2 is converted to SO3 (without addition of any more air) if the gases leaving the converter has
4.3% SO2. Calculate the molar ratio of SO3to SO2 in the exit gas.

Basis: 1 g atom of S = 32 g

S+O SO S + 1.5OSO
22 23
32 32 64 32 48 80

O2 needed = 1.5 g mole

O2 supplied = 1.5 1.2 = 1.8 g moles
N2 supplied = 1.8 79/21 = 6.8 g moles
O2 reacted = 0.7 + (0.3 1.5) = 1.15 g moles
Exit gas stream:

Component SO2 SO3 O2 N2Total 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 SO2 react to form SO3

SO2 + 0.5 O2 SO3

Exit gas stream consists of the following:
SO2 = 0.7 x
SO3 = 0.3 + x
O2 = 0.65 0.5x
N2 = 6.8
Total = 8.45 0.5x

SO
0.7 x0.0432 = 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 SO2) 5% S is oxidized to
SO3 and rest to SO2. 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 SO2 Therefore oxygen supplied = 15.625 1.2
= 18.75 kmoles
N79 = 70.54 kmoles2 entering = 18.75 21

S to SO2 = 15.625 0.95 = 14.845 kmoles

S to SO3 = 15.625 0.05 = 0.780 kmole
Total O2 consumed = [14.845 + (1.5 0.78)] = 16.015 kmoles O2 remaining = (18.75 16.015) =
2.735 kmoles

Exit gas SO2 SO3 O2 N2Total 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 SO2 : 7.2%, O2: 13.2% and N2: 79.6% and
that of the gas leaving is SO2 : 2.8%, O2: 11.7% and N2: 85.5%. Determine the % of SO2 oxidized to
SO3Basis: 100 g moles entering

79.6\ Total
moles in exit = 0.855
= 93.1 g moles (making nitrogen balance) \ SO2 in exit stream = 93.1 0.028 = 2.61 g moles
SO2 converted to SO3
= moles of SO2 entering moles of SO2 in exit stream = 7.2 2.61 = 4.59 g moles

% SO
100 = 63.75% oxidized = 4.59
2 7.2

7.28 Limestone containing (on dry basis) 42.5% CO2 is burnt with coal having an analysis of 81% C;
4.7% H2; 1.8% N2; 4.6% O2 and 7.9% ash. The stack gas analyzes 24.4% CO2, 4.1% O2 and 71.5%
N2. 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% O2; 77% N2 by weight %)

C + O2 CO2
H2 + 0.5O2 H2O
On weight basis,
N2 balance gives, 0.018z + 0.77y = 71.5 28 = 2002 O2 balance gives,

3216
(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
CO2 balance gives: 24.4 kmoles CO2 = 1,073.6 kg 12 kg C gives 44 kg CO2

Carbon in coal = 187

0.81 kg C gives
44187 0.81 12 = 555.4 kg of CO2
\ CO2 obtained from limestone = total CO2 CO2 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 kg44
(a) Lime produced/coal burnt = 659.5= 3.5187
N2 O2 CO2

(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 CO2; 10% to CO; and 10% remains unburnt. Calculate the stack gas composition.

Basis: 100 g moles of gas

we have,
C2H6: 80 g moles
O2: 20 g moles
C2H6 + 3.5O2 2CO2 + 3H2O
C2H6 + 2.5O2 2CO + 3H2O
O2 needed = 80 3.5 = 280 g moles
O2 available in gas = 20 g moles
O2 theoretically needed = 260 g moles
200% excess oxygen is supplied
\ O2 supplied = (260 3) = 780 g moles
Total O2 available = 20 + 780 = 800 g moles
N2 entering = (780 79/21) = 2,934 g moles
CO2 formed = 80 0.8 2 = 128 g moles
CO formed = 80 0.1 2 = 16 g moles
O2 used = (80 0.8 3.5) + (80 0.1 2.5) = 244 g moles

O2 remaining = Oxygen available oxygen used = (800 244) = 556 g moles

H2O formed = (80 0.8 3) + (80 0.1 3) = 216 g moles C2H6 remaining = 80 0.1 = 8 g moles
Composition of stack gases:

Gases g moles mole %

CO2 128 3.318

CO 16 0.415
O2 556 14.412
N2 2,934 76.050
H2O 216 5.598
C2H6 8 0.207

Total 3,858 100.000

7.30 Pure CO2 may be prepared by treating limestone with sulphuric acid. The limestone used in the
process contains CaCO3, MgCO3 and inert compounds. The acid used contains 12% H2SO4 by
weight. The residue from the process had the following composition: CaSO4 : 8.56%, MgSO4 :
5.23%, H2SO4 : 1.05%, Inert : 0.53%, CO2 : 0.12%, H2O : 84.51%. During the process, the mass
was warmed where CO2 and H2O 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, CaSO4: 8.56 kg, MgSO4: 5.23 kg
CaCO3 + H2SO4 CaSO4 + CO2 + H2O
100 98 136 44 18

MgCO3 + H2SO4 MgSO4 + CO2 + H2O

84.3 98 120.3 44 18

8.56 kg of CaSO4 obtained from 8.56

100 = 6.3 kg of CaCO
3 136

5.23 kg of MgSO4 obtained from 5.23 84.3 = 3.67 kg of MgCO3120.3

(a) Limestone analysis CaCO3 MgCO3 Inert Total Weight, kg 6.3 3.67 0.53 10.50 Weight % 60
34.95 5.05 100.0
98 kg of H SO = 6.174 kg3 requires (b) 6.3 kg of CaCO
2 4

3.67 kg of MgCO
3

requires

98 kg of H SO = 4.27 kg
2 4 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 formed = 6.3 CO
2

H
2

O formed =
6.3
18

18 = 1.918 kg
84.3
H2O 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

H2O in residue = 84.51 kg
CO2 in residue = 0.12 kg
\ Amount of H2O vapours = (86.204 84.51) = 1.694 kg

and CO2 in gas phase = (4.689 0.12) = 4.569 kg vapours: H2O 1.694 kg 27 % (weight %) 47.56
mole % CO2 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 kg10.57.31 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
H2 = 0.07 kg = 0.035 kmole

32 16= 2.88 kg [by stoichiometry]2 needed = 0.87 (a) O

O2 supplied = (2.88 1.4) = 4.032 kg
Air supplied = 4.032 = 17.38 kg0.232
kg of air/kg of coal = 17.38
(b) Gases leaving are: CO2, H2O, O2 and N2
CO44 = 3.19kg = 17.41 wt %2 produced = 0.87 12
H2O produced = 0.07 18 = 0.63kg = 3.44 wt %2
O2 remaining = (4.032 2.88) = 1.152 kg = 6.29 wt % N2 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:

CO2: 10.2%, O2: 8.3%, N2: 81.5%; Find the following: (a) % excess air used
(b) the composition of fuel oil in weight %
(c) m3 of air supplied/kg of fuel.
Basis: 100 kmoles dry stock gas

N2 in stack gas = 81.5 kmoles

Air supplied =
81.5 = 103.16 kmoles
0.79

O2 entering = 81.5 21 = 21.66 kmoles79

O2 leaving = 8.3 kmoles
O2 consumed = (21.66 8.3) = 13.36 kmoles

8.3
(a) % excess air =

100 = 62.13%

(b) Let the fuel be CxHy

CxHy + (x + y/4)O2 xCO2 + y/2H2O x = 10.2 kmoles (CO2);
x + y/4 = 13.36 kmoles (O2 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% HNO3; 57% H2SO4; 20% water. This
acid is to be concentrated to 27% HNO3, 60% H2SO4 by addition of 93% H2SO4 and 90% HNO3.
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 H2SO4 and
z kg be the weight of HNO3

Overall balance: x + y + z = 1000

Balance for H2SO4 gives, 0.57x + 0.93y = 1000 0.60 = 600 Balance for HNO3 gives, 0.23x + 0.9z =
1000 0.27 = 270 Solving, x = waste acid = 418 kg

y = con. H2SO4 = 390 kg

z = con. HNO3 = 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

BaSO4 + IM + Na2CO3 BaCO3 + Na2SO4 + IM (IM = infusible matter)

Analysis of product: 11.3% BaSO4; 27.7% Na2SO4; 20.35% Na2CO3 Therefore, (BaCO3 + IM) =
100 (11.3 + 27.7 + 20.35) = 40.65%
BaSO
+ Na CO BaCO + Na SO
423 3 24
233 106 197 142
Na2SO4 = 27.7 kg
Weight of
BaSO4 reacted = 27.7 233 = 45.45 kg142
Na2CO3 reacted = 27.7 106 = 20.68 kg142
BaCO 197 = 38.43 kg3 formed = 27.7 142
BaSO4 initially present = (45.45 + 11.3) = 56.75 kg
Na2CO3 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

BaSO4 = 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 Na2CO3:
Na2CO3 needed for all BaSO4 = 56.75 106 = 25.82 kg233
Excess Na2CO3 = (41.03 25.82) = 15.21
15.21
% excess =

100 = 58.9%

7.35 A fuel oil containing 88.2% C and 11.8% H2 is burnt with 20% excess air. 95% of carbon is
burnt to CO2 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 H2 11.8 5.90 kmoles Total 100.0
C + O2 CO2

C + 0.5O2 CO
H2 + 0.5O2 H2O
95% C is converted to CO2 = 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 H2 to H2O = 5.9 kmoles
Oxygen used for this reaction is = 5.9= 2.952
O2 needed (theoretically) = (7.35 + 2.95) = 10.3 kmoles O2 supplied = 10.3 1.2 = 12.36 kmoles
O2 remaining = [12.36 (6.9825 + 0.18375 + 2.95)] = 2.24375 kmoles
N79 = 46.5 kmoles2 entering = 12.36 21

Component CO2 CO O2 N2Total 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:
CO2: 9.5%, O2: 1.4%, CO : 1.9% and rest is N2. 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 CxHy
Basis: 100 mole of the flue gas
Let us assume the hydrocarbon (HC) to be CxHy
Let a g mole of HC get oxidized to CO2
and b g mole of HC get oxidized to CO
The reactions to take place are

a (CxHy) + a(x + y/4)O2 axCO2 + ay/2H2O

b(CxHy) + b(x/2 + y/4)O2 bxCO + by/2H2O
The composition in percentage of the gases are:
CO2: 9.5%, O2: 1.4%, CO : 1.9%, N2: 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 kmoles0.79
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 + 0.5O2 CO2
One kmole of CO requires 0.5 kmole of oxygen
Therefore, 0.95 mole of O2 will be used for converting CO to CO2 Excess O2 remaining = 1.4 0.95
= 0.45 kmole
Theoretical O2 required = 11.4 (from CO and CO2 values) + 11.33 (for H2O formation) = 22.78
kmoles

0.45
\
Excess air =

100 = 1.98%
Hence, Hydrocarbon = C1H3.975 = CH4 (methane)

7.37 The analysis of gas entering the converter in a contact H2SO4 plant is SO2: 4%, O2: 13% and N2:
83%. The gas leaving the converter contains 0.45% SO2 on SO3 free basis. Calculate the % of SO2
entering the converter getting converted to SO3.

