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Stoichiometry
and Process
Calculations
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K V Narayanan
.
B Lakshmikutty
 STOICHIOMETRY AND
PROCESS CALCULATIONS
SECOND EDITION

K.V. Narayanan
Former Professor and Head
Department of Chemical Engineering
Former Principal
Government Engineering College
Thrissur, Kerala

B. Lakshmikutty
Former Professor and Head
Department of Chemical Engineering
Government Engineering College
Thrissur, Kerala

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PHI Learning D
V 0
a a
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Delhi-110092
2017
STOICHIOMETRY AND PROCESS CALCULATIONS, Second Edition
K. V. Narayanan and B. Lakshmikutty

© 2017 by PHI Learning Private Limited, 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-978-81-203-5289-6

The export rights of this book are vested solely with the publisher.

Eighth Printing (Second Edition) . . . . . . . . . November , 2016

Published by Asoke K. Ghosh, PHI Learning Private Limited, Rimjhim House, 111, Patparganj
Industrial Estate, Delhi- 110092 and Printed by Mudrak, 30- A , Patparganj, Delhi-110091.
 Contents

Preface ix
Preface to First Edition xi

1. Introduction 1-13
1.1 Chemistry versus Chemical Engineering 1
1.2 Chemical Process Industry 2
1.3 Greatest Achievements in Chemical Engineering 4
1.4 Future Avenues and Opportunities 5
1.5 History of Chemical Engineering 6
1.6 Chemical Engineering in India 7
1.7 Unit Operations and Unit Processes 8
1.7.1 Fluid Flow Operations 9
1.7 .2 Heat Transfer Operations 9
1.7 .3 Evaporation JO
1.7 .4 Mass Transfer Operations JO
1.7 .5 Mechanical Separations J2
1.7 .6 Size Reduction J2
1.7 .7 Mixing J2
1.8 Stoichiometry and Process Calculations J2

2 . Units and Dimensions 14- 40

2.1 Units and Dimensions J4
2.2 System of Units J5
2.2 .1 SI Units J6
2.2 .2 Derived Units J6
2.2 .3 SI Prefixes J8
2.2 .4 General Guidelines on the Use of SI Units J9
IV Contents

2.3 Conversion of Units 21

2.3.1 Some Important Derived Quantities and Their Conversion 21
2.3.2 Conversion of Empirical Equations 28
2.4 Dimensionless Equations 22
2.5 Dimensional Analysis 22
2.5.1 Dimensionless Groups in Chemical Engineering Practice 24
Exercises 27

3. Fundamental Concepts of Stoichiometry 41-76

3.1 The Mole Concept 41
3.2 Chemical Calculations and Use of Molal Quantities 42
3.2.1 Molar Volume of Gaseous Substances 45
3.2.2 Equivalent Weight 46
3.3 Density and Specific Gravity 47
3.4 Specific Gravity Scales 48
3.5 Composition of Solids, Liquids and Gases 51
3.5.1 Mass Fraction (Weight Fraction) 51
3.5.2 Mass Percent (Weight Percent) 51
3.5.3 Mass Ratio 52
3.5.4 Dry Basis and Wet Basis 52
3.5.5 Mole Fraction and Mole Percent 54
3.5.6 Volume Fraction and Volume Percent 55
3.6 Other Expressions for Concentrations 57
3.7 Chemical Reactions and Process Calculations 60
3.7.1 Excess and Limiting Reactant 60
3.7.2 Conversion 62
3.7.3 Yield and Selectivity 62
3.7.4 Extent of Reaction 64
Exercises 67

4. Ideal Gases and Gas Mixtures 77-105

4.1 Ideal Gas 77
4.1.1 Ideal Gas Equation 78
4.1.2 Calculations for Ideal Gas 80
4.2 Mixtures of Ideal Gases 82
4.2.1 Dalton’s Law 82
4.2.2 Amagat’s Law of Additive Volumes 84
4.2.3 Average Molecular Weight 85
4.2.4 Density and Specific Gravity 85
4.2.5 Calculations Involving Change in the Mass 88
4.3 Reactions Involving Gases 92
Exercises 97
 Contents V

5. Properties of Real Gases 106-129

5.1 Real Gases 106
5.2 Critical Properties 107
5.3 Equations of State 108
5.3.1 The van der Waals Equation 109
5.3.2 Other Equations of State 111
5.4 Compressibility Charts 114
5.4.1 Compressibility Factor 114
5.4.2 Principle of Corresponding States 115
5.4.3 Generalized Compressibility Charts 115
5.4.4 Methods Based on the Generalized Compressibility Charts 116
5.5 Mixture of Real Gases 122
5.5.1 Equations of State 122
5.5.2 Mean Compressibility Factor 122
5.5.3 Pseudo-critical Properties 123
Exercises 126

6. Vapour Pressure 130-148

6.1 Vapour Pressure and Boiling Point 130
6.1.1 Vapour Pressure 130
6.1.2 Boiling Point 131
6.2 Phase Behaviour of Pure Substances 131
6.3 Vapour Pressure and Temperature 134
6.3.1 The Clapeyron Equation 134
6.3.2 The Clausius Clapeyron Equation
- 134
6.3.3 The Antoine Equation 136
6.4 Vapour Pressure Plots 138
6.4.1 Equal-Temperature Reference-Substance Plots 139
6.4.2 Equal-Pressure Reference -Substance Plots 143
Exercises 146

7. Solutions and Phase Behaviour 149 -197

7.1 Ideal Solutions and Raoult’s Law 149
7.1.1 Ideal Solutions 149
7.1 .2 Raoult’s Law 150
7.1.3 Raoult’s Law and Vapour-Liquid Equilibrium Calculation 150
7.1.4 P -x-y Diagram 151
7.1.5 Boiling-point Diagram ( T-x-y Diagram) 152
7.1.6 Equilibrium Diagram y-x Diagram)
( 153
7.1.7 Flash Vaporization 153
VI Contents

7.2 Non-ideal Solutions 161

7.2.1 Deviation from Ideal Behaviour 161
7.2.2 Henry ’s Law 162
7.2.3 Henry ’s Law and Gas Solubility 163
7.3 Vapour-Liquid Equilibrium Calculatons 163
7.3.1 Vaporization Equilibrium Constants 163
7.3.2 Bubble-point Temperature and Pressure 164
7.3.3 Dew-point Temperature and Pressure 164
7.3.4 Flash Vaporization Calculations 165
7.3.5 Solution of VLE Problems 166
7 A Vapour Pressure of Immiscible Systems 177
7.5 Vapour Pressure of Solutions of Non-volatile Solutes 181
7.5.1 Relative Vapour Pressure 181
Exercises 183

8. Humidity and Humidity Chart 198-240

8.1 Saturation 198
8.2 Humidity, Percent Humidity and Dew Point 200
8.2.1 Humidity 200
8.2.2 Relative Humidity and Percent Humidity 203
8.2.3 Dew Point 207
8.3 Humidity Chart 210
8.4 Humid Heat 214
8.5 Wet-bulb Temperature 215
8.6 Adiabatic Saturation Temperature 218
8.7 Humid Volume and Enthalpy 223
8.7.1 Humid Volume 223
8.7.2 Enthalpy of Humid Air 223
Exercises 226

9. Material Balance in Unit Operations 241-296

9.1 Basic Material Balance Principles 241
9.1.1 Total and Component Balances 242
9.1.2 Steady -state and Unsteady -state Processes 243
9.1.3 Batch and Continuous Processes 244
9.1.4 Tie Element 244
9.1.5 Basis for Calculation 246
9.1.6 Independent Material Balance Equations and Degrees of Freedom 248
9.1.7 Steps for Solving Material Balance Problems 250
9.2 Material Balance without Chemical Reactions 252
9.2.1 Evaporation 253
9.2.2 Crystallization 256
9.2.3 Leaching 261
 ••
Contents Vll

9.2.4 Adsorption 265

9.2.5 Drying 265
9.2.6 Liquid-Liquid Extraction
9.2.7 Absorption 272
9.2.8 Distillation 276
Exercises 281

10. Material Balance with Chemical Reaction 297- 367

10.1 Combustion of Solid, Liquid and Gaseous Fuels 298
10.1.1 Orsat Analy sis 298
10.1.2 Proximate and Ultimate Analysis of Coal 301
10.2 Oxidation of Sulphur Compounds and Related Processes 314
10.3 Carbon Dioxide from Limestone 322
10.4 Reactions Involving Phosphorus and Phosphorus Compounds 325
10.5 Recovery of Metals and Non-metals from Ores 328
10.6 Nitrogen, Ammonia and Nitric Acid 329
10.7 Chlorine, Hydrochloric Acid and Chlorination 333
10.8 Hydrogenation, Hydration and Oxidation 337
10.9 Processes in Biological, Environmental and Energy Systems 338
10.9.1 Yield and Yield Coefficients 339
10.9.2 Elemental Balance 339
10.9.3 Respiratory Quotient 340
10.9.4 Degree of Reduction 340
10.9.5 Oxygen Requirement 341
Exercises 347

11. Bypass, Recycle and Purge Operations 368- 398

11.1 Bypass 368
11.2 Recycle 371
11.3 Blowdown and Purge 378
Exercises 383

—
12. Energy Balance Thermophysics 399- 470
12.1 Law of Conservation of Energy 400
12.2 Components of Energy Balance Equations 401
12.2.1 Heat and Work 401
12.2.2 Kinetic Energy, Potential Energy and Flow Energy 402
12.2.3 Internal Energy 405
12.2.4 Enthalpy 405
12.3 Heat Capacities 408
12.3.1 Mean Heat Capacity 413
12.3.2 Heat Capacity of Mixtures of Gases 414
Vlll Contents

12.4 Prediction of Heat Capacities of Solids and Liquids 416

12.4.1 Heat Capacity of Solids 416
12.4.2 Heat Capacities of Liquids 417
12.5 Enthalpy Change of Phase Changes 419
12.5.1 Estimation of Heat of Fusion 421
12.5.2 Estimation of Heat of Vaporization 422
12.6 Steam Tables 427
12.7 Heat of Mixing 429
12.7.1 Enthalpy-Composition Diagrams 434
12.8 Energy Balance in Cyclic Processes 436
12.9 Energy Balance in Non-flow Processes 436
12.9.1 First Law of Thermodynamics for Non-flow Process 436
12.9.2 Energy Changes in Ideal Gas Processes 439
12.10 Energy Balance for Flow Processes 443
12.10.1 Mechanical Energy Balance 445
12.10.2 Bernoulli’s Equation 445
Exercises 453

13. —
Energy Balance Thermochemistry 471- 505
13.1 Heat Effects Accompanying Chemical Reactions 471
13.1.1 The Standard Heat of Reaction 471
13.1.2 The Standard Heat of Combustion 473
13.1.3 The Standard Heat of Formation 474
13.1.4 Hess’s Law of Constant Heat Summation 475
13.1.5 Heat of Reaction at Constant Pressure and Constant Volume 482
13.2 Effect of Temperature on Standard Heat of Reaction 483
13.2.1 Temperature of Reaction 491
Exercises 494

Appendix: Tables of Properties 507- 519

Objective Type Questions 521- 559
Answers to Objective Type Questions 559
Bibliography 561- 563
Answers to Exercises 565- 592
Index 593- 600
 Preface

Ten years is a long period to revise a book dealing with subjects that undergo very fast changes
on a day -to-day basis. A subject like “ Stoichiometry and Process Calculations” , which is
concerned with the application of law of conservation of mass and energy, law of combining
proportions, etc. to industrial processes, does not undergo drastic changes in its basic content
in such a period. However, the scope and areas of application of the subject get widened with
the introduction of new technologies into the realm of chemical engineering.
In this revised edition, we have briefly reviewed the new avenues and opportunities open
to future chemical engineers and in order to equip them to meet this challenge, we have tried
to extend the principles of stoichiometry and process calculations to new and emerging areas
such as bioprocessing, energy and environment systems, etc. Material balance calculations for
processes with and without chemical reactions involving bypass, recycle and purge operations
have now been discussed separately in a new chapter. Considering the importance of exercise
problems in a book dealing with process calculations, exercise problems at the end of all
chapters are reorganized according to their difficulty level. Section on Objective Type Questions
with answers is augmented by including questions on process calculations from the last
10 years’ Graduate Aptitude Test in Engineering (GATE) questions.
The first edition of the book received appreciable recognition and acceptability from the
academic community. We are extremely thankful to our former colleagues and students for their
suggestions in improving the quality of the contents of the present edition. Earnest attempt is
made to bring out this edition free of errors. However, we will be indebted to those who could
point out errors that escaped our notice.