Basis: 100 g mole of gas entering the converter

Let x g mole SO2 get converted to SO3
SO2 : 4 SO2: 0.45% O2 : 13 Converter O2N2 : 83 N2
SO
+ 0.5O SO 22 3

xx/2 x

gases leaving SO2 (4 x) (SO3 free basis) O2 (13 x/2) N2 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 SO3 = 3.57 4

7.38 A producer gas made from coke has the composition CO : 28%, CO2: 3.5%, O2: 0.5% and N2:
68%. This gas is burnt with 20% excess of the net O2 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

CO2 3.5 44 3.5 44 = 154

O2 0.5 32 0.5 32 = 16
N2 68.0 28 68 28 = 1,904
Total 100.0 2,858

we have CO + 0.5O2 CO2

Oxygen balance
O2 needed = 28 0.5 = 14 kmoles
O2 available in feed = 0.5 kmoles
Net O2 needed = 13.5 kmoles
O2 supplied = 13.5 1.2 = 16.2 kmoles
O2 consumed = 14 0.98 = 13.7 kmoles
O2 remaining = (16.2 + 0.5 13.7) = 3 kmoles

Carbon balance
CO2 formed = (28 0.98) = 27.44 kmoles CO2 total = (27.44 + 3.5) = 30.94 kmoles CO unreacted =
(28 0.02) = 0.56 kmole Nitrogen balance

N2 from air = 16.2

79 = 60.9 kmoles
21
N2 in exit = (68 + 60.9) = 128.9 kmoles
Exit gas kmole Molecular mole % = Weight, Weight % weight volume % kg

CO2 30.94 44 18.93 1,359.0 26.60

CO 0.56 28 0.34 15.7 0.31
O2 3.00 32 1.84 96.0 1.88
N2 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: Na2CO3: 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 Na2CO3: 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 Na2CO3 extracted per tonne of black ash.
Black Water
ash Residue x

Feed I Unit II Unit Na2CO3: 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
Na2CO3 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 kg95
Total weight = 105.25 kg
Freight charge alone = 105.25 0.6 = ` 0.63100
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 = ` 9.72105.25

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
P2O5 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 O25 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

Ca3(PO4)2 1.0 310 310

SiO2 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 O formed = 47.07
2 5 310
Phosphorus produced = (21.6 0.7) 62 = 6.6 kg142

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
Cl2 HCl

O2 Converter O2
N2N2 H O
2

(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 air146
(b) O2 entering = 1.22 0.23 = 0.281 kg
N2 entering = (1.22 0.281) = 0.939 kg
Gases Weight, kg Weight %

HCl 1.000 45.0

O2 0.281 12.7
N2 0.939 42.3

2.220 100.0
(c) HCl consumed = 0.6 kg HCl remaining = 0.4 kg
32= 0.1495 kg2 remaining = O

Cl2 formed = 0.6 142 = 0.585 kg146

H36 = 0.148 kg2O formed = 0.6 146
Gases Weight, kg Weight %

HCl 0.4000 18.0 Cl2 0.5850 26.33 O2 0.1495 6.73 N2 0.939 42.27 H2O 0.1480 6.66

2.2215 100.00

7.43 In the manufacture of H2SO4 by contact process, iron pyrites are burnt in dry air. Iron is oxidized
to Fe2O3. SO2 formed is further oxidized to SO3 by passing the gases mixed with air over hot catalyst.
Air supplied is 40% in excess of the sulphur actually burnt to SO3. 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 SO3. Calculate the composition (by weight %) of
gases leaving I unit. (c) The catalyst converts 96% of SO2 to SO3. Calculate the weight of

SO3 formed.
(d) Calculate the composition (by weight %) of gases leaving the II
unit.
(e) Calculate the overall degree of completion of sulphur to SO3

FeS2 Unit I SO3,SO2 Unit II Gases

Air (Burner)O2,N2 (Converter)
FeS2 Fe2O3

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 FeS2.

(a) Air supplied = 85 1.4= 517.4 kg; (40% excess oxygen)0.23
O2 = 119 kg; N2 = 398.4 kg
(b) SO3 produced (Unit I) = (85 0.4) 320 = 45.3 kg240
SO256 = 54.4 kg2 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
O2 remaining (entering Unit II) = (119 71.4) = 47.6 kg

Gases Weight, kg Weight % SO2 54.4 9.97

SO3 45.3 8.30

O2 47.6 8.72
N2 398.4 73.01

Total 545.7 100.00

(c) SO
3

produced (II Unit) =

320
= 65.28 kg256
\ Total SO3 produced = (45.3 + 65.28) = 110.58 kg
232
(d) O
2

consumed =

= 13.05 kg
O2 remaining = (47.6 13.05) = 34.55 kg
SO2 remaining = (54.4 0.04) = 2.176 kg

Gases Weight, kg Weight % SO2 2.176 0.400

SO3 110.580 20.264

O2 34.550 6.332
N2 398.400 73.004
Total 545.706 100.000
(e) Sulphur in FeS2 = 100
64 = 53.3 kg
120
Sulphur in SO32 = 44.32 kg3 = 110.58 80
% conversion of S to SO3 = 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%
H2SO4. 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 HNO3 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 HNO3 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 NaNO3 charged.
Na 142 = 83.5 kg2SO4 formed = 100 170
HNO 126 = 74.0 kg3 formed = 100 170
H2SO4 required = 100 98 = 57.65 kg170

HNO3 remaining in cake = 74 0.02 = 1.48 kg

(H2SO4 + H2O)% in cake = (34 + 1.5) = 35.5%
Niter cake has Na2SO4, H2SO4, HNO3 and H2O \ (Na2SO4 + HNO3) % 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 %

HNO3 1.48 1.12

Na2SO4 83.50 63.38
H2SO4 44.80 34.00
H2O 1.97 1.50

Total 131.75 100.00

(b) H2SO4 in the cake = 131.75 0.34 = 44.8 kg H2SO4 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 formed = 126
3 98
HNO3 in cake = 1.48 kg
HNO3 distilled off = 72.64 kg

Composition of vapours removed:

Components Weight, kg Weight %

HNO3 72.64 95.50 H2O 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 Na2CO3 to precipitate BaCO3.

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 Na2CO3 and the precipitated mass of CaCO3,
BaCO3 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 BaCO3 90.1% and CaCO3 9.9%. The analysis of
filtrate is reported to be Na2S : 6.85%, Na2CO3: 2.25% and H2O : 90.9%. The Na2CO3 for the
precipitation used contained CaCO3 as impurity.

(a) Determine the percentage excess Na2CO3 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.

BaritesH2O Na2CO3 (X)

Carbon(CaS

impurity) Cake FilterFiltrate

Reactions in (X): BaS + Na2CO3 BaCO3 + Na2S CaS + Na2CO3 CaCO3 + Na2S

Molecular weights Na2CO3: 106, BaCO3: 197.4, BaS : 169.4, CaCO3: 100, CaS : 72, Na2S : 78.

Basis: 100 kg of filtrate

Precipitate 16.45 kg
Amount of BaCO3 in precipitate = 16.45 0.901 = 14.82 kg Amount of CaCO3 in precipitate = (16.45
14.82) = 1.63 kg (a) Na2CO3 required for forming 14.82 kg BaCO3

= 14.82
106 = 7.96 kg
197.4
Na2S formed along with BaCO3 = 14.82 78 = 5.85 kg197.4
\ Na2S formed along with CaCO3 = (6.85 5.85) = 1.00 kg
CaCO 100 = 1.28 kg3 formed along with Na2S = 1 78
CaCO3 impurity in soda ash = (1.63 1.28) = 0.35 kg
Na2CO3 required for 1.28 kg CaCO3 = 1.28 106 = 1.357 kg100
Na2CO3 present in filtrate = 2.25 kg (2.25% in filtrate) Total Na2CO3 needed = (7.96 + 1.357) =
9.317 kg
100 = 24.1%\ Excess Na CO = 2.25
2 3 9.317
(b) BaS formed = 14.82 169.4 = 12.72 kg197.4
CaS formed = 1.28 72 = 0.9216 kg100
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 Na2CO3 = Na2CO3 used in reaction + Na2CO3 in filtrate = 9.317 + 2.25 = 11.567 kg
We have CaCO3 as impurity in Na2CO3 = 0.35 kg
Composition of dry Na2CO3 is shown as follows:

Components Weight, kg Weight % Na2CO3 11.567 97.06 CaCO3 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% H2SO4. 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 H2SO4 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 CaSO4 formed in kg (1 gallon = 4.4 litres).
Basis: 5000 gallons = (5000 4.4) = 22,000 litres
CaO + H SO

CaSO
24 +4 2H 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) CaSO4 formed = 11,000 136 = 26,714 g = 26.714 kg56

7.47 The available nitrogen content in a urea sample is 45%. Find the actual urea content in the
sample.
CO(NH2)2 = Molecular weight 60

Therefore, N
28 = 0.4666 in urea is =
2 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 CCl4 33.3%; S2Cl2 33.3%; CS2 1.4% and Cl2 32%. Calculate
the following:
(a) the percentage of the excess reactants used.