K.V. NARAYANAN
B. LAKSHMIKUTTY

ix
 Preface to
First Edition

Chemical engineers are concerned with the transformation of raw materials into useful products
on a commercial scale. Chemical process industries achieve this transformation through chemical
conversions and physical operations. As the major areas of their expertise lie in the development,
design, construction, operation and management of process industries, chemical engineers have
to answer questions such as: What is the raw material requirement for the specified production
capacity or what yield of products results from a given supply of raw materials? If the
unconverted materials are to be sent back to the processing unit, what should be the ratio of
the recycled stream to the fresh feed admitted? If heat is to be supplied to the process, how
many kilograms of steam would be necessary to maintain the temperature at the desired levels?
How many kilojoules of heat are to be removed from the processing unit to prevent temperature
from shooting up? The answers to these problems concerning the entire plant or individual units
can be provided by performing process calculations involving material and energy balances.
Process calculations are also necessary to provide a variety of information such as the
composition of flue gases that result from the combustion of fuels in the plant, the amount of
liquid solvent to be used in an absorption column for removing undesired components from a
gas stream, the rate at which air is to be sent through a dryer to reduce the moisture content
of solid products before being packed for marketing, the temperature and humidity of such air,
the rate of circulation of cooling water in the condenser and steam supply to the reboiler of
a fractionating column, the fraction of the air to be subjected for dehumidification or the
fraction to be bypassed if air of controlled humidity and temperature is desired for a certain
operation in the plant and so on. The subject of “ Stoichiometry and Process Calculations”
covers these and many other problems related to chemical process industries.
This book is intended as a textbook for undergraduate courses in chemical engineering and
related disciplines such as biotechnology, polymer technology, petrochemical engineering,
electrochemical engineering, environmental engineering, safety engineering and industrial
chemistry. The subject is taught in the early semesters of the undergraduate programme as
“ Stoichiometry ” , “ Process Calculations” or “ Chemical Process Principles” . As the students at
xi
xii Preface to First Edition

this stage are not yet exposed to different unit operations and unit processes, they usually find
the subject difficult due to their inability to comprehend the physical situations being analyzed
in the problems. An attempt is made in this book to introduce to the students the fundamentals
of chemical engineering and the various unit operations and unit processes before problems on
these topics are dealt with. The materials in this book are organized in such a way as to help
the students to develop a systematic approach to making stoichiometric calculations.
The word “ stoichiometry ” in chemical engineering is not just the application of law of
combining proportions to chemical reactions; it has got a wider meaning and encompasses all
calculations involving material and energy balances related to process industries. A number of
physical and chemical properties are required to make these calculations. These include density,
heat capacity, latent heat, heat of reaction, calorific values, vapour pressure , humidity, etc . In
the absence of experimental data on these properties, methods for their estimation should be
known. In addition, it is essential to know the dependence of these properties on process
parameters such as temperature and pressure . Other thermodynamic concepts such as the
--
P V T behaviour of fluids, the phase behaviour of pure materials and solutions are also important
to perform process calculations. The first eight chapters of the book deal with these concepts
in detail and provide a solid foundation for developing skills necessary for solving complex
chemical engineering process problems. Material and energy balances in processes with and
without chemical reactions are covered in the last four chapters.
The basic philosophy of process calculations is to prepare the students to make analysis
of processes through calculations and also to develop in them systematic problem -solving skills.
Through these calculations, the students get equipped with fundamental information and skills
that are repeatedly employed in subsequent courses as well as in professional life . With this
purpose in mind, we have taken care to include a large number of exercise problems at the end
of each chapter, and all of them are provided with answers. Objective type questions provided
at the end of the book help the students prepare for competitive examinations such as GATE.
We are extremely thankful to our colleagues in the Department of Chemical Engineering at
Government Engineering College, Thrissur for providing a helpful environment for writing this
book. Suggestions and critical comments for further improvements are welcome.

K.V. NARAYANAN
B. LAKSHMIKUTTY
 ] Introduction

Chemical engineering is concerned with the transformation of raw materials into useful products
making use of chemical conversions and physical operations . Industries engaged in this
transformation are known as chemical process industries. The reactions developed by the
chemists in the laboratory are utilized by the chemical engineer for the commercial production
of a wide variety of materials. A chemical engineer is interested more than anything else in the
application of chemistry and the various branches of engineering sciences to the design,
construction, operation, control and improvement of equipment for carrying out chemical
processes on an industrial scale with the ultimate objective of making a profit out of the
process. Therefore, we can treat chemical engineering as a branch of engineering which deals
with the application of mathematics, physics and chemistry to the manufacturing processes of
modern process industries. The official definition of chemical engineering put forward by the
American Institute of Chemical Engineers is sufficiently broad to make the position clear
regarding where a chemical engineer stands among other engineers and pure chemists: Chemical
engineering is the application of the principles of physical sciences together with the principles
of economics and human relations to fields that pertain directly to processes and process
equipment in which matter is treated to effect a change of state, energy content or composition .

LI CHEMISTRY VERSUS CHEMICAL ENGINEERING

Both chemists and chemical engineers can be treated as members of the chemical profession
since both should possess sound training in the principles of chemistry to be successful in their
respective areas. However, there is a wrong tendency of equating a chemical engineer with a
chemist forgetting the broad scope of problems encountered by the former. For a chemical
engineer his or her interest in chemistry is from the point of view of its industrial applications.
The bench scale techniques of the chemists as practised in the laboratory may be effective in
making original and exploratory investigations. However, these techniques are unsuitable for
large-scale production. It falls on the chemical engineer to convert the results of the laboratory
l
2 Stoichiometry and Process Calculations

scale investigation to commercial production. For effecting the transformation of the raw
materials to the final desired products, a large number of physical changes are also involved.
And processes involving only physical operations and which do not involve any chemical
reactions such as distillation are also not uncommon in chemical engineering practice. A typical
chemist has little knowledge of the theory and practice of such operations.

1.2 CHEMICAL PROCESS INDUSTRY

The chemical process industry is one whose principal products are manufactured by the
processes based upon chemical and physical principles, now being recognized as chemical
engineering principles. A chemical engineer is skilled in the development, design, construction
and operation of process industries . He /she finds employment primarily in research and
development, design and construction, manufacturing operations, management and administration,
waste treatment and disposal, technical services and sales related to process industries. The
chemical process industry generally employs “ chemical changes” for the production of useful
materials. We refer to chemical changes here in a broad sense as they include not only chemical
reactions, but also many physiochemical changes such as the separation and purification of the
components of a mixture . Purely mechanical changes are usually not considered part of a
chemical process, unless they are essential to later chemical changes. For example, the
manufacture of plastic polyethylene using ethylene produced from petroleum or natural gas
involves a chemical process. On the other hand, the moulding and fabrication of the resulting
plastic resin into final shapes for consumer products would not be considered part of a
chemical process. The huge metallurgical industry is usually distinguished from the chemical
process industry because of the special nature of the processes and the vast quantity of
products, but the processing of metals might also be considered to be merely a segment of the
chemical process industry. It follows that chemical engineering principles find applications in
any industry which, though not producing chemicals, makes use of chemical change. Examples
which suggest themselves are iron and steel production, the carbonization of coal, atomic
power generation, ceramics and the pulp and paper industries. Although a chemical engineer
working in such an industry might never be asked to carry out a complete plant design, his/
her knowledge would be invaluable particularly in the development of new ideas and procedures.
Table 1.1 lists the important chemical process industries and their end products.
Table 1.1 Major chemical process industries

Industry Products End uses

Inorganic chemicals Sulphuric acid Fertilizers, chemicals, petroleum refining, paint

pigments, metal processing, explosives
Nitric acid Explosives, fertilizers
Sodium hydroxide Chemicals, rayon and film processing
industries, petroleum refining, lye, cleansers,
soap, metal processing

( Contd. )
 Introduction 3

Table 1.1 Major chemical process industries (Contd .)

Industry Products End uses

Organic chemicals Acetic anhydride Rayons, resins, plastics

Ethylene glycol Antifreeze, cellophane, dynamite, synthetic
fibres
Formaldehyde Plastics
Methanol Formaldehyde manufacture, antifreeze, solvent
Petroleum and Gasoline Motor fuel
petrochemicals Kerosene Jet fuel , domestic fuel
Oils Lubricating, heating
Ammonia Fertilizers, chemicals
Ethyl alcohol Acetaldehyde , solvent , other chemical
manufacture
Alkyl aryl sulphonate Detergents
Styrene Synthetic rubber and plastics
Pulp and paper Paper, cardboard, Books, records, news paper, boxes, building
fibre board, etc. materials
Pigments and paint Zinc oxide, titanium Pigments for paints, ink, plastic, rubber,
oxide, carbon black, ceramic, linoleum
lead chromate,
Linseed oil Drying oil
Phenolic, alkyd resins Basic lacquers, varnishes and enamel paints
Rubber Natural rubber, synthetic Automobile tyres, moulded goods and
rubber (GR-S, Neoprene, sheeting, footwears, electrical insulation, etc.
Butyl )
Plastics Phenol formaldehyde, Various uses in all areas of everyday life
polystyrene, polymethyl -
methacrylate, PVC,
polyethylene, polyesters
Synthetic fibres Rayon, nylon, polyesters, Cloth and clothing
acrylics
Minerals Glass, ceramic, cement Windows, containers, bricks, pipes, concrete
for construction of buildings, highways
Cleansing agents Soaps, synthetic detergents, Household and industrial cleansing
wetting agents
Biochemicals Pharmaceuticals and drugs Health and medicinal applications
Fermentation products: Medicinal use, solvent, beverage
Penicillin, ethyl alcohol
Food products Human sustenance
Metals Steel, copper, aluminium, Building material , machinery, etc.
zirconium
Uranium Nuclear fuel
4 Stoichiometry and Process Calculations

1.3 GREATEST ACHIEVEMENTS IN CHEMICAL ENGINEERING

Products of the chemical process industries are used in all areas of everyday life. The ability
to bring once scarce materials to all members of society through industrial creativity is a
defining characteristic of chemical engineering. The American Institute of Chemical Engineers
has compiled a list of 10 greatest contributions of chemical engineering to improve the standard
of living of modem human beings. They are as follows:
1. The contribution of chemical engineering towards isolation of isotopes by splitting
atoms revolutionized such varied areas as biology, medicine, power generation, metallurgy
and archaeology.
2 . Mass production of plastics was made a viable economic reality by chemical engineers
in the twentieth century that had had its positive impact on all aspects of modem life.
3 . The concept of unit operations was extended to analyze the functioning of human body
that have helped improve clinical care, diagnostic and therapeutic devices and development
of artificial organs.
4 . Chemical engineers could improve the yield of antibiotics through mutation and special
brewing techniques. Low priced, high-volume drugs and pharmaceuticals owe their
existence to the work of chemical engineers.
5 . Introduction of synthetic fibres such as nylon, polyester, etc. had a profound impact
on many areas of life and it also reduced the strain on natural sources of cotton and
wool.
6. The liquefaction and subsequent separation of air into pure nitrogen and oxygen was
another major contribution of chemical engineering. Nitrogen can be used to recover
petroleum, freeze food, produce semiconductors or prevent unwanted reactions while
oxygen is used to make steel, smelt copper, weld metals together and for artificial
respiration.
7. Chemical engineers’ contribution in the areas of waste treatment and pollution abatement
helps keep the environment clean. Catalytic converters, reformulated gasoline and smoke
stack scrubbers and new recycling technologies are notable achievements in this area.
8. A tremendous increase in food production was made possible by the manufacture of
chemical fertilizers. Chemical engineers today play a very vital role in food processing
also.
9. One of the greatest contributions of chemical engineering is in the area of petroleum
processing and petrochemicals, which is now regarded as an enabling technology
without which modem life would cease to function. Chemical engineers have developed
processes such as catalytic cracking to break down complex organic molecules found
in crude oils to simpler species which serve as building blocks for the production of
many useful products such as gasoline, lubricating oils, plastics, synthetic rubber, and
synthetic fibres.
10. Chemical engineers played a prominent role in developing today ’s synthetic rubber
industry. Modern society is heavily dependent on synthetic rubber for products such as
tires, gaskets, hoses, conveyor belts and shoes.
 Introduction 5

Among other products of importance are insecticides, food supplements and disinfectants
that are essential for raising food plants and animals. Many building materials have been
chemically processed, for example, metals, concrete, roofing materials, paints, and plastics.
Clothing utilizes many synthetic fibres and dyes. Written communication uses paper and ink;
and electronic communication requires many chemically processed insulators and conductors.
Soaps, detergents, insecticides and disinfectants have a vital role in maintaining nation’s health
in addition to drugs and pharmaceuticals. There are many chemicals that never reach the
consumer in their original form but are sold within the industry for further processing or use
in the production of other chemicals for common use. It is often said that the chemical industry
is its own best customer.

1.4 FUTURE AVENUES AND OPPORTUNITIES

Over the decades, chemical engineers were making great contributions to improve the quality
of our life through their activities in diverse fields such as atomic science, polymers, paper,
dyes, drugs, plastics, fertilizers, foods, petrochemicals, etc. What does the future hold for the
next generation of chemical engineers? What are the challenges and opportunities that the new
generation of chemical engineers have to face in the coming years?
The role of chemical engineers in the fields of biotechnology, pharmaceuticals,
nanotechnology, molecular engineering, medical devices, and biomaterials is likely to expand
dramatically in the coming years. They are expected to make significant contribution in developing
improved polymer processing and devices relevant to bio-medical engineering. The physical and
biological treatment of hazardous wastes is an area in which chemical engineers have a significant
role to play. Development of separation techniques and technologies for solving separation
problems in the chemical, environmental, food, pharmaceutical, and biotechnological industries
offers further avenues for chemical engineers. With the broadening of their interest area to
encompass genetic engineering, nanotechnology and molecular engineering, computer simulation
and computational methods now extensively used in modeling studies are going to help the
chemical engineers in a big way in the analysis of such processes. Large-scale centralized
production that had been the hallmark of chemical processes in the past is going to be
supplemented by small-scale distributed production, which will allow localized production of
chemicals and energy.
The most dramatic change in chemical engineering is the result of the increasing importance
of biology and biochemistry and the evolution of biotechnology as a real commercial activity.
A switch from traditional sources of energy and raw materials to biological resources will be
the most dominant change. Energy intensive reactors and separators can be replaced with a
single vessel containing rationally engineered microorganisms capable of performing multiple
catalytic steps. Chemical engineers are now focusing on the use of alternative feedstocks such
as biomass and societal waste to produce chemicals and energy. Their aim is to use less carbon
in the manufacturing processes by making them more carbon efficient and this lower carbon
process is sometimes termed as “ Green Chemistry ” or sustainable processing. Great possibilities
of advances in catalytic conversion of biomass and C02 into practical forms of energy and
useful chemicals will require new advances in catalytic chemistry and processes most likely
based on nanocomposite materials.
6 Stoichiometry and Process Calculations

Nano-scale phenomena have always been a part of the profession because chemical engineers
work with molecules. Advances in nanotechnology have opened the door to new possibilities,
especially in materials. Some of these opportunities are products for biomedicine. Advanced
materials, such as bifunctional materials, conducting polymers, biomaterial (tissue engineering),
continue development for specialized applications. Microelectronicmechanical system (MEMS)
devices are being commercialized . A successful approach for the chemical engineers will be in
the integration of nano and biological platforms for commercial production of devices for
specific applications.
Other exciting frontier areas of importance in chemical engineering include molecular and
nano-scale engineering, molecular simulation, surface modification, protein separation processes
and supercritical fluid extraction. Molecular engineering is an important part of pharmaceutical
research and material science. Molecular engineering deals with any means of manufacturing
molecules or creating new manufacturing materials using them . The field can be seen as a
precision form of chemical engineering that includes protein engineering.

1.5 HISTORY OF CHEMICAL ENGINEERING

Chemical engineering was practised long before it was recognized as a distinct engineering
profession. It can be said that even the ancient Greeks and Romans practised it when they were
making soap or wine or were treating ores. However the evolution of chemical engineering as
a distinct profession occurred concurrently with expansion in the chemical industry during the
later half of the nineteenth century. The political changes that took place in France and Germany
during the mid nineteenth century had its impact on the industrial processes that were in
practice at that time. The chemical engineering profession emerged from the need to revise
these processes with an emphasis on safer and more efficient methods . Despite these
developments, education in these areas was not formalized . Students obtained some superficial
knowledge about these processes in chemistry courses. In those days, the predominant chemical
industries were built up in Germany whose achievements in the field of dyestuffs, synthetic
nitrates, and coal hydrogenation were the work of chemists collaborating with mechanical and
civil engineers. As a result, the process vessels of German chemical plants of that time and even
of a later period , were larger size replicas of laboratory apparatus used in research. The
“ chemical engineer” of those years was either a mechanical engineer who had gained some
knowledge of chemical process equipment with a lifetime of experience but little education, or
an applied chemist with knowledge of large scale industrial chemical reactions. “ From their
experience in chemical plants, both chemists with an instinct for engineering and engineers with
a taste for chemistry grew into chemical engineers without realizing it and without being willing
to admit it” (Sir Harold Hartley, 1958).
One of the earliest attempts to organize the principles of chemical processing and to clarify
the professional area of chemical engineering was made in England by George E. Davis
(1850-1906). He was an industrial inspector by profession and the daily inspection rounds he
used to take through various chemical plants of that time brought him close to the intricacies
of chemical processes and the innovations in the operation of those plants. He was convinced
of the necessity for a new branch of engineering that was equally comfortable with both applied
 Introduction 1

chemistry and traditional engineering. In 1880 he acted upon these ideas and proposed formation
of a “ Society of Chemical Engineers” which proved unsuccessful. In 1887 he gave a series of
12 lectures, which were later published in the Chemical Trade Journal. The lecture was
organized around individual chemical operations as practised by the British chemical industry.
Though the material was quite empirical in nature, it convinced others that the time for chemical
engineering had arrived.
In 1888, one year after Davis’s lectures at Manchester, Professor Lewis M. Norton (1855-93)
of the Chemistry Department of MIT started teaching a course in chemical engineering, which
was the first four-year bachelor program in chemical engineering. (However, as a department,
chemical engineering did not become independent until 1920!) Soon other colleges, such as
University of Pennsylvania and Tulane University followed MIT’s lead starting their own
four -year programs. When Norton died in 1893, Professor Frank H . Thorpe (1864-1932) took
responsibility of Norton’s course at MIT and published in 1898 the first textbook in chemical
engineering entitled Outlines of Industrial Chemistry.
In 1901 in England, Davis proceeded with the publication of his Handbook of Chemical
Engineering. Davis was responsible for adopting the idea of “ unit operations” in the second
edition of his book (1904) although the term was coined by Arthur D. Little at MIT much later
in 1915.
In the early years of the twentieth century, chemical engineering began to gain professional
acceptance. To survive, chemical engineers had to claim industrial territory by defining themselves
and demonstrating their uniqueness and worth. With this goal in mind, the American Institute
of Chemical Engineers (AIChE) was formed in June 1908. Just weeks after the formation of
AIChE, the American chemical society organized a “ Division of Industrial Chemistry and
Chemical Engineering” and authorized the publication of the Journal of Industrial and Engineering
Chemistry.

1.6 CHEMICAL ENGINEERING IN INDIA

In India Dr. H.L. Roy introduced chemical engineering in the curriculum of the then Bengal
Technical Institute, the nucleus of the present Jadavpur University as early as 1921 when
chemical engineering was still at its infancy in the West. It started with a four-year diploma
in chemical engineering. Full-fledged degree courses and master’s programmes were introduced
in the mid-forties and early fifties respectively. The University Department of Chemical Technology
of the Bombay University (UDCT), which came into being in 1934 had a full-fledged chemical
engineering section offering a two-year post BSc course in Textile Chemistry and Chemical
Engineering. The chemical engineering section at the University Department of Chemical
Technology has modernized the earlier courses and in 1951, the four-year post inter-sciences
course offering B. Chem . Engg. was introduced. Andhra University College of Engineering
established in 1933, offered graduate and postgraduate courses in Sugar Technology and
Chemical Technology, and in 1958 the B.Tech degree course in chemical engineering with
different electives was offered. The Indian Institute of Science founded in 1909 started offering
courses in chemical engineering from the Department of General Chemistry. In 1951, the
chemical engineering section got a separate status as the Department of Chemical Technology
8 Stoichiometry and Process Calculations

and Chemical Engineering. Harcourt Butler Technological Institute, Kanpur set up in 1921
though offered training in oil and paints, leather and sugar technology with chemical engineering
input, a formal course in chemical engineering was started only in 1954. In the fifties, Indian
Institutes of Technology (IITs) were established in different parts of the country all offering
degree courses in chemical engineering. The Indian Institute of Chemical Engineers came into
being in 1947.

1.7 UNIT OPERATIONS AND UNIT PROCESSES

The manufacturing processes of chemical and allied industries can usually be classified into
—
coordinate series of unit physical operations and unit chemical processes steps that are similar
in principle if not identical in applications. The unit operations involve the addition or removal
of some form of energy in the contacting, transport, and the conditioning of materials by
physical means with or without any chemical changes taking place. The unit processes on the
—
other hand, result in chemical changes in composition, character, and properties of materials —
and are most often affected or controlled by temperature and pressure changes, catalysis,
intimacy of mixing, and other physical phenomena.
Chemical reactions that have common chemical characteristics underlying their industrial
applications are grouped together for study as a unit process. This grouping of similar reactions
into a unit process simplifies their study, since all the reactions in a group have similar
requirements of raw materials, reaction conditions of concentration, temperature and pressure,
and processing equipment. The process engineer applies the same basic principles to all the
reactions. Also, the reactions require similar equipment, utilities, and technology. The principal
unit processes are: combustion, oxidation, nitration, halogenation, sulphonation, ammonolysis,
reduction, hydrogenation, esterification, hydrolysis, alkylation, polymerization, fermentation,
etc. This classification of chemical conversions into unit processes is not as strong as the
concept of unit operations for dealing with physical operations. Many exceptions and disparities
exist among processes falling within a particular classification.

Table 1.2 Different types of unit operations and unit processes

Unit operations Unit processes

Fluid flow Size reduction Oxidation Polymerization

Heat transfer Sedimentation Reduction
Mass transfer Filtration Nitration Pyrolysis
Drying Mixing Sulphonation Hydrolysis
Distillation Evaporation Electrochemical reactions
Crystallization Sublimation Industrial microbiological processes
Extraction Centrifugation Halogenation
Adsorption Materials handling
Gas absorption Ion exchange

The concept of unit operations distinguishes chemical engineering from all other professions
and gives the chemical engineering education programmes a common focus. Practising chemical
 Introduction 9

engineers come across a large number of chemical and physical operations for transforming
matter from inexpensive raw materials to highly desired products. Many similarities exist in the
manner in which the feed materials are converted to end products in different process industries.
When we break the diverse processes employed by different industries into a series of separate
and distinct steps called unit operations, we can find that many similarities exist between these
operations employed by different industries for entirely different purposes. These seemingly
different operations are common to all types of process industries. Identifying the operations
such as filtration, drying, distillation, crystallization, grinding, sedimentation, heat exchange,
evaporation, extraction, extrusion, etc. as unit operations became a convenient method for
organizing chemical engineering knowledge and provided a central theme for chemical engineering
education to rally around . The knowledge gained concerning a unit operation governing one set
of materials can easily be applied to others. Whether one is using distillation for the manufacture
of alcohol or for production of gasoline from petroleum, the underlying principle remains the
same .
The unit operations concept became the basic theme in the chemical engineering profession
ever since George Davis’s lectures on the topic. However, it was Arthur D. Little in 1915 first
recognized the potential of using this concept for distinguishing chemical engineering from
other professions . While mechanical engineers focused on machinery, industrial chemists
concerned themselves with products, and applied chemists studied individual reactions, no one
before chemical engineers had concentrated upon the underlying process common to all chemical
products, reactions and machinery. The uniqueness and worth of chemical engineers is now
evident to all concerned with large-scale chemical manufacture. The important unit operations
are discussed in the following paragraphs.

1.7.1 Fluid Flow Operations

These operations include the transportation of fluid from one point to the other. Since
transportation, storage and handling of fluids are more convenient than those of solids, the fluid
flow operations play a very significant role in process industries. A chemical engineer has to
deal with movement of fluid through pipes, pumps and all kinds of process vessels. Sometimes
reactant streams have to be passed through a bed of solid catalyst, sometimes a bed of solid
will be fluidized to effect better conversion. The quantitative relationship between the rate
of flow and pressure difference, the power requirement of the flow system , measurements
of rate of flow, etc . are therefore very important to his/her profession than any other
branch of engineering .