(b) the percentage conversion.

(c) kg of CCl4 produced per 100 kg Cl2 converted.
Basis: 100 kmoles of product gas
(a) CS2 reacted = 33.3 kmoles

CS2 remaining = 1.4 kmoles

CS2 taken = 34.7 kmoles
% excess reactant, CS2 = 1.4
100 = 4.2%
33.3

CS2 is the limiting reactant and Cl2 is the excess reactant. (based on the kmole left in the product)
Cl2 required (theoretical) = 34.7 3 = 104.1 kmoles (100% conversion) Cl2 reacted = 99.9 kmoles
But Cl2 unreacted = 32.0 kmoles
\ Cl2 taken = 99.9 + 32.0 =131.9 kmoles

% excess reactant = 32.0

100 = 30.73%
104.1
(b) % Conversion:
CS2 = 33.3 100 = 95.97%34.7
100 = 75.74%\ Cl = 99.9
2 131.9
(c) Cl2 reacted = 99.9 kmoles = 7084.91 kg
212.76 kg Cl2 gives 153.84 kg CCl4
7087.91 = 5122.87 kg CCl \7084.91 kg Cl gives 153.84
4 2 212.76
100
CCl4 produced/100 kg Cl2 reacted = 5122.87 = 72.31 kg7084.91

7.49 Limestone is a mixture of calcium and magnesium carbonates and inert. Lime made by calcining
the limestone by heating until the CO2 is driven off. When 100 kg of limestone is calcined 44 kg of
CO2 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 CaCO3 and y kg of MgCO3 \ x + y = 90 (1)

CaCO

CaO + CO
32
100 56 44

MgCO

MgO + CO
32
84.3 40.3 44

CO2 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 MgCO3; x = 35 kg CaCO3
(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 MgCO3; 3.5 kg CaCO3; and 1 kg inert

2 kg Coke = 1.52 kg Carbon; 0.06 kg moisture.
Gases leaving kiln CO2, O2, N2 and H2O

CO2 From CaCO3 = 3.5

88 = 3.08 kg
100
From MgCO88 = 5.74 kg3 = 5.5 84.3
Total CO2 = 8.82 kg = 8.82= 0.2 kmole44
O2 Carbon present = 1.52 kg = 0.1266 k atom
O2 supplied (100% excess) = (0.1266 2) = 0.2532 kmole
N79 = 0.9525 kmole2 entering = 0.2532 21
H2O (3%) = 0.06 kg = 0.06= 0.00333 kmole18

Total CO2 in gases leaving

= CO2 from limestone + CO2 from Carbon (Coke) = 0.2 kmole + 0.1266 kmole
= 0.3266 kmole

Composition of gases leaving:

Gas kmole mole %

CO2 0.3266 23.18

O2 (Excess) 0.1266 8.99
N2 0.9525 67.60
H2O 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 CO2 and H2O.
Formation of CO2 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 CO2:
9.6%, O2: 3%, C2H4: 6.4% and N2: 81%. Of the ethylene entering the reactor, what percent is
converted to oxide?
CO2,O2,
C
2
H
4
Reactor
N
2
Exit Gases
ReactorAir EO, CO ,O , C H ,N
2 2 2 4 2H2O

Reaction (1): 2C2H4 + O2 2C2H4O

Reaction (2): C2H4 + 3O2 2CO2 + 2H2O
Basis: 100 g moles of exit gas
6.4 g moles of C2H4 unreacted.
9.6 g moles of CO2 4.8 mole of C2H4 converted to CO2 81 g moles of N2 (81 21/79) = 21.53 g
moles of O2 supplied. O2 consumed = oxygen supplied oxygen remaining

= (21.53 3) = 18.53 g moles

O2 consumed by Reaction (2) = (4.8 3) = 14.4 g moles Therefore, O2 consumed by Reaction (1) =
18.53 14.4 = 4.13 g moles \ C2H4 converted to C2H4O = 8.26 g moles
C2H4 supplied = C2H4 remaining + C2H4 consumed by Reaction (1)

+ C2H4 consumed by Reaction (2) = 6.4 + 8.26 + 4.8 = 19.46 g moles

C2H4 converted to C2H4O = 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 + O2 CO2
O2 needed for the above reaction is 7.5 g moles
O2 supplied: 7.5 1.25 = 9.375 g moles (25% excess)

N2 from air:
9.375 79= 35.27 g moles
21
O2 remaining 9.375 7.5 = 1.875 g moles
Exit gases CO2 O2 N2Total 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 acidSolvent Extract E Isopropyl etherExtraction 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 CaCO3 : 68%, MgCO3: 30% and rest silica. Acid used is 94% pure. Find: (a) CO2
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 CaCO3: 680 kg, MgCO3: 300 kg and SiO2: 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) CO2 produced by

Reaction (i): 680 44= 299.2 kg100
Reaction (ii): 300 44= 156.6 kg84.3
Total weight of CO2 produced = 299.2 + 156.6 = 455.8 kg (b) H2SO4 required during
Reaction (i): 680 98= 666.4 kg100
Reaction (ii): 300 98= 348.8 kg84.3
Total weight of H2SO4 required = 1,015.2 kg
1,015.2
Commercial acid required =

= 1,080 kg
(c) The solid residue contains CaSO4, MgSO4 and SiO2
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
CaSO4: 67.36%, MgSO4: 31.18% and SiO2 : 1.46.%

7.56 A fuel gas contains 70% methane, 20% ethane and 10% oxygen. The fuel-air mixture contains
200% excess O2 before combustion. 10% of the hydrocarbon remains unburnt. Of the total carbon
burnt 90% forms CO2 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:
CH4 + 2O2 CO2 + 2H2O
CH4 + 1.5O2 CO + 2H2O
C2H6 + 3.5O2 2CO2 + 3H2O
C2H6 + 2.5O2 2CO + 3H2O

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 CO2 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 O2 used: (63 0.9 2) + (63 0.1 1.5) + (18 0.9 3.5)

+ (18 0.1 2.5) = 184.1 moles H2O 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

CH4 7.0
C2H6 2.0
CO2 89.1
CO 9.9
O2 415.9
N2 2,257.0
Total (dry) 2,780.9
H2O 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. CO2:
13.4%, O2: 3.6% and N2: 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

H2: 12 kg = 6 kmoles
The reactions are:
C + O2 CO2
H2 + 0.5O2 H2O

CO2 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 kmoles2
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 C8H18. 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:

C8H18 + 8.5O2 8CO + 9H2O;

C8H18 + 12.5O2 8CO2 + 9H2O.
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

CO2 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 CO2 CO O2 N2Total 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 SO2 is carried out in a packed tower containing Raschig
rings. The gases enter the bottom of the tower with 14.8% of SO2. 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 m3/h. The gases leaving the tower are found to contain 1% of SO2. Calculate the percentage
of SO2 in the outlet water and express it in weight %. Basis: One hour.

Volume of the gases at standard conditions:

273 = 1283.9 m3

1283.9
Amount of gases =

= 57.281 kmoles

SO2 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

SO2 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: CO2:
10.2%, CO : 1%, O2: 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.
N2 in flue gas = 100 (10.2 + 1 + 8.4) = 80.4 kmoles Let the hydrocarbon be CxHy.
Let a kmole of it get oxidized to CO2 and b kmole of it get oxidized to CO.
The reactions are:
CxHy + (x + y/4)O2 xCO2 + y/2H2O;
CxHy + (x/2 + y/4)O2 xCO + y/2H2O.
We also know that,
2C + O2 2CO
i.e. 2 kmoles of CO requires 1 kmole of O2.
\ 1 kmole of CO requires 0.5 kmole of O2 for conversion to CO2

21 =21.37 kmoles\ O2 supplied = 79

O2 reacted = (21.37 8.4) = 12.97 kmoles for forming CO and CO2 For converting CO to CO2
additional O2 required is 0.5 kmoles \ O2 excess = 8.4 0.5 kmoles

= 7.9 kmoles
i.e. O2 required = 21.37 7.9
= 13.47 kmoles
7.9 t100 58.65% excess air = 13.47

Carbon balance = a + b = 11.2

CO2 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 C2H2, 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.Xf = D.XD + W.Xw (2) Substituting,
F = 100 kmoles/h, Xf = 0.4, XD = 0.95 and Xw = 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
ABCD
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
x
Feed Extractor
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

xC =
53.5=0.594590
xD = 36.5= 0.405590

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%, CO2: 50%, O2: 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% N2 and 21% O2 by mole %. Let 1 kmole of gas be mixed with y kmole
of air to give final product containing 40 mole % N2 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 O2 : 21% N2 : 79%

1 kmole
CO = 10% (1 + y) kmoleCO = 50% Mixer
2 N2 = 40%O2 = 5%
N2 = 35%

Leaving stream:

Component Weight, kmoles mole % CO 0.1 8.86

CO2 0.5 44.32
O2 0.05 + 0.128 0.21 = 0.07688 6.82
N2 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% SO2, 10% O2, and rest 85% N2 enters a catalytic chamber where the
leaving gas contains only 0.5% SO2. Estimate the fractional conversion of SO2 to SO3 and also the
composition of gases leaving catalytic chamber.