1.7.2 Heat Transfer Operations

As pointed out earlier all unit operations involve the transfer of energy into and out of the
system . Also all chemical reactions are accompanied by characteristic and unavoidable heat
effects. Heat transfer during boiling of liquids and condensation of vapours are frequently
encountered by a chemical engineer. The transfer of heat at the desired rate is thus a major
operation for carrying out all operations and reactions efficiently as is clear from the daily
— —
requirements of two important plant utilities the cooling water and steam by any process
10 Stoichiometry and Process Calculations

industry. Above all heat recovery will be a major concern from the point of view of conser-
vation of energy and the environment. The major heat transfer equipment the chemical engineer
has to work with includes a wide variety of tubular heat exchangers, plate heat exchangers,
boilers and condensers. The transfer and control of heat in process plants, design and operation
of heat transfer equipment employed by chemical process industries are therefore important
areas of chemical engineering activity.

1.7.3 Evaporation
Evaporation is used in industries for concentrating aqueous solutions by vaporizing the solvent
water and removing it as vapour. Typical industrial applications of evaporation include
concentration of cane-sugar juice in a sugar factory, concentration of ammonium sulphate in
a fertilizer unit, and concentration of spent soap lye to produce glycerine in a soap industry.
Depending upon the properties of materials being handled, there are a number of different types
of evaporators and different modes of feeding a multiple effect system consisting of a number
of evaporators arranged in series. Short-tube vertical evaporators, long-tube evaporators, climbing
film and falling film evaporators, etc . are some industrially important evaporators in use.
Evaporators and evaporator accessories like steam -jet ejectors, condensers, steam trap, etc.
require careful monitoring by chemical engineers.

1.7.4 Mass Transfer Operations

Mass transfer operations are employed by process industries for separation of mixtures into
their component parts. There is no chemical process industry that does not require a preliminary
purification of raw materials or final separation of products from by -products or other undesired
contaminants. Mass transfer operations are thus very important in process industries. When a
chemical reaction is implemented on a commercial scale, the investment on mass transfer
equipment generally exceeds the capital investment associated with the reactions as such. The
important mass transfer operations are reviewed in the following paragraphs.

Distillation: Distillation is used to separate liquid mixtures into component parts by boiling.
The difference in the volatilities of the constituents is the property that is exploited to effect
separation. The industrially important distillation method known as fractionation or fractional
distillation has got very wide application in chemical and petroleum industries. The products
obtained on distillation are commonly referred to as distillate (or top product which is rich in
more volatile components) and residue (or bottom product which is rich in less volatile
components).

Absorption: In absorption, the soluble constituents of a gas mixture are separated by absorbing
—
in a suitable liquid solvent. The reverse process the removal of certain constituents of a liquid
—
mixture by contacting with a gas phase is known as desorption or stripping. Ammonia is
absorbed from a mixture of ammonia and air by contacting the gas with water in equipment
known as absorption columns. Benzene vapours present in coke-oven gases can be absorbed
in hydrocarbon oils and hydrogen sulphide can be absorbed from gas mixtures using ethanolamine
solutions.
 Introduction 11

Liquid-liquid extraction: The process of separation of the components of a liquid mixture

by treating with an immiscible liquid solvent in which the constituents are differently soluble
is known as liquid liquid extraction . Aqueous acetic acid solution is mixed with isopropyl ether
-

solvent in order to extract the acid into the ether phase . Extraction results in two immiscible
phases, the solvent rich phase called the extract and the original solution from which the solute
is extracted known as the raffinate . The mutually insoluble extract and raffinate phases are then
separated from one another by settling and gravity separation.

Leaching: Leaching is the separation of the components of a solid mixture by selectively

dissolving the soluble components in the solid mixture in a liquid solvent. The recovery of
minerals from naturally occurring ores, oils from cakes, tannin from wood barks, sugar from
sugar beets, etc . are some of the industrial applications of leaching.

Adsorption: Components of a gas or liquid mixture can be adsorbed on the surface of a solid
adsorbent. The adsorption of organic vapours on activated charcoal, decolourization of
cane -sugar solution by adsorbing the colouring matter on activated carbon, drying of gases by
adsorbing water on silica gel, etc. are examples to cite a few. The adsorbed constituent can
be removed from the solid and thereby separation can be completed and the adsorbent regenerated
for further use.

Humidification: Humidification and dehumidification operations are used by process industries

for preparing air of desired temperature and humidity, water cooling, gas drying and other such
purposes. A gas phase (usually air) is contacted with pure liquid (usually water). The transfer
of vapour from liquid to gas occurs in humidification operations and the reverse process occurs
in dehumidification. Cooling towers, spray chambers, humidifiers, etc. are pieces of equipment
used for these operations.

Drying: Drying is usually one of the last operations in a process industry. Drying is an
integral part of the process in industries such as paper industries, where as drying is done in
other processes for reducing the cost of transportation of the product, to give some useful
properties to the product like the free -flowing nature of salt, to prepare the product in a form
that is suitable for handling and use. In drying a wet solid or a slurry is contacted with dry
gas (usually air or flue gas) so that water is vaporized from the solid and is carried away by
the gas. Depending upon the characteristics of the solid being dried, several types of dryers
are in common use. Tray drier (for pasty materials and lumpy solids), rotary drier (for granular
and free flowing solids), freeze driers (for foodstuffs and pharmaceuticals) and spray driers
(for slurries and pastes) are typical driers in use.

Crystallization: Crystallization is the process in which solid particles are formed from liquid
solution by evaporating and/or cooling of a saturated solution. The process is important since
a variety of materials is marketed in crystalline form and also as a method of purification. Tank
crystallizers, agitated batch crystallizers, Swenson-Walker crystallizer, vacuum crystallizers and
Krystal crystallisers are typical industrial equipment used for crystallization.
12 Stoichiometry and Process Calculations

Ion exchange: In ion exchange operations, the solute from a solution is retained on the solid
by reaction with the solid ion-exchange resins. Ions in solution can be removed by this process
as in purification of water.
In addition to the above separation methods in which the phases are in direct contact,
separation can be achieved by transferring materials through membranes separating the two
phases. Dialysis, electrodialysis, ultrafiltration, etc. are some membrane separation techniques.

1.7.5 Mechanical Separations

In a process plant the chemical engineer may have to deal with separation of solids from solids,
solids from gases, solids from liquids and liquid drops from gases. Mechanical separations are
based on physical differences among the particles such as size, shape or density. Important
operations falling under this category are screening, filtration, sedimentation, centrifugation, etc.

Screening: Screening is a method of separating solid particles from a mixture of solids based
on their size difference alone . Screens are available in variety of mesh sizes and depending upon
the size of the feed handled by the screens, screening devices are classified as grizzlies,
trommels, shaking screens and vibrating screens.
Filtration: In filtration, suspended solid particles in a fluid, either a gas or a liquid, is removed
by passing through a filtering medium such as canvas cloth that retains the particles as a
separate phase or cake and allows the passage of clear filtrate. Filter presses, leaf filters, rotary
drum filters, etc. are the filters used for separating solids from liquids. Centrifugal filters are
another class of filters in which the filtering medium is attached to a rotating basket and the
centrifugal action forces the liquid through it.

Sedimentation: In settling and sedimentation, the particles are separated from the fluid by
gravitational force acting on the particles. The particles can be solid particles or liquid drops.
The separation of a dilute slurry or suspension by gravity settling into a clear fluid and a slurry
of higher solids content is called sedimentation. Removal of solids from liquid sewage wastes,
settling of crystals from mother liquor, separation of solid food particles from a liquid food,
etc. are some important applications of settling for separation. Gravity settling tanks, Spitzkasten
classifier and continuous thickener are pieces of equipment coming under this group. Settling
of solid particles aided by centrifugal forces can be used to separate particles that will not settle
easily in gravity settlers. Centrifugal separation is employed in many food industries such as
breweries, vegetable oil processing, fruit juice processing, etc.

1.7.6 Size Reduction

Solids generally occur in sizes that are too large for conveniently handling them for either
separation of constituents or for chemical processing. The reduction in size is achieved by
means of crushing and grinding. Grinding operations are very prominent in ore processing and
cement industries. Food processing industries also employ size reduction operations extensively
as in grinding wheat, corn and rye to flour, in rolling, pressing and grinding of soybeans to
produce oil and flour. Jaw crushers, gyratory crushers, roll crushers, hammer mills and ball
mills are typical size reduction equipment used by processing industries.
 Introduction 13

1.7. 7 Mixing
Mixing of solids and pastes and blending of liquids are among the fundamental operations in all
chemical processes. Purpose of these operations are to produce product of uniform properties.
Kneaders, mixing rolls, pugmills, ribbon blenders, screw mixers and tumbler mixers etc . are
some typical vessels used for mixing pastes and dry powders.

1.8 STOICHIOMETRY AND PROCESS CALCULATIONS

There are certain fundamental principles underlying all unit operations and unit processes. These
can be broadly categorized into four groups. They are the material and energy balances and the
laws of equilibrium and the rate processes. As pointed out earlier, the unit operations deal mainly
with the transfer and change of energy and the transfer and change of materials by physical
or in some instances by physiochemical means. The study of material and energy balances in
these operations is very vital for better assimilation of the course materials that constitute the
undergraduate chemical engineering curriculum . The main thrust in the course offered under
different names such as Process Calculations, Stoichiometry, or Chemical Process Principles is
the study of material and energy balances involved in unit operations and unit processes. In
addition, there are certain principles and techniques that the student should master at an early
stage itself that will enable him /her a lot in the evolution into a good chemical engineer and later
in his/her professional life. These include the behaviour of gases and gas mixtures, both real
and ideal, estimation of their properties, phase behaviour of pure liquids and solutions, vapour
pressure and how it is influenced by changes in temperature and pressure, humidity and
saturation, application of psychrometric charts, steam tables, enthalpy -composition diagrams,
etc. to cite a few. A course in Process Calculations or Stoichiometry covers all the above topics.
It is clear that we use the word “ stoichiometry ” with a wider meaning: stoichiometry for a
chemical engineer is not just the application of the laws of combining proportions of elements
or compounds involved in chemical reactions.
The basic philosophy of process calculations is to assist the student in the analysis of
processes through calculations and develop in him /her systematic problem -solving skills. Through
these calculations the student gets equipped with fundamental information and skills that are
repeatedly employed in subsequent courses as well as in professional life. Although the theory
underlying the solution of these problems is well defined and unquestioned, the solution cannot
be achieved by application of just some theoretical formulae or some semiempirical equations.
Rather, using these principles for the solution of stoichiometric problems is an art, and like
every art, its mastering requires practice.
 s [ Units and Dimensions

A given physical quantity can be measured using a variety of units. For example, the length of
an object may be given in metres or in feet. The mass of an object may be given in kilograms
or in pounds. In engineering calculations, it is frequently necessary to convert quantities
measured in one system of units into another. In the absence of rigorous theoretical models,
engineers may have to use many empirical equations developed based on the experience and
experimental observations. These equations contain quantities that are measured in the specified
units. Familiarity with the various systems of units and conversion of quantities from one
system to another is, therefore, of prime importance in process calculations.

2.1 UNITS AND DIMENSIONS

A physical quantity is always expressed as the product of a number and a unit. For example,
P = 105 N /m 2 or L = 10 ft. The numbers by themselves have no meaning in the language of
measurements unless they are accompanied by units. For example, if you say the mass of an
object is 50, the object may weigh 50 kg or 50 lb or even 50 g. To avoid confusion and to
eliminate errors in calculations, the unit should be explicitly stated. Unit is any measure or
amount used as a standard for measurement. By dimension we mean the measurable extent of
a physical quantity. In the above example mass (represented by the symbol M ) is a dimension
and kilogram (kg) or pound (lb) is a unit. Units provide standards to measure the quantities
called dimensions. Each unit is associated with a dimension which is unique. Or, a unit refers
to one and only one dimension. The kilogram is a unit used to measure the dimension mass.
It cannot be used to measure the dimension time or temperature. Thus the dimension of the
unit metre is length (L). Primary quantities such as length, mass, time and temperature are
commonly used as the basis of measurement. These are called primary dimensions and are
represented by the symbols L, M, T and K respectively. The set of primary dimensions should
satisfy the requirement that all quantities that need to be measured can be assigned one or a
combination of primary dimensions. The derived unit is a combination of primary units and the
14
 Units and Dimensions 15

derived quantity is a combination of two or more primary dimensions and their units are a
combination of primary units. Thus the mass of an object has a dimension M and its unit is
kilogram whereas the density of a substance has a dimension ML 3 derived from primary
dimensions and its unit is kg/m 3 which is a derived unit. Quantities like heat capacity, viscosity,
specific volume, thermal conductivity, etc . are derived quantities.
Though each unit is associated with a unique dimension, the unit used to describe a given
dimension need not be unique. Thus kilogram and pound are just two of the different units
available for expressing the mass, newtons per square metre (N /m 2) and pounds per square
inch (psi) are just two of the different units available for expressing the quantity of pressure.
This difference is due to the different system of units used for measurements.

2.2 SYSTEM OF UNITS

There are four systems of units in common use. They are the metric system (MKS system),
the English system (FPS system), the CGS system, and the latest the Systeme International
(SI system). A system of units adopts a set of primary units each of which corresponds to a
primary dimension. All other units and dimensions allowed within a particular system are
derived units and derived dimensions.
The FPS system developed in England uses the unit foot (ft) for the dimension of length,
pound (lb) for the dimension of mass, second (s) for the dimension of time, and degree
Fahrenheit (°F) for the dimension of temperature. In the MKS system (the metric system)
developed in France in 1791, the unit for length is metre (m), the unit for mass is kilogram
(kg), the unit for time is second (s) and the unit for temperature is degree Celsius (°C). India
adopted the MKS system in 1957. The CGS system employs centimetre (cm), gram (g) and
second (s) for the units of length, mass and time respectively and uses the same standards for
the base units as the MKS system . In practice, it is difficult to work with MKS or CGS system
alone, and so both were used in engineering practice depending upon the convenience.
The different systems of units not only have different sets of base units, they use different
standards to physically represent these base units. For example, the kelvin, unit of thermo-
dynamic temperature in SI, is the fraction 1/273.16 of the thermodynamic temperature of the
triple point of water. Similarly, a standard alloy block of platinum and iridium maintained at the
International Bureau of Weights and Measures at Sevres in Paris is taken as the base unit of
mass, the kilogram . Table 2.1 gives the primary quantities and their units and dimensions
adopted in different systems of units.

Table 2.1 Primary dimensions and units in different system of units

Quantity Units Symbol Dimension

FPS MKS CGS FPS MKS CGS

Length foot metre centimetre ft m cm L

Mass pound kilogram gram lb kg g M
Time second second second s s s T
Temperature Fahrenheit Celsius Celsius °F °C °C K
16 Stoichiometry and Process Calculations

2.2.1 SI Units
The International System of Units (abbreviated SI for Systeme International) was adopted at
the Eleventh Conference Generate des Poids et Measures (CGPM) in 1960 with length, mass,
time, temperature, electric current and luminous intensity as the six basic quantities. The SI
system is a modification of the original metric system and it uses the metre for length, kilogram
for mass, second for tf /we, and degree kelvin (K) for temperature . The primary quantity mass
is long felt to be unsuitable for use in chemistry, where the number of molecules constituting
the system is much more important than the mass. Taking this into consideration, the Fourteenth
Conference Generate des Poids et Measures in 1971 expanded the list of primary dimensions
by including the amount of substance as a primary quantity with unit mole . Table 2.2 gives the
list of seven primary dimensions and their units used in the SI system .
Table 2.2 SI base units

Quantity Unit Symbol Standard/Definition Dimension

Length metre m The metre is the length of the path travelled by light L
in vacuum during a time interval of 1/299 792 458 of
a second .
Mass kilogram kg The kilogram is equal to the mass of the international M
prototype of the kilogram .
Time second s The second is the duration of 9 192 631 770 periods of T
the radiation corresponding to the transition between
the two hyperfine levels of the ground state of the
caesium 133 atom .
Electric current ampere A The ampere is that constant current which would I
produce between two straight parallel conductors of
infinite length and negligible circular cross-section,
and placed 1 metre apart in vacuum, a force equal to
2 x io-7 newton per metre of length .
Thermodynamic kelvin K The kelvin is the fraction 1/ 273.16 of the thermo- K
temperature dynamic temperature of the triple point of water.
Amount of mole mol 1. The mole is the amount of substance of a system n
substance which contains as many elementary entities as
there are atoms in 0.012 kilogram of carbon 12 .
2 . When the mole is used , the elementary entities
must be specified and may be atoms, molecules,
ions, electrons, other particles, or specified groups
of such particles.
Luminous candela Cd The candela is the luminous intensity, in a given direc- K
intensity tion, of a source that emits monochromatic radiation
of frequency 540 * 1012 hertz and that has a radiant
intensity in that direction of 1/683 watt per steradian .

2.2.2 Derived Units

The derived units can be represented by a combination of two or more primary dimensions and
their units are a combination of the primary units. For example, velocity can be defined as the
 Units and Dimensions 17

time rate of change of distance. The dimension of velocity (u ) can be written as length divided
by time ( L'T 1 ). The quantity acceleration ( a ) can be defined as the time rate of change of
velocity. The dimension of acceleration could be written as u!T (velocity divided by time), or
written in terms of the accepted fundamental dimensions, L'T 2 and its unit in SI is ms-2. Table 2.3
gives SI derived units having special names and symbols. Table 2.4 gives some derived quantities
in different systems of units that are commonly used in chemical engineering calculations.
Table 2.3 SI derived units having special names

Derived quantity Name and In terms of In terms of SI

symbol derived SI units base units
Plane angle radian (rad ) m ITT1 = 1
Solid angle steradian (sr ) m 2 in-2 = 1
Frequency hertz (Hz ) s-1
Force newton (N) m kg s-2
Pressure, stress pascal (Pa) N ITT2 rrr1 kg s-2
Energy, work, quantity of heat joule ( J) N m m 2 kg s-2
Power, radiant flux watt (W ) J s1
"

m 2 kg s-3
Electric charge, quantity of electricity coulomb (C) SA
Electric potential difference, electromotive force volt ( V) WA1 -
m 2 kg s-3 A-1
_ _
Capacitance farad (F) CV1 m 2 kg 1 s 4 A 2
Electric resistance ohm (D) VA >
-
m 2 kg s-3 A-2
Electric conductance siemens (S) AV1-
m-2 kg-1 s 3 A 2
Magnetic flux weber (Wb) Vs m 2 kg s-2 A-1
Magnetic flux density tests ( T ) Wb nr2 kg s-2 A-1

Table 2.4 Derived units in SI

Units ( symbolic abbreviation in brackets) Dimension

(Quantity ( Based on SI)
SI MKS/CGS FPS
2) (cm 2)
Area square metres ( m square centimetre square feet (ft 2 ) L2
Volume cubic metres ( m 3) cubic centimetre (cm 3), cubic feet (ft 3) L3
litre (L )
Density kilograms per cubic metre grams per cubic centimetre pounds per cubic foot ML ~3

(kg nr3) (g cm 3) (lb ft 3) ~

Mass flow kilogram per second gram per second g s-1 pounds per hour (lb h ) "

' MT ~ X

rate ( kg s 1)
-

_1
Molar flow moles per second moles _per second pound moles per hour nT
rate ( mol s-1) (mol s 1) (lb- mol h-1)
Volumetric cubic metres per second cubic centimetre per cubic feet per hour t3r -

‘
flow rate (m 3 s 1)
-
second (cm 3 s-1), (ft 3 h 1)
litre per second (L s-1)
Mass flux moles per square _metre moles per square metre
_ pound moles per hour nT 7 . 2

per second ( mol s 1 m-2) per second (mol s 1 m-2) per square foot
(lb-mol h 1 ft 2)
" "

( Contd. )
18 Stoichiometry and Process Calculations

Table 2.4 Derived units in SI (Contd .)

Units ( symbolic abbreviation in brackets) Dimension

( Based on SI )
SI MKS/CGS FPS

Force newton (N) kilogram-force ( kgf ) pound force ( lbf ) MLT 2 ~

Pressure newton per square metre kilogram force per square pound force per square ML XT
~ ~ 2

or pascal (N m-2 or Pa) centimetre ( kgf cm-2) foot (lbf ft-2)

Energy joule (J) metre kilogram force foot pound force (ft lbf ) ML 2T ~ 2

( m kgf )
Power watts or joules per
_ horse power (HP) foot pound force per ML2T ~ 3

second (W or J s 1) second (ft lbf s-1)

Heat, joule (J) kilocalories ( kcal ) British Thermal Unit ML 2T ~ 2

Enthalpy (Btu )
Heat joules per kilogram per kilocalories per kilogram Btu per pound per L2T 2K l
capacity degree kelvin (J kg-1 K-1) per degree Celsius, degree Fahrenheit
(kcal kg 1 °C l )
" ~
(Btu lb 1 ° ¥ l )
" ~

Molar heat joules per mole per degree kilocalories per mole per Btu per pound mole per MI?T 2K ' n 1

capacity kelvin (J mol-1 K -1) degree Celsius, _ degree Fahrenheit

(kcal mol-1 °C 1) (Btu lb- mol 1 0F-!)
"

Heat flux joules per square metre kilocalories per hour Btu per hour per square MT 3
per second per square metre foot (Btu h-1 ft-2)
_
(J s 1 m-2, W m-2) ( kcal h-1 m-2)

2.2. 3 SI Prefixes
Table 2.5 lists the SI prefixes that are used to form decimal multiples and submultiples of SI
units. They allow very large or very small numerical values to be avoided. A prefix attaches
directly to the name of a unit, and a prefix symbol attaches directly to the symbol for a unit.
For example, one kilometre, symbol 1 km, is equal to one thousand meters, symbol 1000 m or
103 m . When prefixes are attached to SI units, the units so formed are called multiples and
submultiples of SI units in order to distinguish them from the coherent system of SI units.

Table 2.5 SI prefixes

Factor Prefix Symbol Factor Prefix Symbol

1024 yotta Y to-1 deci d
1021 zeta Z io-2 centi c
1018 exa E io-3 milli m
1015 peta P lO^5 micro F
1012 tera T 10 9
-
nano n
109 giga G 10 12
-
pico P
106 mega M 10 15
-
femto f
103 kilo k 10-18 atto a
102 hecto h 10 -21 zepto z
101 deka da 10 -24 yocto y
 Units and Dimensions 19

2.2.4 General Guidelines on the Use of SI Units

The general guidelines for using SI units are given in Table 2.6.

Table 2.6 General guidelines on the use of SI units

Guideline Correct usage Incorrect usage

(examples) or usage not
recommended
(examples )

Unit symbols are printed in lower-case letters. m (metre) M ( Metre )

Exception: The symbol or the first letter of the symbol Pa ( pascal ) pa (Pascal )
is an upper- case letter when the name of the unit is s ( second ) S (Second )
derived from the name of a person . Also, the recom - kW (kilowatts) kw (Kilowatts)
mended symbol for the litre is L . V ( volt) v ( Volt)
Unit symbols are unaltered in the plural . Length is 50 cm . Length is 50 cms.
Unit symbols are not followed by a period . Unit Mass should be 25 kg Mass is 25 kg .
symbols will be followed by a period at the end or more. Mass should or more.
of a sentence . be 25 kg.
Symbols for units formed from other units by multi - -
N m or N m m s-1 - As ms-1 means
plication are indicated by means of either a centred or m s-1 reciprocal milliseconds.
dot or a space . it is incorrect to write
ms-1 for indicating
metre per second .

Symbols for units formed from other units by division m/s, — , or m s 1 m/s/s
are indicated by means of a solidus (oblique stroke, /), m/s2 or m s-2 _ _
a horizontal line, or negative exponents. However, to m - kg/(s3-A ) or m - kg - s 3 -A 1 mkg/s3/A
avoid ambiguity, the solidus must not be repeated on
the same line without using parentheses.
Unit symbols and unit names are not used together. W/ m 2 or watts per watts/ m 2 or W/square
square metre metre
Because acceptable units generally have inter - s or second sec or Sec
nationally recognized symbols and names, it is not mm 2 or square millimetre sq. mm
permissible to use abbreviations for their unit symbols cm 3 or cubic centimetre cc or ml
or names, such as sec (for either s or second ), mins, min ( minutes) mins
(for either min or minutes), hrs (for either h or hours), h ( hours) hrs
lit (for either L or litre), amps (for either A or amperes), L or litre lit
AMU (for either u or unified atomic mass unit), or mps m/s or metre per second mps
(for either m/ s or metre per second ).
Prefix symbols are printed in roman ( upright ) type mL (millilitre) m L (milli litre)
regardless of the type used in the surrounding text , pm ( picometre ) p m ( pico metre )
and are attached to unit symbols without a space bet- GQ (gigaohm) GO (giga ohm)
ween the prefix symbol and the unit symbol . This last THz ( terahertz )
rule also applies to prefixes attached to unit names.