Basis: 100 kmoles of gas entering the chamber

The reaction is
SO2 + O2 SO3
Let x be the kmoles of SO2 reacted
So, unreacted SO2 = 5 x
Then, SO3 formed is x and the corresponding O2 reacted is x/2 moles (by stoichiometry)

Balance O
2

10x 2
Total amount of gas leaving = 85 + 10x + x + [5 x]2
x= 100
2
Mole fraction of SO2 in the leaving stream = 0.005 i.e. 5 -x= 0.005 100
-

x
2
Solving, we get
x = 4.511

Fractional conversion of SO2 to SO3 = 4.511 100 = 90.22%

Gas analysis:

Component Weight, kmoles mole % SO2 5 4.511 = 0.489 0.500

SO3 4.511 4.615
O2 10 4.511/2 = 7.744 7.923
N2 85.000 86.962
Total 97.744 100.000

EXERCISES

7.1 The waste acid from a nitrating process contains 25% HNO3, 50% H2SO4 and 25% water. This
acid is to be concentrated to 30% HNO3, 60% H2SO4 by addition of 95.3% H2SO4 and 90% HNO3.
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

CO2: 10.2%, O2: 7.9%, N2: 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. CO2: 11.73%,
CO: 0.2%, H2: 0.09% ,O2: 6.81% N2: 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%, H2: 5%, O2: 5%, N2: 1%, H2O: 9% S: 1% and ash: 5%.

7.4 A fuel gas contains CO2: 2%, CO: 34%, H2: 41%, O2: 1%, C2H4: 7%, CH4: 11% and rest N2. 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% CO2, 5% O2, and rest
N2. 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 SO2 and
rest to SO3. 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 CO2 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% SO2 and 3% O2 and rest nitrogen on SO3 free basis.
Gases leave the burner at 800 C and 760 mm Hg pressure. Calculate

(a) fraction of sulphur burnt to SO3

(b) % excess air over the amount required to oxidize sulphur to SO2. 7.10 Butane is burnt with 80%
of the theoretical air. Calculate the analysis of the gases leaving assuming that all H2 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
CO2: 2%, O2: 2.8% and N2: 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% SO2, 2.7% O2
and 83.9% N2. No sulphur is left in the cinder. Calculate the % of sulphur fired that burnt to SO3.

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: CaSO4 2H2O) is produced by the reaction of calcium carbonate and
sulphuric acid. A certain limestone analyzes: CaCO3: 96.89%, MgCO3: 1.41% and inerts : 1.70%.
For 5 metric tonne of limestone reacted completely, determine:
(a) kg of anhydrous gypsum (CaSO4) 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 N2 + 3H2 2NH3
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 % H2O), 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 CH4: 80.0% and N2: 20.0%. It is burnt under a boiler and most of the
CO2 is scrubbed out of the flue gas for the production of dry ice. The exit gas from the scrubber
analyzes CO2: 1.2%, O2: 4.9% and N2 : 93.9%.
Calculate:
(a) percentage of the CO2 absorbed.
(b) percent excess air used.

7.19 A synthetic gas generated from coal has the following composition: CO2: 7.2%, CO : 24.3%,
H2: 14.1%, CH4: 3.5% and N2 : 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% CO2, 14% CO, and rest
O2 in mole %.
(a) What is the percentage of excess oxygen used?
(b) What is the yield of CO2 in kg per kg of carbon burnt?

7.21 A producer gas has the following composition by volume: CO: 23%, CO2: 4.3%, oxygen: 2.7%,
and nitrogen: 70% (a) Calculate the average molecular weight.

(b) Calculate the gas (in m3) 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 m3 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% CO2, 32% CO, 12% H2, and 51% N2.
(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% CO2, 3% O2, and rest N2. 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 C4H10 20 71.2 8.6 C5H12 30 23.8 C6H14 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 CO2 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 CO2. The producer is producing gas having CO:CO2 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 C5H12:7%

C4H10 : 10%
C3H8 : 16%
C2H6:9%
CH4 : 55%
N2:3%

at rate of 200 m3/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 CO2: moles of CO in the flue gas is 20:1.
Calculate

(a) m3/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 P4:8%
CO : 89%
N2:3%
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:
CO2 : 0.9%

CO : 22.5%
N2 : 68%
O2 : 8.6%

It may be assumed that oxidation of phosphorus is complete and phosphorus exists in the flue gas
partly as P4O6 and partly as P4O10. Calculate what % of CO entering the burner is oxidized to CO2,
and what % of P4 is oxidized to P4O10?

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% H2, 3.2% S, 0.4% O2 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 Nm3/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:
CO2:4%
CO : 29%
N2 : 52.4%
H2 : 12%
CH4 : 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%
H2 15%

Calculate the ratio of air to petrol consumption by weight if the volumetric analysis of the dry exhaust
gas is:

Composition Volume %
CO2 11.5
O2 0.9
CO 1.2
N2 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 Feedunit

Gross product
SepaNet 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
RD Benzene 95% B 10,000 kg/h Fcolumn
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
= 0.584Actual 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% KNO3
50% KNO3 0.6 kg KNO /kg water (i.e. 0.6/1.6 = 0.375 KNO solution) M
3 3
R
Crystallizer100F
C
Crystal with 4% H2O
Figure 8.3
Basis: One hour. KNO3 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)

KNO3 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 Ag2SO4,
what is the recycle stream in kg/tonne of product?

Cu CuSO4
F
Reactor
S
1
S

2
90% Ag; 10% Cu

Ag2SO4
Recycle R Ag2SO4
Figure 8.4

Ag SO
24 + Cu 2Ag + CuSO4
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 kg2SO4 needed = t2107.9
CuSO4 formed = 1,300 t159.5= 665 kg312
Cu needed = 1, 300 t63.5= 265 kg (for forming CuSO4)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 (Ag2SO4) was unconverted
which goes in the recycle steam.

Ag2SO4 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
H1= 0.0152 g B of wv/g
0.099 g H2O/g
dry solid
CD H = 0.0525 g 52.5 g dry air (e)of wv/g DA Drier 1.562 g H O/g dry solid
2 2
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.
Aw 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 = Aw + 33.3 + 0.05P Overall balance: 100 = Aw + P
Solving: Aw= 15.81 units Product, P = 84.19 units

8.6 Methanol is produced by the reaction of CO with H2 according to the equation CO + 2H2
CH3OH. 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 H2 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 atmReactor CH3OH CO, 2H2 6,600 kg/h
Unreacted CO, H2
Figure 8.7 Basis: One hour of operation
Methanol produced =
6,600= 206.25 kmoles
32
CO + 2H2 CH3OH
15% conversion of CO entering gives 206.25 kmoles of methanol
206.25=
1,375 kmoles\ CO entering the reactor = 0.15
and H2 entering the reactor = 1,375 2 = 2,750 kmoles Total amount of CO and H2 = 4,125 kmoles

CO unconverted (goes into recycle)

= CO entering CO converted = (1,375 206.25) = 1,168.75 kmoles
H2 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 H2 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 m3
(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 H2 = 4,675 kg
Recycle stream of CO and H2 = 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 CaCO3 and 5% SiO2 is being calcined. Heat for the reaction is
supplied from a furnace burning coke. The hot flue gases analyze 5% CO2. The kiln gas contains
8.65% CO2. 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% CO2

(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 KilnP
X RAir
F Burner
Coke
Figure 8.8

Basis: 12 kg of coke
represent F kmole of flue gas (5% CO2) K, kmole of kiln gas (8.65% CO2)
R, kmole of gas recycled (8.65% CO2) P, kmole of product gas (8.65% CO2) X, kmole of gas entering
the kiln (7% CO2)

XR F
Figure 8.9

X = F + R (overall balance) (a) 0.07X = 0.05F + 0.0865 R (CO2 balance) (b)

CaCO

CaO + CO
32
100 56 44

Assuming complete combustion

0.05F = 1 kmole CO2\ F = 20 kmoles
(Q 1 kmole of CO2 comes from 12 kg of Carbon)
C + O2 CO2
Solving (a) and (b), we have R = 24.2 kmoles; X = 44.2 kmoles Let m kmole of CO2 be added in kiln
from the calcinations of limestone \ K = 44.2 + m
Making CO2 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= 0.538K 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 H2-N2
molar ratio in the feed to the ammonia unit. The H2-N2 mixture is heated to reaction temperature and
fed to a fixed bed reactor where 20% conversion of reactants to NH3 is obtained per pass. The
products from the reactor are cooled and NH3 is removed by condensation. The unreacted H2-N2
mixture is recycled and mixed with fresh feed. On the basis of 100 kmoles per hour of fresh feed
determine the NH3 produced and recycle rate.

Fresh
feed Reactor NH3

Figure 8.11 Basis: 100 kmoles of feed

Given that H2 : N2 = 3 : 1
hydrogen: 75 kmoles and nitrogen: 25 kmoles N2 + 3H2 2NH3
Overall balance gives:
Feed NH3

NH3 formed = 50 kmoles

One mole of N2 gives 2 moles of NH3Reactor balance gives:

3x, H2 Reactor NH , N and H

3 2 2x, N2

Let 3 x kmole of H2 and x kmole of N2 enter the reactor Since 20% conversion takes place,
NH3 formed = x 0.2 2 = 0.4x = 50 kmoles \ x = 125 kmoles of N2; and 3x = 375 kmoles of H2
Unreacted N2 = 100 kmoles, and H2 = 300 kmoles Ans.: NH3 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 m2 area is present and
the degreased surface per day is 105 m2.
Greased metal Solvent S
0% grease
G
Cleaned
metalB
15% Grease solvent Separator ADegreasing

40% grease 1% grease Rwith

Solvent Recyclesolvent

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.
DegreasingB (15%) S (100%
free fromR-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
feedF 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: C2H4 + 0.5O2 C2H4O.

Separator
Ethylene ReactorGasesAir
Figure 8.14
Basis: 1 kmole of ethylene.
Oxygen supplied: 10 kmoles
Nitrogen entering: 10
79 = 37.62 kmoles
21
C2H4 reacted: 1 0.23 = 0.23 kmole
C2H4O formed: 0.23 kmole
Oxygen reacted = 0.23= 0.115 kmole2
Oxygen remaining = 10 0.115 = 9.885 kmoles (a)

Inlet gases mole mole % C2H4 1.0 2.056

O2 10.0 20.560
N2 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 % C2H4O 0.230 0.48

O2 9.885 20.71
N2 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% C2, 40% C3, 40% C4,

E = 95% C2, 4% C3, 1% C4,

P = 99% C3, 1% C4,
B = 8.4% C3, 91.6% C4.

Basis: 100 kg of feed

EP
A Feed, FI Unit II Unit
B
Figure 8.15

Let us assume that the compositions given are in weight %. Overall balance: feed = 100 = E + P + B.
C2 balance: 20 = 0.95E. So, the value of E = 20/0.95 = 21.053 kg C3 balance: 40 = (0.04 21.053) +
0.99P + 0.0084B
C4 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:
C3 balance: (0.99 35.9006) + (0.084 43.0464) = 39.1575 Weight % = 49.6. C4 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% SO3 (rest inert) enters a
SO3 absorption tower at the rate of 28 kmoles/h 98.5% of SO3 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 SO3 entering = 672 0.08 = 53.76 kmoles
= 53.76 80 = 4,301 kg
SO
HO
+H SO
32 24
80 18 98

SO3 absorbed = 4,301 0.985 = 4,236.3 kg

Acid formed = 4,236.3 98 = 5,189.5 kg80
Water reacted = 4,236.3 18 = 953.17 kg80
97.3% SO3Exit r
Absorptiony 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:
H2O 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 NH3 with 20% excess O2: 4NH3 + 5O2 4NO + 6H2O

The reaction is 70 percent complete. The NO is separated from the unreacted NH3, and the latter
recycled. Compute (a) moles of NO formed per 100 moles of NH3 fed, and (b) moles of NH3
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, Dr r, B

where DH, i is the standard heat of formation of ith 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. [DH = SDH ,

reaction SDH , ]
c (reactants) c 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) H2 (g) + I2 (s) 2HI(g) DH = 57.9 kJ

(b) H2 (g) + I2 (g) 2HI(g) DH = 9.2 kJ
The desired reaction is I2(s) I2 (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) C2H5OH (l) + 3O2(g) 2CO2 (g) + 3H2O(l) 1367.8 (2) C
(graphite) + O2(g) CO2(g) 393.5 (3) H2(g) + O2(g) H2O(l) 285.8 Solution: [2 (2) (1)
+ (3 (3))] = 2C + 3H2 + O2 C2H5OH. 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, Cp = (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

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 kg210

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 = 38.1 104 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 = Msls = Ms 540 kcal.
Heat balance:
Heat input by steam + heat in, by feed

= Heat out, in vapour + Heat out, thick liquor or, [Ms.(540) + 38.1 104] = (32,20,000 + 5,04,000)
\ Ms (540) = 33,43,000.
Thus the weight of steam required, Ms = 6,190.75 kg/hr.

9.5 Calculate the standard heat of reaction:

CaC2 + 2H2O Ca(OH)2 + C2H2
DHf cal/mole 15,000 68,317.4 2,35,800 54,194

Solution:
DHrxn = (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.Cp.t)1 (mCpt)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?
CpSO3 = 34.33 + 42.86 103T 13.21 106T2 J/mole K Solution:

Number of moles of the trioxide = 60 = 0.75 kmole80

At 373.16 K,

Q = nCpSO3 dt
At 273.16 K
Q = [{34.33 (373.16 273.16)} + {(42.86 103/2)(373.162 273.162)}

+ {(13.21 106/3)(373.163 273.163)}] 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) C6H6 (l) to CO2 (g) and H2O (l) = 7,80,980

(ii) C6H6 (g) to CO2 (g) and H2O (g) = 7,59,520
(iii) H2 (g) to H2O (l) = 68,317
(iv) H2 (g) to H2O (g) = 59,798
(v) Graphite to CO2 (g) = 94,052
Desired reactions:
(a) C6H6 (l) + 7.5O2 6CO2 (g) + 3H2O (l)
(b) C6H6 (l) C6H6 (g)
(a) Equation (i) itself gives value, DHc = 7,80,980 cal/g mole. (ii) C6H6 (g) + 7.5O2 6CO2 (g) +
3H2O (g)
(iii) H2 (g) + O2 H2O (l)
(iv) H2 (g) + O2 H2O (g)
(v) C + O2 CO2 (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 ZnSO4 from its elements and from these

data: kcal/mole

(i) ZnS Zn + S 44
(ii) 2ZnS + 3O2 2ZnO + 2SO2 221.88

(iii) 2SO2+ O2 2SO3 46.88

(iv) ZnSO4 ZnO + SO3 55.1
Desired equation: Zn + S + 2O2 ZnSO4 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 Cp 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) ls = 734.9 Btu/lb we have, Q = msls = (ms) (734.9)
= 3,66,000 Btu
\ ms = 498.2 lb/h

lb of steam/lb of charge = 498.2= 1.533325

9.11 Pure ethylene is heated from 30 C to 250 C at a constant pressure. Calculate the heat added per
kmole
Cp = 2.83 + 28.601 103T 87.26 107T2 where

Cp is in kcal/kmole K and T in K
T2

DH = n CdTp T1 = 303 K, T2 = 523 K

T1

n = 1 kmole
Or, DH = [2.83 {T2 T1} + (28.601 103/2) {T2 T2}2 1
{87.26

10
7/3}{T3 T32 1}] Heat added = 2,886.11 kcal
9.12 Calculate the amount of heat given off when 1 m3 of air at standard conditions cools from 500 C
to 100 C at constant pressure. Cp air = 6.386 + 1.762 103 T 0.2656 106 T2, where Cp is in
kcal/kmole K and T in K.
1 m3 =1 = 0.0446 kmole22.414
173

Q = 0.0446 C dT= 0.0446 [6.386 600 + (1.762 103/2)(1732 7732)p

773

(0.2656 6/3) (1733 7733)] 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.

(Ws = shaft work, Btu/lb v: velocity, ft/s)
Ws = (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 HP2545
[1 Btu = 778 ft. lbf; 1 HP = 2545 Btu/h]
9.14 Find the heat of reaction at 1200 K. C2H6 C2H4 + H2 'Hf,C H26 84,720 kJ/kmole
'Hf,C H24 52,280 kJ/kmole
DHrxn, 298 K: 52,280 (84,720) = 1,37,000 kJ
DHrxn = DHrxn nCpReactants(1200 298) + nCpProducts (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 CO2 from 100C to 1000C.
Perform the calculation in the following ways. (a) by integrating the expression for Cp and (b) by
using mean heat capacity value Cp in kcal/kmole K.

Cp = 6.85 + 8.533 103 T 2.475 106 T2, kcal/kmole K Basis: 132 kg of CO2 132/44 = 3
kmoles
T2

(a) DH = n CdTp = 3 [6.85 900 + (8.533 103/2)(12732 3732)

T1

(2.475 6 /3)(12733 3733)] 10

DH = 3[10,826.29] = 32,478.87 kcal
Cp values at 1273 K and 373 K are:

Cp at 1273 K = 13.702 kcal/kmole K

and Cp at 373 K = 9.6884 kcal/kmole K
Cpav = 11.6952 kcal/kmole K
DH = m Cpav dT
= 3 11.6952 (1273 373)
= 31,577.04 kcal

9.16 SO2 gas is oxidized in 100% excess air with 70% conversion to SO3. 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 SO2 sent?

Basis: 1 kmole SO2.

SO2 + O2 SO3 O2 sent = 0.5 2 = 1. SO3 formed = 0.7 kmole N2 in air = 1 79/21 = 3.76 kmole.
SO2 remaining = 0.3 kmole

SO3 SO2 O2 N2 Total gases leaving kmoles 0.7 0.3 0.65 3.76 5.41 Cp mean, cal/g mole C 15.5 11.0
7.5 7.1

Hrxn = 23, 490 cal/g mole (given)D

DHrxn = 23,490 0.7 = 16,443 kcal
Datum: 0C
Heat in Heat out

SO2 = 1 11 400 = 4,400 kcal SO2 = 0.3 11 450 = 1,485.00 kcal O2 = 1 7.5 400= 3,000 kcal O2 = 0.65 7.5 450 = 2,193.75 kcal
N2 = 3.76 7.1 400 = 10,676 kcal N2 = 3.76 7.1 450 = 12,013.20 kcal

SO3 = 0.7 15.5 450 = 4,882.50 kcal Total = 18,076 kcal Total = + 20,574.45 kcal DHrxn 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 NH3 at 480 C.