( Contd. )
20 Stoichiometry and Process Calculations

Table 2.6 General guidelines on the use of SI units (Contd .)

Guideline Correct usage Incorrect usage

(examples) or usage not
recommended
( examples )

The prefix symbols Y ( yotta ), Z ( zetta), E ( exa ), THz G £2 tHz gft

P ( peta), T (tera), G (giga), and M (mega) are printed
in upper-case letters while all other prefix symbols
are printed in lower-case letters. Prefixes are normally
printed in lower-case letters.
The grouping formed by a prefix symbol attached millimetre (mm) milli metre (m m)
to a unit symbol constitutes a new inseparable symbol 5 cm 3 = 5.0 (cm )3
(forming a multiple or submultiple of the unit con - millimetre, micropascal ,
cerned ) which can be raised to a positive or negative meganewton,
power and which can be combined with other unit are single words
symbols to form compound unit symbols. Prefixes are
also inseparable from the unit names to which they
are attached .
Compound prefix symbols, that is, prefix symbols nm (nanometer ) mjim
formed by the juxtaposition of two or more prefix (millimicrometer)
symbols, are not permitted . This rule also applies to
compound prefixes.
In a derived unit formed by division, the use of a 10 MV/m ( preferred because 10 kV/mm (is
prefix symbol ( or a prefix ) in both the numerator it contains only one prefix acceptable but not
and the denominator may cause confusion . In a symbol and it is in the preferred ) 10 MV- ms
derived unit formed by multiplication, the use of more numerator ) ( not preferred )
than one prefix symbol (or more than one prefix ) 10 kV- s ( preferred )
may also cause confusion .
6
For historical reasons, the name kilogram for the SI 10 -
kg = 1 mg (1 milligram ) 10 6 kg = 1 pkg
-

base unit of mass contains the name kilo, the SI (1 microkilogram)

prefix for 103. Thus, because compound prefixes are
unacceptable, symbols for decimal multiples and
submultiples of the unit of mass are formed by
attaching SI prefix symbols to g, the unit symbol for
gram, and the names of such multiples and submulti-
ples are formed by attaching SI prefixes to the name
gram . Example: 1 mg but not 1 microkg .
When writing numbers, digits should be separated 83 254 346 83,254,522
into groups of three , counting from the decimal 56 235.175 73 56,235.175 73
marker towards the left and right, by the use of a thin, 0.562 345 5 0.5623455
fixed space . Comma should not be used for the 8765 or 8 765 8,765
purpose . However, this practice is not usually follo-
wed for numbers having only four digits on either
side of the decimal marker except when uniformity
in a table is desired .

( Contd. )
 Units and Dimensions 21

Table 2.6 General guidelines on the use of SI units (Contd .)

The SI unit of volume is the cubic metre ( m 3) and may be used to express the volume of any substance, whether
solid , liquid, or gas. The litre (L ) is a special name for the cubic decimetre (dm 3) but the CGPM recommends
that the litre not be used to give the results of high accuracy measurements of volumes.
Celsius temperature ( /) is defined in terms of thermodynamic temperature (7) by the equation t = T - T0 , where
T0 = 273.15 K by definition. This implies that the numerical value of a given temperature interval or
temperature difference whose value is expressed in the unit degree Celsius (°C) is equal to the numerical value
of the same interval or difference when its value is expressed in the unit kelvin (K ); or { At } oC = { AF} K. Thus
temperature intervals or temperature differences may be expressed in either the degree Celsius or the kelvin
using the same numerical value. Example : The difference in temperature between the freezing point of gallium
and the triple point of water is At = 29.7546°C = AT = 29.7546 K .

2.3 CONVERSION OF UNITS

Most of the physical or chemical data available in literature are expressed equivalently with a
variety of units. Operating manuals of equipment and instruments using different systems of
units still abound in the process plants. It is imperative that chemical engineering students or
practising chemical engineers be well versed with the conversion of units from one system to
another. Conversion factors which relate the units in one system of units to those in another
system can be made use of for this purpose . Table 2.7 provides a condensed list of conversion
factors of certain units frequently encountered in chemical engineering calculations. To convert
the units to the desired system of units, the original expressions are multiplied or divided by
the conversion factor. For example, the length measured in inches is multiplied by 2.54 x 10 2 ~

to express it in metres. Here, 2.54 x 10 2 or to be accurate 2.54 x 10 2 m /in is the conversion

~ ~

factor for inch to metre . Thus a length measuring, say, 10 inches is equivalently written as

10 in = 10 in x
f 2.54 x!0 2 irT = 0.254 m
“

in j
V

Here, the length in metres is multiplied by the conversion factor 2.54 x 10 2 m /in so that -

the resulting expression has the desired units of metre. The choice of whether the original
expression is to be multiplied or divided by the conversion factor is to be made so as to cancel
_ only the desired units. Thus the mass expressed
all the units in the original expression leaving
in kilogram is divided by 4.535 924 x 10 1kg/lb to obtain mass in pounds. Thus
r \
lb
50 kg = 50 kg _ = 110.23 lb
V
4.535924 x 10 1 kg /

2.3.1 Some Important Derived Quantities and Their Conversion

Force: According to Newton’s second law of motion, the force acting on a body is directly
proportional to the time rate of change of momentum . For a body of constant mass, Newton’s
law reduces to
F = cma (2.1)
where F is the force, m is the mass of the body, a is the acceleration and c is a proportionality
22 Stoichiometry and Process Calculations

Table 2.7 Conversion factors

To convert from To Multiply by

atmosphere, standard (atm) pascal (Pa ) 1.013 25 x 105

bar ( bar ) pascal (Pa ) 1.0 x 105
British thermal unit (Btu) joule (J) 1.055 056 x 103
British thermal unit per pound degree joule per kilogram kelvin 4.1868 x 103
Fahrenheit (Btu lb-1 °F-1 ) (J kg-1 K-> )
calorie (cal ) joule (J) 4.1868
centimetre (cm) metre (m) 1.0 x 10-2
centipoises (cP) pascal second (Pa s) 1.0 x 103
centistokes (cSt) metre square per second ( m 2 s-1) 1.0 x lO^5
cubic foot (ft3) cubic metre ( m3) 2.831 685 x 10-2
3
cubic foot per minute (ft min )-1 cubic metre per second ( m 3 s-1) 4.719 474 x 10 4 -

dyne (dyn) newton (N) 1.0 x 10 5

erg (erg ) joule ( J) 1.0 x 10 7
-

foot (ft ) metre (m) 3.048 x 101

foot per hour (ft h-1) metre per second ( m s-1) 8.466 667 x 10 7
gram per cubic centimetre (g cm-3) kilogram per cubic metre ( kg m-3) 1.0 x 103
horsepower (550 ft lbf s-1), (hp) watt (W) 7.456 999 x 102
horsepower (metric) watt (W) 7.354 988 x 102
inch in
( ) metre (m) 2.54 x 10-2
kilocalorie (kcal ) joule (J) 4.1868 x 103
kilogram-force ( kgf ) newton (N) 9.806 65
kilogram -force per square centimetre pascal (Pa ) 9.806 65 x 104
(kgf cm-2)
kilowatt hour (kW h) joule (J) 3.6 x 106
mile ( based on U. S. survey foot), ( mi ) metre (m) 1.609 347 x 103
mile per hour ( mi h 1)
-
metre per second ( m s-1 ) 4.4704 x 10- '
poise (P) pascal second (Pa s) 1.0 x 10- '
pound (avoirdupois) (lb) kilogram (kg ) 4.535 924 x 10 “

'
poundal newton ( N) 1.382 550 x 10- '
pound -force (lbf ) newton (N) 4.448 222
pound -force per square inch, psi, (lbf in 2) pascal (Pa)
-
6.894 757 x 103
pound per cubic foot (lb ft-3) kilogram per cubic metre ( kg m-3) 1.601 846 x 10 '
square foot (ft 2) square metre ( m 2) 9.290 304 x 10-2
stokes (St) metre square per second ( m 2 s-1) 1.0 x 10 4
“

ton, metric (t ) kilogram (kg) 1.0 x 103

torr ( Torr) pascal (Pa) 1.333 224 x 102
watt second (W s) joule (J) 1.0
degree Celsius (temperature) (°C) kelvin (K ) 77K = tl°C + 273.15
degree Fahrenheit (temperature) ( °F) degree Celsius ( °C) t/°C = ( //°F - 32)/1.8
degree Fahrenheit (temperature) (°F) kelvin (K ) 77K = (//°F + 459.67)/1.8
degree Rankine ( °R) kelvin (K ) 77K = (77°R)/1.8
 Units and Dimensions 23

constant. In the SI system, the constant c is unity and we have

F = ma (2.2)
When a body of mass 1 kg is accelerated by 1 the force acting on the body is 1 kg m/s2,
m/s 2,
which is designated as 1 newton or (1 N).
The force unit poundal in FPS system is similar to newton . It is the force that gives an
acceleration of 1 ft/s2 when applied to a body having a mass of one pound.
1 poundal = 1 ft lb/s2
In engineering practice, two technical units of force, kilogram force (abbreviated as kgf )
in MKS system and the pound force (abbreviated as lbf ) in FPS system were in force for quite
a long time . These are defined by letting c in Eq. (2.1) as equal to 1lgC where gc is called the
9

Newton’s law conversion factor. That is

ma
F= (2.3)
gc
The value of gc is 9.806 65 kg m (kgf )-1 s-2 in MKS system and 32.174 lb ft (lbf )-1 s-2 in
FPS system . The numerical value of gc corresponds to the acceleration due to gravity at mean
sea level. Although g (acceleration due to gravity ) varies from locality to locality, gc does not.
The dimension of g is LT 2 whereas the dimension of gc is MLF lT 2 where F stands for the
~ ~ ~

technical dimension of force.

The force acting on a body under gravitational acceleration is called the weight of the body.
Thus weight W is given as
mg
W= (2.4)
Sc
Although g is a local variable, in ordinary calculations g/ gc is taken as 1 kgf/kg or 1 lbf/lb,
so that the weight of the body in technical force units is numerically equal to the mass of
the body.

Pressure: The pressure is defined as the normal component of the force per unit area exerted
by the fluid on a real or imaginary boundary. The unit of pressure in the SI system is newton
per square meter (N /m 2), also called the pascal (Pa). A multiple of pascal, called the bar is also
used as a unit of pressure.
1 bar = 105 Pa = 105 N /m 2
The pressure exerted by the atmosphere is called the atmospheric pressure and it varies with
location and elevation on the earth’s surface. One standard atmospheric pressure abbreviated
as atm is used in all systems of units as an empirical unit of pressure. It is the average
pressure exerted by the earth’s atmosphere at sea level. Although actual atmospheric pressure
varies from place to place, its value at mean sea level is taken to be 1.013 25 x 105 N /m2 (or
1.013 25 bar).
In engineering practice the pressure is frequently reported as gauge pressure . The absolute
pressure is related to the gauge pressure by the following relation:
absolute pressure = gauge pressure + atmospheric pressure
24 Stoichiometry and Process Calculations

Similarly, pressures below atmospheric (subatmospheric) are reported as vacuum such that
absolute pressure = atmospheric pressure - vacuum
Pressure can also be expressed in terms of the height of the column of mercury, which
it will support at a temperature of 273.15 K in a standard gravitational field . At standard
atmospheric pressure this height is 0.76 m (760 mm or 760 torr) with density of mercury taken
as 13.5951 x 103 kg/m 3.
1 standard atmosphere (atm) = 1.013 25 bar = 1.013 25 x 105 Pa
= 1.013 25 x 105 N/m 2 = 760 mm Hg
Other important pressure units are the kgf/cm 2 in MKS system and lbf/in2 (commonly
written as psi ) in FPS system .

Work: Energy is expended in the form of work when a force acts through a distance. Thus,
dW = F dZ (2.5)
where W is the work done, F is the force acting and Z is the displacement. The unit of work
in the SI system is N m (newton-metre) or J ( joule).