D Hf at 25C for NH3 = 10.96 kcal/kmole

Cp N2 = 6.76 + (6.06 104T) + (13 108T2)
Cp H2 = 6.85 + (2.8 105T) + (22 108T2)
Cp NH3 = 6.703 + (0.0063T) where T is in K,
Reaction: N2 +3H2 2NH3
D Hf /kmole 0 0 10.96
Basis: 1 mole of N2 (Feed at 273 K)
DHrxn 298 K: (2 10.96) = 21.92 kcal.
Find DCp = 2NH3 (N2 + 3H2)
Da = (2 6.703) [7.76 + (3 6.85)] = 13.9
Db = (2 0.0063) [6.06 104 + (3 2.8 105)] = 0.0119 Dg = (2 0) (13 108 + 3 22 108)
= 7.9 107

D
H
o

=
D
H
rxn

Da
T

' T2 ' T3

0.0119
t
298
27.9 10 73
D
H
o

= 21.92 (13.9

298)
2

t t298 3
DHo= 3,598.87 kcal
480 C = 753 K
Hrxn, 480C = DHo + DaT + ' T2 + ' T3D
0.0119
= 3,598.87 + (13.9

753) +
(753)2

7.9 107 (753)3+ t


\DHrxn 480C = 3,606.56 kcal/kmole

9.18 Calculate the calorific value of a blast furnace gas analyzing 25% CO, 12.5% CO2 and 62.57%
N2.
(a) C + O2 CO2; DHrxn: 94 kcal
(b) C + O2 CO; DHrxn: 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.

Cp = a + bT + cT2, cal/kmole K
where a, b and c are all dimensional constants and available in literature 3c 105Gas a b 10
CO2 10.55 2.16 2.04 N2 6.66 1.02
C CO
CO
2

CO II Combustion2I CombustionO2 N2Air N2

Basis: 100 g moles of inlet gas
CO entering 25 g moles, CO2 exit = 25 + 12.5 = 37.5 g moles

79 = 109.52 g moles2 needed 12.5 g moles, N2 = tO

CO + O2 CO2
Reaction (a) (b) gives
DHrxn = 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:
17 105 cal = 37.5 [{10.55 (T 298)} + 2.16 103(T2 2982)/2

2.04 105(T3 2983)/3] + 109.52[6.66 (T 298) + 1.02 103(T2 2982)/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 CO2
+ 4H2 CH4 + 2H2O 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).

DHf CO2 CH4 H2O kcal/kmole 94,052 17,889 57,798 at 298 K

\D Hrxn = [17,889 (2 57,798)] [94,052]

= 39,433 kcal/kmole of CO2
Cp for CO2 = 6.339 + 10.14 103T 3.415 106T2 H2 = 6.424 + 1.039 103T 0.078 106T2
H2O = 6.97 + 3.464 103T 0.483 106T2 CH4 = 3.204 + 18.41 103T 4.48 106T2
Da = [3.204 + (2 6.97) 6.339 (4 6.424)] = 14.891
Db = [18.41 + (2 3.464) 10.14 (4 1.039) = 11.047 103
= [4.48 (2 0.483) {3.415 (4 0.078)}] = 1.719 106Dg
DCp = 14.891 + 11.047 103T 1.719 106 T2
We find DHo using data at 298 K

' T2 ' T3DH = DHrxn DaT

o

= 39,433 (14.891

298)
11.047
10
2 tt2
3
3

1.716
10
6

tt 3 DHo= 39,433 + 4,430 491 + 15.16 = 35,479 kcal Next we find DHrxn at 500 C (or) 773
K:
' T3DH DHo + DaT + ' T2 +
773 =
= 35,479 + (14.891

773) +
11.047
10
32 tt 773
2
1.719
10 63
+

t t773 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, O2 needed = 0.5 lb mole CO + O2 CO2

O2 supplied = 0.5 1.5 = 0.75 lb mole (50% excess)
Air supplied = 3.57 lb mole and N2 = 2.82 lb moles
DHrxn = 1,21,745 Btu/lb mole
Q = DHrxn + DHproducts DHreactants
O2 remaining = 0.25 lb mole
CO2: 1 lb mole, N2: 2.82 lb moles
Datum: 32F
Data: DH (Btu/lb mole)

Temperature , F CO Air O2 N2 CO2

50 125.2

77 313.3 312.7 315.1 312.2 392.2 800 5,690 5,443 8,026 1000 6,984

DH products = DH
800F DH
77F

= 1(8,026 392.2) + 2.82(5,443 312.2) + 0.25(5,690 315.1) = 23,446 Btu/lb mole

DH reactants: (DH1000F DH77F)air + (DH50F DH77F)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 + O2 CO2
O2 supplied = 1 lb mole, N2 = 3.76 lb moles
Exit: CO2 : 1 lb mole, O2 : 0.5 lb mole, N2 : 3.76 lb moles

Assuming a base temperature of 25 oC, (77 oF) and using mean heat capacities,

D H = Hp HR; Q = DH
DH = SnCppr(77 200) + DHrxn77 F + SnCpR (t 77)
Reactants: DHrxn = 1,21,745 Btu/lb mole

Gas n Cp nCp

CO 1 6.95 6.95
CO 1 6.95 6.95
O2 1 7.10 7.10
N2 3.76 6.95 26.13

Total 40.18
\SnCppr(77 200) = (40.18 123) = 4,942 Btu DH = 4,942 1,21,745 + SnCpR (t 77)
200 F 500 F 1000 F 1500 F 2000 F 3000 F n Cp nCp Cp nCp Cp nCp Cp nCp Cp nCp Cp
nCp

CO2 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
O2 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
N2 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
SnCpR 38.83 39.85 41.51 43.04 44.44 46.32
SnCp
(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: CO2 : 9.2, CO : 1.5, O2: 7.3, N2: 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?

Cp of N2 = 6.895 + 0.7624 103 T 0.7 107 T2Cp of O2 = 7.104 + 0.7851 103 T 0.5528 107
T2Cp of CO2 = 8.448 + 5.757 103 T 21.59 107 T2 + 3 1010 T3Cp of CO = 6.865 + 0.8024
103 T 0.736 107 T2Basis: 1 lb mole of CO2:

Multiplying these equations by the respective mole fractions of each component and adding them
together, we have

for N2 = 0.82 CpN2

for O2 = 0.073 CpO2
for CO2 = 0.092 CpCO2
for CO = 0.015 CpCO
Cpnet = 7.049 + 1.2243 103 T 2.6164 107 T2 + 0.2815 1010 T3
200

Cp dT\DH
net =
550

= 7.049 (200 550) +

1.2243
103
t(2002 5502) 2

2.6164
107(2003 5503) + 0.28151010
t
3
t

4
(2004 5504)

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 + O2 CO2
Basis: 1 g mole CO
Temperature of reactants: 200 F = 93.3 C
Gases entering: CO1, O21, N23.76 (all in moles)
Gases leaving: CO21, O20.5, N23.76 (all in moles)
\DHrxn 25 C = 67,636 cal.

Gas mole DTCpm DH = nCpmDT 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 DHproduct = (DHreactants DHrxn)

= (2,746 + 67,636) = 70,382 cal Let us assume exit temperature as 1800 C, then DT = (1800
25) = 1775 C Gas mole DTCpm DH

CO2 1.0 1775 12.94 23,000

O2 0.5 1775 8.35 7,400
N2 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% N2 when burnt
with 150% excess air. Both air and gas being at 25 C.
Data: Heat of formation of CO2 = 94,052 cal/g mole, CO = 26,412 cal/g mole at 25 C.
Cpm: CO2: 12.1, O2: 7.9, N2: 7.55 cal/g mole K (from literature) Basis: 1 g mole CO, CO + 0.5O2
CO2

O2 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 moles21

Exit gas: CO2: 1 g mole, O2: 0.75 g mole, N2: 8.7 g moles Q = SHproducts + SHrxn SHreactants. (Datum
298 K)
SHreactants is zero, since air and gas are at 25 C.
DHrxn = DHCO2 DHCO
= 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% N2 when burnt with
100% excess air. The reactants enter at 298 K.
DHf CO2 = 3,93,700 kJ/kmole; DHf CO = 1,10,600 kJ/kmole Mean molar specific heat, kJ/kmole
K at different temperatures is given below:

Temperature K CO2 O2 N2

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

N2 in feed = 70/30 = 2.34 kmoles
O2 supplied = 0.5 2 = 1 kmole
N2 from air = 3.76 kmoles
Exit gas consists of:
CO2: 1, O2: 0.5, N2: (3.76 + 2.34) = 6.1 kmoles
Let us consider the equation

Q = SH products + DH SH
rxn reactants

where SHreactants = Zero at 298 K (Q Datum is 298 K)

\DHrxn = (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
DHpr = (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
DHpr = (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: SO2: 10%, O2:
12% and N2: 78%. How much heat must be added to this gas to change its temperature from 30 C to
425 C?

The Cpm values are in cal/g mole C

Gas SO2 O2 N2Cpm 30 C 10 6.96 6.80 Cpm 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
SO2 : 669.2 0.1 = 66.92 g moles
O2 : 669.2 0.12 = 80.30 g moles
N2 : 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% N2 when burnt with 100% excess air. Both air and
gas are initially at 25 C.

Cp CO2 = 6.339 + 10.14 103 T 3.415 106 T2

Cp O2 = 6.117 + 3.167 103 T 1.005 106 T2
Cp N2 = 6.457 + 1.389 103 T 0.069 106 T2
The values of Cp are in kcal/kmole K and temperature is in K DHrxn 25 C = 67,636 kcal
Basis: 1 kmole of CO; N2 = 4 kmoles
Air supplied: O2: 1 kmole, N2 from air: 3.76 kmoles
Exit gas: CO2: 1, O2: 0.5, N2: 7.76 kmoles
Datum 25 C = 298 K
DHrxn = DH products + 67,636 = [1 CpCO2 (T 298)] + [0.5 CpO2 (T 298)]
+ [7.76 CpN2 (T 298)]
22

67,636 = 6.339(
T
298) + 10.14

10
3T 298
2
33 T 298 3.415 106 T 298

3+ 6.117 2
22 33T
+ 3.167

10
3 T 298 1.005 106 298 4 6 T
22

+ 7.76

6.457

(
T
298) + 7.76

1.389

10
3298
2T
33

7.76

0.069

10
6298
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: Cpm values (J/g mole K) for the components are: O2: 31.9, N2: 32.15, H2O : 40.19, CO2 :
51.79.
Basis: 1 g mole of methane.
Datum: 298 K

CH4 + 2O2 CO2 + 2H2O

\ Oxygen supplied = 2 2 = 4 g moles
N2 entering = 4
79 = 15.05 g moles
21

Gases leaving are: CO2: 1, H2O : 2, O2: 2, and N2: 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)] = 641.6 103 J.
\ T = 1242 K = 969 C.

9.29 An iron pyrite ore contains 85% FeS2 and 15% gangue. It is roasted with 200% excess air to get
SO2. The reaction is given. All the gangue plus Fe2O3 end up in the solid waste produced which
analyzes 4% FeS2. 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.

4FeS2 + 11O2 2Fe2O3+8SO2 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 FeS2 = 0.85 kg and gangue = 0.15 kg Let x kg of FeS2 be in the solid
waste,

319.4
then, FeS2 reacted: (0.85 x) kg; Fe2O3 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
FeS2 0.029 3.99
Fe2O3 0.547 75.35
Total 0.726 100.00

FeS2 reacted = (0.85 0.029) = 0.821 kg = 6.85 103 kmole\

Fe2O3 formed = 0.547 kg = 3.424 103 kmole
SO
2

formed =

512= 1.068 kg = 0.016688 kmole 479.4

Heat of reaction = [(0.016688 296.9) + (3.424 103 822.3)
(6.85 103 177.9)]

= 6.55 kJ
9.30 For the following reaction, estimate the heat of reaction at 298 K. A + B C + D
Compound DHf (kcal/g mole)

A 269.8
B 195.2
C 337.3
D 29.05
DH at 25 C = SDHf, Products SDHf, reactants
= [337.3 29.05] [269.8 195.2]
= 98.65 kcal
9.31 Estimate the standard heat of reaction DH298 for the reaction. A + B C
Standard heats of combustion are:
DHc, 298 for A = 328000 cal/g
DHc, 298 for B = 212000 cal/g
DHc, 298 for C = 542000 cal/g
DHc, 298 = SDHc, reactants SDHc, products
= [328000 212000] [542000]
= 2000 cal
9.32 Calculate the heat of formation of CHCl3 from the following data:

CHCl3 +
1 O + H O CO + 3HCl, DH = 509.93 kJ (1)
2 2 2 2

H2 + 1 O2 H2O; DH = 296 kJ (2)2

C + O2 CO2; DH = 393.78 kJ (3) 1 H2 + 1 Cl2 HCl; DH = 167.5 kJ (4)2 2

CO2 + 3HCl 1 O2 + H2O; DH = 509.93 kJ CHCl3 + 2

H2 + 1 O2 H2O; DH = 296 kJ2
C + O2CO2; DH = 393.78 kJ
Eq. (4) 3 + Eq. (3)/2, gives
3H + Cl2 + 1 C + 1 O2 3HCl + 1 CO22 2 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, DHf, 298 for the reaction
2FeS2 + 1.5O2 Fe2O3 + 4SO2

The standard heats of formation are:

FeS2 = 42,520 cal/g mole
Fe2O3 = 1,96,500 cal/g mole
SO2 = 70,960 cal/g mole
From the reaction,
DHr, 298 = DHFe2O3 + 4 [DHSO2] 2[DHFeS2]

= 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.
Cp 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

H600 = DH300 + 'Cp.dTD

300
600

= 30,000 + [{303 10 + 0.4} 0.1T] dT

300

= 30,000 + 0.4
T
0.1

T2
2
= 30,000 + 0.4[600 300] [0.05 (6002 3002)] = 43,380 cal/g mole of A

9.35 Calculate the theoretical flame temperature of a gas containing 20% CO and 80% N2 when burnt
with 150% excess air, with both air and gas being at 25 C.

D Hf Cpm
CO2= 393.137 kJ/g mole CO2 = 50.16 kJ/kg K CO = 110.402 kJ/g mole O2 = 33.02 kJ/ kmole H2 =
31.56 kJ/kmole K
Basis: 100 g moles of feed
CO = 20 g moles

CO +
1 O CO
2 22
O2 needed = 1 20 = 10 g moles2

O2 supplied = 2.5 10 = 25 g moles

N2 supplied = 25 79/21 = 94.05 g moles Gases leaving
CO2= 20 g moles
O2 = 25 10 = 15 g moles
N2 = 94.05 + 80 = 174.05 g moles
Atmospheric temperature = 25 C
Heat in reactants + DHR = Heat in products Standard heat of reaction,

D Hf products DHf 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.
DHr = 1,91,760 cal/g mole
Mean heat capacities (cal/g mole K)

Component Temperature 2000 C 1800 C CO2 13.1 12.95 H2O 10.4 10.25 O2 8.4 8.3 N2 8.0 7.9

9.2 Determine the heat of reaction at 720 K and 1 atm for the reaction

SO2 + 0.5O2 SO3

Mean molar specific heats of
SO2 : 51.5 kJ/kmole K
O2 : 45.67 kJ/kmole K
SO3 : 30.98 kJ/kmole K
Standard heat of formation for
SO2 : 2,97,000 kJ/kmole
SO3 : 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, Cp = R (A + BT + CT2) cal/g mole where, R is Gas constant, T is temperature
in K. A, B and C are constants and Cp is the heat capacity at constant pressure.

Component Value of constant in Cp equation AB 103C 106 CH4 1.702 9.081 2.164 C2H6 1.131
19.225 5.561

9.4 Chlorine is produced by the reaction

4HCl(g) + O2(g) 2H2O(g) + 2Cl2(g)
The feed stream to the reactor consists of 67 mole % HCl, 30 mole %

O2 and 3 mole % N2. 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
H2O(g) : 2,41,818 J/g mole

(b) Mean heat capacities: (cal/g mole K)

HCl(g) : 7.06
O2(g) : 8.54
H2O : 7.52
Cl2(g) : 8.61
N2(g) : 7.16
9.5 Calculate the number of joules required to calcine completely 100 kg of limestone containing
80% CaCO3, 11% MgCO3 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 CaCO3 : 2,88,450 cal/g mole
MgCO3 : 2,66,000 cal/g mole
CaO : 1,51,900 cal/g mole
MgO : 1,43,840 cal/g mole
CO2 : 94,050 cal/g mole
Mean molal heat capacity, cal/g mole K
H2O : 8.2
CO2 : 10.5
CaCO3 : 25.0
MgCO3 : 23.0
CaO : 14.0
MgO : 10.0
9.6 In the reaction
4FeS2(s) + 11O2 (g) 2Fe2O3(s) + 8SO2(g) the conversion from FeS2 to Fe2O3 is only 80%
complete. If the standard heat of formation for the above is calculated to be
197.7 kcal/g mole, what DHreaction should be used in energy balance per kg of FeS2 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 + O2 CO2
The heat capacities are 29.23 for CO, 29.28 for air, 54.18 for CO2, 34.5 for O2 and 33.1 for N2 in J/g
mole K. Standard heat of reaction:
283.13 kJ/g mole.
9.8 A gaseous mixture of 1000 m3 containing 60% hydrogen and 40% ammonia is cooled from 773 K
to 313 K at 1 atm pressure. Calculate the heat removed. The Cp values in kcal/kmole K, and T in K
are: for hydrogen Cp = 6.9 0.2 103 T + 0.48 106 T2 for ammonia Cp = 6.08 + 8.81 103 T 1.5
106 T29.9 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 m3 of air at standard condition cools from 600 C
to 100 C at constant pressure Cp air = 6.386 + 1.762 103 T 0.2656 106 T2
Cp 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: DH298 K = 67,636 kcal
Mean specific heats are: 7.017 for CO, 7.225 for air, 11.92 for CO2, 7.941 for O2 and 7.507 for N2 in
kcal/kmole K.

Problems on Unsteady10State 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?
FiXi
M, X
Fo , Xo = X
221

Here inlet flow rate, Fi = 500 kg/min

Outlet flow rate, Fo= 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()= FiXi Fo X (2)dt
dXdM
MX= FiXi Fo X (3)dtdt

Here, dM= 0 (Since inlet and outlet flow rates are the same)dt
Therefore, M dX = FiXi Fo X(4)dt
dX
Now substituting values, 10,000

= 500 0.0 500X (5)

dX
(i.e.) = 0.05Xdt
(i.e.)dX= 0.05dtX
Integrating, we get
Xt

dX 0.05dtX

o Xt 0
X
ln

= 0.05(t 0)

= 0.05t (6) Therefore, X= e0.05t (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 e0.05 (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, Fi = 2 kg/min

Outlet flow rate, Fo= 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()= FiXi FoX (2)dt

or, M dX + X dM = FiXi FoX (3)dt dt

Here,dM= 0.5dt
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 2Xdt
or, dXdt (5)0.06 2Xt

Integrating, we get

Xtdt Xt
o

Xt 0
Xt

also,
0.5
dXdt

Xt
oXt0
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 = 204 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 1.5Xdt
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

yePdx = QePdx dx + constant (11)
Using the same analogy we can solve Eq. (9) in the following manner 24P = 10 0.5 20tt

and

0.06 0.12 Q tt

Substituting for P and Q in Eq. (11), we get

44
dtdt

X
tt
0.12eedt + constant (12)20 t
X 4 exp[ln(20 + t)]
X(20 + t)
0.12
= 4 exp[ln(20 + t)] dt + constant20t
0.12
4 = [20 + t]4dt + constant
20t
or, X(20 + t)4 = [0.12][20 + t]3dt + 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
1600and (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, Fi = 1.5 litres/min at a salt concentration of 1 g/litres Outlet flow rate, Fo = 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 = 0.5dt
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 C F C (2)
i i o dt
V dC + C dV = FiCi Fo C (3)dt dt
Here, dV = 0.5dt
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)
-
3C - =
(7)120+

\ 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% Na2SO4 solution is fed at the rate of 12 kg/min into a mixer that initially holds 100 kg of
a 50 : 50 mixture of Na2SO4 and water. The exit solution leaves at the rate of 9 kg/min. Assuming
uniform mixing, what is the concentration of Na2SO4 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 Ho. 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 H1.