Energy: Energy is a quantity that can be stored within the system and can be exchanged
between the system and the surroundings. The exchange of energy occurs either as heat or
as work . Heat and work cannot be stored within the system : they can be treated as energy in
transit. Energy stored within the system due to its position above some arbitrary reference plane
is referred to as its potential energy (PE). If mass m is at an elevation z above the ground, the
potential energy of the mass is
PE = mgz (2.6)
where g is the acceleration due to gravity. The energy possessed by the body by virtue of its
motion is called its kinetic energy (KE). If a body of mass m is moving at a velocity u, the
kinetic energy of the body is

KE = - mu 2 (2.7)

The unit of energy in SI system is the joule (J).

1 J = 1 N m = 1 kg m 2/s 2
Heat: Heat is that quantity which is transferred between bodies due to the difference in
temperatures existing between them . Earlier, this quantity was thought of as a substance called
caloric. Heat is now recognized as a form of energy that cannot be stored as such within the
system . And like work, it is expressed in J ( joule). Two other units used for heat are the calorie
and the Btu (the British thermal unit).
1 calorie = 4.1868 J; 1 Btu = 1055.06 J

Power: The power is defined as the time rate of doing work. Its unit in the SI system is
J /s, commonly designated as W ( watts ). In engineering calculations, power is generally expressed
as horsepower (hp).
 Units and Dimensions 25

1
1 metric hp = 75 m kgf s = 735.5 W
1 British hp = 550 ft lbf s "
1 = 745.7 W
EXAMPLE 2.1 The flow rate of water through a pipe is reported as 15 cubic feet per minute.
Taking density of water as 1 g/cm 3, calculate the mass flow rate in kg/s.
Solution Volumetric flow rate = 15 ft3/min
Using the relationship 1ft = 0.3048 m and 1 min = 60 s, the volumetric flow rate can now
be expressed in m 3/s.
y \

15 ft 3 0.30483 m 3
v ft 3 / 3
Volumetric flow rate 7.079 x 10 "

m 3/s
min
( 60 s ^
v mm /

lg
f 10 3 k g )
“

v g
Density of water is 1 g/cm 3 =
/
= 1000 kg/m 3
cm 3
'
10 -6
m 3
^
3
v cm '
y

Mass flow rate = Volumetric flow rate x density of water

= 7.079 x 10 3 m 3/s x 1000 kg/m 3 = 7.079 kg/s
“

EXAMPLE 2.2 Determine the conversion factor for poundal to newton

y y
0.3048 m \ 0.4536 kg \
Solution 1 poundal is 1 ft lb/s 2 = 1 (ft)
v ft
kg m
/
(lb)
V lb / /’
*

= 0.1383 = 0.1383 N
s2
The conversion factor is 0.1383 N /poundal.

EXAMPLE 2.3 Express kgf/cm 2 and lbf/in 2 as N /m 2.

Solution 1 kgf = 9.806 65 N
2
9.806 65 N !
(kgf )
, kgf kgf
= 0.981 x 10s N/m 2
_ y
2 / 4 2'
cm
~

10 m
(cm 2 )
V cm 2 j

lb ft
The Newton’s law conversion factor relates lbf to poundal. 1 lbf = 32.174 . Using
kg m m
—
this and other conversion factors like 0.453 59 24 , 0.3048 and 0.0254 , we get the
lb ft in
— —
following.
26 Stoichiometry and Process Calculations

/
32.174 lb ft \ / 0.453 59 24 kg X 0.3048 m \
dbf )
lbfs 2 / V
-
^
V lb ft /
1 1
2 2
in (0.0254) m
(in 2 )
in 2
kg m .
= 6894.75 2 2 = 6894.75 N/m 2
s m
lbf
(Table 2.7 gives 6.894 757 x 103 as the value for the conversion factor for to pascal.)

EXAMPLE 2.4 In the SI system, thermal conductivity has the unit W/(m K). The thermal
xQ
conductivity of a solid material can be calculated as k = , where Q is the rate of heat
AAT
transfer, x is the thickness of solid, A is the area of heat transfer and AT is the temperature
difference across the solid. The following values were obtained experimentally : Q = 10 000 kJ/h,
A = 1 m 2, x = 100 mm and AT = 800 K.
(a) Calculate the thermal conductivity of the solid in W/(m K).
(b) Express the thermal conductivity in kcal/(h m °C).
( c ) If thermal conductivity of a second material is 0.15 Btu/(h ft °F), which one will make
a better thermal insulator?
Solution ( 1000 J \
10000 kJ
Q = 10000 kJ /h = V kJ J = 2777.78 J/s
h f
(a) The rate of heat transfer,
l
3600
h ^
s
J
We have:
x = 100 mm = 0.1 m, A = 1 m 2, AT = 800 K
Substituting these values in the given equation, we get
xQ 0 1 x 2777.78
,
" ~

AAT 1 x 800
J W
= 0.347 = 0.347
sm K mK
W J
(b) 0.347 = 0.347
mK smK
r \
cal
J
v 4.1868 J / = 298.557
cal
= 0.347 r \
h °C h m °C
s x m * Kx
v 3600 s / K
 Units and Dimensions 27

( c ) The thermal conductivity of the material in the FPS system is

W J
0.347 = 0.347
mK sm K
r \
Btu
J
= 0.347 v 1.055 056 x 103 J / = 0.2
Btu
\
h ft 1.8 °F h ft °F
s xmx xKx
v 3600 s/ 0.3048 m K
The second material will make a good thermal insulator as its thermal conductivity is
0.15 Btu/(h ft °F) which is less than the thermal conductivity of the first material
calculated above (0.2 Btu/h ft °F).
EXAMPLE 2.5 The weight of an object is 300 N at a location where acceleration due to
gravity is 9.81 m /s 2.
(a) Determine the mass of the object in kilograms.
(b) Express the mass in the FPS system .
Solution (a) Force is equal to the product of mass and acceleration, i.e.
F = ma
300 = m x 9.81
300
Therefore, w= = 30.58 kg
9.81 *
_
(b) The conversion factor for pound to kilogram is 4.535 924 x 10 1 kg/lb. Therefore the
mass of the object in the FPS system is
/ \
lib
30.58 (kg) _1 = 67.42 lb
V
4.535 924 xl 0 kg /

EXAMPLE 2.6 The potential energy of a body at a height of 15 m is 2 kJ. If the body is
moving at a velocity of 50 m /s what is its kinetic energy ? (Take g = 9.8067 m /s 2)
Solution Potential energy (PE) = mgz
Here z = 15 m, PE = 2000 J.
Therefore, 2000 = m x 9.8067 x 15
Thus the mass of the body m = 13.596 kg.

Kinetic energy, KE = —12 mu ?

= - (13.596)(50) 2 = 16 995 J = 16.995 kJ

2.
*

EXAMPLE 2.7 Nitrogen gas is confined in a cylinder and the pressure of the gas is maintained
by a weight placed on the piston. The mass of the piston and the weight together is 100 lb.
28 Stoichiometry and Process Calculations

The acceleration due to gravity is 9.81 m /s2 and the atmospheric pressure is one standard
atmosphere. Assuming the piston is frictionless, determine:
(a) The force exerted by the atmosphere, the piston and the weight on the gas in N if the
piston diameter is 4 in.
(b) The pressure of the gas in bar and psi.
( c ) If the gas is allowed to expand pushing up the piston and the weight by 400 mm, what
is the work done by the gas in kJ?
(d) What is the change in the potential energy of the piston and the weight after the
expansion in part (c)?
Solution (a) One standard atmosphere = 1.01325 x 105 N/m 2
The area of the piston is

x D 2 = — (4 x 2.54 x 1(T2 ) 2 = 8.1073

— X 10 3
m2
4 4
Force exerted by the atmosphere = pressure x area
= 1.013 25 x 105 x (8.1073 x 10 3) = 821.47 N"

Force exerted by the piston and weight = m x g

= (100 x 0.4536) x 9.81 = 444.98 N
Total force acting on the gas is
821.47 + 444.98 = 1266.45 N
1266.45
(b) Pressure = force /area =
(8.1073 x 10-3 )
= 1.562 x 105 N/m 2 (= 1.562 bar)
From Table 2.7 the conversion factor for converting psi to pascal (Pa) is 6.894 757 x
, —Pa
l (r r Therefore, pressure in psi is
psi

1.562 xlO5
-7 = 22.65 psi
6.894 757 xlO 3
(b) Work done = force x displacement = 1266.45 x (400 x 10 3) = 506.58 J = 0.507 kJ
~

( c ) Change in the potential energy,

A ( PE) = mgbz = 100 x 0.4536 x 9.81 x (400 x 10 3) = 177.99 J
"

2.3.2 Conversion of Empirical Equations

Empirical equations are available for estimating thermodynamic properties, transport coefficients,
frictional losses and pressure drop for flow through different geometries, etc. These equations
are correlations of experimental results by empirical means without regard to dimensional
homogeneity and they provide the desired results only if we stick to the units specified for the
 Units and Dimensions 29

quantities involved . For example, the rate of heat loss from a cylindrical pipe to the ambient air is
correlated by the equation
AT 1.25
q = 7.38 x
DP0.25
where q is the rate of heat loss in W/m 2, AT is the temperature difference in K, and DP is the
diameter of the pipe in mm . The dimension of q on the right-hand side is not the same as the
dimensions on the left-hand side. Such equations are also known as dimensional equations.
These give incorrect results when used for calculations in case we fail to use quantities in the
specified units. If, for example, we want to use the FPS units in the calculation of heat loss using
the equation given above, we have to convert the equation into the equivalent FPS form . In the
following paragraphs, we illustrate through some examples the conversion of dimensional equations
into their equivalent forms in other systems of units.
EXAMPLE 2.8 For the absorption of sulphur dioxide in water in towers packed with wood
grids, the following empirical equation is proposed for evaluating mass transfer coefficient:
0.8
6.7 x 1 0-4 G ( ds i- dp ^)
“

kG -
44 42 ds
where kG is the mass transfer coefficient in lb-mol/(h ft 2 atm), G is the superficial mass velocity
in lb/(ft 2 h), ds represents clearance between grids in feet, dG represents the height of grids in
feet, and dT is the thickness of the grid slats in feet. What is the corresponding equation if kG
is given in kmol/(m 2 h atm ), G is in kg/(m 2 h) and the lengths are given in m ?
Solution Suppose that the mass velocity is G' in kg/(m 2 h), and d's, dG and d'T are the
clearance between grids, height of grids and thickness of grid, respectively, all measured in m .
Then

kE lib V 0.30482 m 2
f
, lb 1
G - G/ 2 2 = 0.2048G 2
m h \ 0.4536 kg / \ lft /
ft h
f \
lft
d = d' ( m )
v 0.3048 m /
•
—
= 3.2808d' ft

Since G and d are in the units specified for the given equation, we can substitute these and
get the following result.
0.8
6.7 x 10-4 0.2048G' x 3.2808 (4 + 4 )
°—
kri , 0.2
(3.2808 )° (3.2808 )
4

^ 3.2808
^ ^
\

-5 0.8
9.2374 x 10 G' ( d's + 4 )
kG - dS' 0 4 d'G 0 2
, ,
4
where kG is given in lb-mol/(ft 2 h atm). Since
30 Stoichiometry and Process Calculations
N
lb-mol lb-mol \ ' 0.4536 kmol \ ' ft 2 kmol
2
x x = 4.8825
h ft atm ft 2 h atm lb mol
/ / V
0.30482 m 2 2
m h atm ’
the right-hand-side of the above result is to be multiplied by 4.8825 so that the mass transfer
coefficient is expressed in kmol/(m 2- h - atm). Therefore, the desired equation is

, 4.5102 x 10^ G\d's + d'T )

~
, 0.4 , / 0.2
ds dG ds
where k'G is in kmol/(m2 h atm), G' is in kg/(m 2 h), and the clearances and thickness are in
metres.
Alternative
An alternative to the above technique is to first determine the units for the constant appearing
in the original equation, in the present case it is 6.7 x 10-4 and convert the units into the desired
system by multiplying with appropriate conversion factors. The constant gets a new numerical
value after this manipulation . For example, let the constant be 6.7 x 10- 4 ( lb - mol /
(lb / (ft)c(atm /(h)e. Now equate the exponents of the units on both sides and we get
0.8
lb-mol
(ft )c (atm (h )e
1 V lb
\