10.8 A solution is having solute A at a concentration CAf 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 Cao. 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 1010

6microns (m)m 10

Area in2 m2 6.452 104 ft2 m2 0.0929 cm2 m2 104

Volume ft3 m3 0.02832

cm3 m3 106 litre m3 103 Gallons (UK) m3 4.546 103 Gallons (US) m3 3.285 103

Mass Pound (lb) kg 0.4536 Gram (g, gm) kg 103 Density

Force lb/ft3 kg/m3 16.019 g/litre kg/m3 1.0 g/cm3 kg/m3 1000

lbf N 4.448
kgf N 9.807
Pa N 980.7
dyne N 105TABLE I Important Conversion Factors (contd.)
(Contd.) 229
Quantity To convert Multiply by from to
Pressure lbf/ft2

lbf/in2 (psi) in Hg
in water
mm Hg
atm
torr
bar
kgf/cm2
N/m2 = Pa 47.88 N/m2 = Pa 6895
N/m2 = Pa 3386
N/m2 = Pa 249.1 N/m2 = Pa 133.3 N/m2 = Pa 1.0133 105 N/m2 = Pa 133.3 N/m2 = Pa 105
N/m2 = Pa 9.807 104

Heat or energy
Volumetric flow rate Btu
erg
cal
kcal
kW.h

ft3/s
ft3/h, ft3/h cm3/s
lit/h
J = N.m 1055 J = N.m 107 J = N.m 4.187 J = N.m 4187 J = N.m 3.6 106

m3/s 0.02832 m3/s 7.867 106 m3/s 106

3/s 2.777 107m

Mass flow rate (Mass flux)

lb/ft2.h

g/cm2s kg/m2s 1.356 103 kg/m2s 10

Molar flow rate (Molar flux)

Enthalpy lb mole/ft2.h g mole/cm2s

Btu/lb
cal/g = kcal/kg kmole/m2s 1.356 103 kmole g/m2s10

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
Cp = a + bT + cT2, where T is in Kelvin; g-cal/(g-mole) (K) Temperature range 300 to 1500 K
Gas a b 103c 106

H2 6.946 0.196 0.4757

N2 6.457 1.389 0.069
O2 6.117 3.167 1.005
CO 6.350 1.811 0.2675
NO 6.440 2.069 0.4206
H2O 7.136 2.640 0.0459
CO2 6.339 10.140 3.415
SO2 6.945 10.010 3.794
SO3 7.454 19.130 6.628
HCl 6.734 0.431 +0.3613
C2H6 2.322 38.040 10.970
CH4 3.204 18.410 4.480
C2H4 3.019 28.210 8.537
Cl2 7.653 2.221 0.8733
Air 6.386 1.762 0.2656
NH3(*) 5.920 8.963 1.764

* Gas

TABLE III(b) Molal Heat Capacities of Hydrocarbon Gases For 10 to 760 oC, Cp = a + bT + cT2
oC, C = 7. 95 + mTn For 180 to 95
p
T in Rankine (oF + 460)

Compound a b3 c 106m n 10

Methane 3.42 9.91 1.28 6.4 1012 4.00

Ethylene 2.71 16.20 2.80 8.13 1011 3.85
Ethane 1.38 23.25 4.27 6.20 108 1.79
Propylene 1.97 27.69 5.25 2.57 103 1.26
Propane 0.41 35.95 6.97 3.97 103 1.25
n-Butane 2.25 45.40 8.83 0.93 102 1.19
i-Butane 2.30 45.78 8.89 0.93 102 1.19
Pentane 3.14 55.85 10.98 3.9 102 1.00

Answers to Exercises

CHAPTER 1
1.1 (a) 10.84 cm2/s
(b) 39.67 psia
(c) 0.03929 hp-hr
(d) 0.627 lbf/ft2
(e) 0.01355 cal/s cm2C
(f) 1163 W/m K
1.2 10.93 [Cp G0.8/D0.2]
1.3 4.55 * 103 [P/T0.5]
1.4 (0.09453) [h2.5/g0.5] 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 O2
(b) 12.77 g of KClO3
2.4 (a) 2.8%
(b) 0.088
(c) 5.378 g moles/kg of water
2.5 Mole ratio: 0.0425
Mole %: Na2CO3: 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 H2O 76.7 89 91.46 Total 100.00 100
100.00

Atomic %:
Na: 2.93%; Cl2: 2.93%; H2: 62.76%; and O2: 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/m3 solution
(c) 136.56 g sugar/litre

2.11 (a) Nitrogen

(b) 16.17% and
(c) 59.97%

2.12 0.945 g of Cr2S3

2.13 9.3445 kg of AgNO3
2.14 (a) Mole fraction of H3PO4: 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% H2SO4
2.17 (a) H2SO4
(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/m3

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/m3
Ethane: 0.02231 kmole/m3
Hydrogen: 0.01338 kmole/m3
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 C3H8
3.11 300.37 atm 3.12 (a) and (c)
Component Volume % mole fraction N2 64.75 0.6475
CO2 9.52 0.0952

H2O 18.62 0.1862

O2 6.11 0.0611
CO 1.00 0.0100

Total 100.00 1.0000

(b) Average density: 0.792 kg/m33.13 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 m3
(c) 2.06 g/litre

3.16 (a), (b) and (c)

Component mole fraction Concentration, Partial pressure g mole/cc mm Hg

CH4 0.1 1.058 105 200

C2H6 0.3 3.173 105 600
H2 0.6 6.347 105 1,200

(d) 1.058 104 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 m3
(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/m3

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 xA 1.0 0.724 0.415 0.134
0.0

yA 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
C2H6 : 0.139, n-C3H8 : 0.639, i-C4H10 : 0.039, n-C4H10 : 0.179 and C5H12 : 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 m3/kg dry air
5.3 2961.6 m3/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 m3/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 m3/h
5.8 27.5 C and 0.019 kg/kg
5.9 (a) 96.5%, (b) 115.08 m3/h
5.10 (a) 0.0351 kmole/kmole
(b) 0.00857 kmole/kmole
(c) 1.830 kg of water
(d) 49.858 m3
5.11 46.5 C; 0.0475 kg/kg dry air
5.12 (a) % RH: 29.6%
(b) Humid volume: 0.974 m3/kg dry air
5.13 (a) 3703.7 kg dry air/h
(b) 0.8586 and 0.9739 m3/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 m3/kg dry air
Enthalpy: 106.6 kJ/kg dry air
5.18 (a) 809.4 m3/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 m3/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 H2SO4: 5,310.86 kg, HNO3: 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 CO2: 11.41%, H2O: 14.4% O2: 3.53% and N2:70.66%
7.5 Excess air: 39.06%, 471.06 kg of lime/100 kg coke burnt
7.6 O2: 12.14%, N2: 79.34%, SO2: 7.67% and SO3: 0.85%
7.8 54.22% Excess air
7.10 CO2: 4.9%, CO: 9.1% H2O: 17.51% and N2: 68.49%

7.11 CO2: 11.183%, O2: 3.956%, SO2: 0.158%, N2: 75.693%, and H2O: 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 m3 (b) 6.41 m3
(c) Component Condition (a) Condition (b)

CO2 0.23 0.14

H2O 0.14 0.08
N2 0.63 0.74
O2 0.04

Total 1.00 1.00

7.20 (a) 4.49%

(b) 3.08
7.21 (a) 28.8
(b) 7.55 m3/kg carbon burnt
(c) 50.285 m3/100 m3
(d) CO2: 19.66%, O2: 1.28%, N2: 79.06%
7.22 (a) 446.7 m3
(b) 0.642
7.23 (a) 18
(b) CO2: 17.5%, O2: 6.3%, H2O: 3.5%, and N2: 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, C5H12 : 31.38, C6H14 : 60.06
7.26 Air supplied = 12.24 kg , air required theoretically for completekg of fuel

combustion = 15.3 kg, volumetric analysis = (mol. basis) N2 = 82.8%

CO = 10.9%
CO2 = 6.5%

7.27 (a) Moles of CO: 5.444 kmoles; moles of CO2: 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): CO2 = 273.0933 kg, CO = 9.1467 kg, N2 =
1091.3911 kg, O2 = 118.5901 kg, H2O = 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 m3/h
(b) Composition of flue gas on dry basis (mol. basis): CO2: 10.74%, CO: 0.5373%, N2: 85.487%,
O2: 3.2267%
7.30 (a) 3.846% (b) 70.3%
7.31 Airfuel ratio =12.59478, flue gas analysis:

Composition Weight % Volume % CO2 17.7382 11.9749

O2 7.2088 6.69
N2 72.5086 76.92
H2O 2.4726 4.08
SO2 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) CO2 3.113

O2 0.6408
N2 12.8717
H2O 1.026
SO2 0.064

Total = 17.7155 kg/kg of fuel

7.33 Air requirement = 432.433 kmoles, volume = 15416.56 Nm3/h
Flue gas analysis:

Composition Weight (kg) CO2 16.63 O2 1.2 H2O 8.032 N2 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 + t2]/(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 Na2SO4/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