= (lb mol )* (lb / /

or
ft 2 h atm ft 0 6 J[ ft 2 h /

(lb-mol)1 (ft) 2 (h) 1 (atm) 1

= (lb-mol)a (lb/ + 08 (ft)c 22 (atm / (h)e 08

Thus we get, a = 1, h = - 0.8, c = 0.2, d =_ -1, e = -_0.2. _

And the constant is 6.7 x 10 4 (lb-mol) 1 (lb) 0- 8(ft)0 ;2(h) 0- 2(atm) 1.
-

6.7 x 10 - 4 (lb mol)(lb) -08(

ft)02(h) -

° 2(atm) 1-

( 0.4536 kmol "

= 6.7 x 10-4 lb mol x
V
lb mol /
0.8 0.2
0.4536 kg 0.3048 m 02 1
x lbx X ft X x (h) x (atm)
lb ft
= 4.51 x 10-4 (kmol)(kg) 08 (m )0 2 (h)
, 02 (atm) 1

We can use the given equation with the constant 6.7 x 10-4 replaced by 4.51 x 10-4 where
kG is given in kmol/(m2 h atm), G is in kg/(m2 h) and the distances are given in m.
EXAMPLE 2.9 The effective heat capacity of a mixture of gases is given by
CP = 7.13 + 0.577 x 10-3 t + 0.0248 x 10 “ 6
t2
where CP is in Btu/(lb-mol °F) and t is in °F.
( a) What are the units of the constants in the equation?
(b) Change the equation into the form in which CP is given in kJ/(kmol K) and temperature
is in K.
 Units and Dimensions 31

Solution (a) Since the unit of CP on the left-hand-side is Btu/(lb-mol °F), each term on
the right-hand side of the equation has the same units. These terms are:
First term = 7.13 Btu/(lb-mol °F)
Second term = 0.577 x 10-3 1 Btu/(lb-mol °F)
Third term = 0.0248 x 10 6 t 2 Btu/(lb-mol °F)
~

The constant 7.13 has the same unit as heat capacity, i.e. — — .
lb-mol °F
Btu
Now, the second term 0.577 x 10 3t can be written as
lb-mol °F

3
Btu X t ( ° F)
0.577 x 10 "

lb-mol (°F) 2
Btu
which means that the units of the constant 0.577 x 10-3 is •
lb-mol (°F) 2

Similarly, the third term 0.0248 x 10 6t2 ~ _ Btu

mo op can be written as
^ ^
Btu
0.0248 x 10 "
6 xr2 (°F) 2
/ OT7\

lb-mol (°F)3
6 Btu
Therefore, the units of the constant 0.0248 x 10 is •
lb-mol (°F)3
The units of the constant are respectively
Btu Btu Btu
and
lb-mol ° ’ '

F lb-mol (°F) 2
lb-mol (°F)3
(b) Suppose that the temperature of the gas is T K, then the equivalent Fahrenheit temperature
is
t = ( T - 273.15) x 1.8 + 32.0 = 1.8T - 459.67
Substituting this in the equation for CP, we get the heat capacity in Btu/(lb-mol °F)
when T is in K .
CP = 7.13 + 0.577 x 10 "
3 (1.8T - 459.67) + 0.0248 x 10 6 (1.8T - 459.67)2
~

= 6.87 + 9.976 x 10 ~ 4 r+ 0.0804 x 10 ~

r
6 2

The heat capacity given by the above equation is in Btu/(lb-mol °F). Since
1.055 056 x 103 J
Btu x
Btu Btu
1 = 1
lb-mol °F „ , x 0.453 5924 x 103 mol , x K
lb-mol °F OT

1 lb-mol 1.8°F
kJ
= 4.1868 — -— = 4.1868
mol K kmol K
32 Stoichiometry and Process Calculations

the above equation is to be multiplied by 4.1868 to obtain the heat capacity in kJ/kmol
K when the temperature is in K . The resulting equation is
CP = 28.763 + 4.763 x 10 "
3
r+ 0.3366 x 10 6T2
~

This equation evaluates heat capacity in kJ/kmol K when temperature T is in K .

2.4 DIMENSIONLESS EQUATIONS

Equations that are derived mathematically from basic principles are dimensionally homogeneous.
All terms in such equations have the same dimensions and the constants are dimensionless. For
example, the distance S covered in time t units by a body moving with an initial velocity u and
an acceleration a is given as
1
—
So = ut + at 2
2
In this equation all terms on both sides of the equation have the dimension of length and it is
immaterial whether we are using FPS, MKS or SI system of units. In using dimensionally
homogeneous equations, no conversion factors are required for using any system of units so
long as we are using consistent units for the primary dimensions of length, mass, time and
temperature. In contrast, an empirical equation is not necessarily dimensionless and therefore
must always be used with the same units in which it was developed.

2.5 DIMENSIONAL ANALYSIS

The dimensional analysis serves as a very useful tool in chemical engineering practice, especially
in heat flow, fluid flow and mass-transfer processes where even though the variables influencing
the system are known, an exact theoretical equation cannot be derived in terms of these
variables. The dimensional analysis stands intermediate between a fully empirical analysis and
a systematic mathematical development starting from basic principles. The dimensional analysis
is based on the principle of dimensional similitude by which it is possible to express all natural
interrelationships in terms of functions and coefficients that are universal in form and numerical
value, completely independent of the arbitrary system of units employed in making the
measurements themselves, provided the system is inherently consistent. It means that if a
theoretical equation exists among the variables affecting a physical process, that equation must
be dimensionally homogeneous. Therefore, it is possible to group the variables of such an
equation into a smaller number of dimensionless groups.
By dimensional analysis, the total number of variables affecting the system is reduced and
the equation can be equivalently written in terms of a lesser number of dimensionless groups.
Assume that a process is influenced by a large number of physical factors and we want to
study the effect of each factor on the rate of the process. Experimental investigations to study
the effect of each separate factor are to be carried out by systematically varying that factor
while keeping all others constant. It means that a laborious series of experiments is necessary
to obtain the exact nature of the functional relationship existing between the variables. It is
difficult to establish a relationship of this sort even by conducting such a large number of
 Units and Dimensions 33

experiments. Consider for instance, the experimental investigation of the variation of the heat
transfer coefficient with velocity of a fluid flowing through a pipe by conducting a series of
experiments with a pipe of diameter, say 25 mm . This is done by varying the velocity, say from
1 m /s to 30 m /s in steps, keeping all other factors constant. The results obtained can be utilized
to predict the heat transfer coefficient for a given velocity. However, these results as such,
cannot be used to predict the heat transfer coefficient in a pipe of a different diameter, say
50 mm for which another set of experiments will have to be done. It has been shown by the
dimensional analysis that the variables, diameter, velocity, density and viscosity must appear as
a dimensionless group, Dup/ p, known as the Reynolds number. If the experimental data are
reported in terms of this group, the evaluation of the heat transfer coefficient, which will
appear in another dimensionless group for a fluid flowing through any diameter pipe is
possible as long as the Reynolds number of the system falls within the range covered in the
experiment. In deriving a working equation from the experimental results, it is necessary to
derive it only in terms of the values of the dimensionless group, not in terms of each of the
variables separately.
To conduct dimensional analysis on a given problem, the first step is to identify the
variables affecting the system . These must be determined by the judgment of the investigator,
exercised in the light of such knowledge of the mechanism as is available. For example,
consider again the heat transfer from the walls of a pipe to the fluid flowing in turbulent flow
through the inside of the pipe . It is known that the heat transfer process is affected by the
following variables: the pipe diameter (D), the fluid velocity ( u ) , the viscosity of the fluid (p),
the density of the fluid (p), the heat capacity of the fluid (CP), the thermal conductivity of the
fluid 0k), and the heat transfer coefficient ( h ). The equation describing the heat transfer process
can be written as
/ (/?, A w, p, p, CP ,k ) = 0
There are different techniques for conducting dimensional analysis. The method due to the
Buckingham - /? theorem is based on the fact that the functional relationship between n factors
required to describe a system can be equivalently written in terms of n m dimensionless groups,
-

where m is the number of primary dimensions required to represent these variables. In the heat
transfer process described above there are seven variables and four primary dimensions are
necessary to represent them . Thus n = 7, m = 4. Thus we can write the relationship for heat
transfer as a function of three dimensionless groups, Kh n2 and /r3. Therefore
f\nx , n2 , %) = 0
The complete analysis, which is beyond the scope of this book, will show that these groups
are the Nusselt number (ihD/ k), the Prandtl number ( CPpJk ) and the Reynolds number ( Dup/ p ).
The results of a dimensional analysis are, however, useless unless experiments are done to
supplement the results. This is because the dimensional analysis does not give a numerical
equation, and experiments are required to complete the solution. A dimensional analysis cannot
be performed unless enough is known about the physics of the situation to decide what factors
are important in the problem and what physical laws would be involved in a mathematical
solution if such a solution were possible.
34 Stoichiometry and Process Calculations

2.5.1 Dimensionless Groups in Chemical Engineering Practice

Some important dimensionless groups in chemical engineering practice, their basic definitions
and the variables involved are given as follows.
1. Biot number: It is the ratio of conductive (internal) resistance to heat transfer to the
convective (external) resistance to heat transfer. It is used in the analysis of unsteady -
state conduction problems.

Bi = i
k
where is the volume is the surface area and k is the thermal conductivity of the
V , S
solid object and h is the heat transfer coefficient of the surrounding fluid.
2. Drag coefficient: It is the ratio of the average drag per unit projected area to the
product of the density of the fluid and velocity head.

CD = pFDiAP
( u 2 / 2)
where FD is the drag force exerted on the solid whose projected area in the direction
of flow is AP , p is the density of the fluid and u its velocity.
3. Euler number: It is the ratio of pressure force to inertial forces acting on a fluid
element.
P
Eu =
pu 2
where P is the pressure, p is the density of the fluid and u its velocity.
4 . Fanning friction factor: It is the ratio of shear stress to the product of density and
velocity head .

f —
p( u 212)
where rw is the shear stress at the pipe wall, p is the density of the fluid and u its
velocity.
5 . Fourier number: It is used in unsteady -state heat conduction.
at
K = -ST
Z7

where a is thermal diffusivity of the solid, t is time and 5 is half the thickness of a
slab or radius of a solid cylinder or sphere.
6. Froude number: It is the ratio of inertial force to gravity force.
u. 2
Fr = Lg
where u is the velocity, g is the acceleration due to gravity, and L is the characteristic
linear dimension for the flow system .
 Units and Dimensions 35

7. Graetz number: It is used for treating heat transfer to fluids in laminar flow.

kL
where m is the mass flow rate, Cp and k are respectively, the heat capacity and thermal
conductivity of the fluid, and L is the characteristics linear dimension for the flow
system .
8. Grashof number: Used to explain natural convection heat transfer.
_ I? p 2 g{i AT
2
P
where L is the characteristic linear dimension, p is the density, g is the acceleration due
to gravity, /J is the coefficient of volume expansion of the fluid, AT is the temperature
difference between the wall and bulk fluid, and p is the viscosity of the fluid.
9. Lewis number: The ratio of thermal diffusivity to mass diffusivity.
k
Le =
CpP
^ AB

where the ratio is the thermal diffusivity, sometimes abbreviated as a, is the

CPp
mass diffusivity of a mixture of components A and B, k is the thermal conductivity,
CP is the heat capacity and p is the density.
10. Mach number: It is the ratio of speed of the fluid to speed of sound in the fluid
under conditions of flow.

c
where u is the speed of the fluid and c is the speed of sound in the fluid .
11 . Nusselt number: It is the ratio of temperature gradient in the fluid in contact with
a solid wall to a reference temperature gradient applicable to the entire fluid and
represents a dimensionless heat transfer coefficient.

k
where h is the heat transfer coefficient, L is the characteristic linear dimension, and
k is the thermal conductivity.
12. Peclet number: It is the product of Reynolds number and Prandtl number.

pc _ LuCpp
k
L is the characteristic linear dimension for the flow system, Cp k and p are respectively,
9

the heat capacity, thermal conductivity and density of the fluid and u is the velocity.
36 Stoichiometry and Process Calculations

13 . Power number: It is the ratio of the drag force to inertial force and is proportional
to the drag coefficient.

where P is the pressure, n is the rotational speed of impeller of diameter D and p is

9

the density.
14. Prandtl number: It is the ratio of momentum diffusivity to thermal diffusivity.

Pr
k
where CP is the heat capacity of the fluid, p is the viscosity of the fluid, and k is the
thermal conductivity of the fluid .
15 . Reynolds number: It is the ratio of inertial force to viscous forces acting on a fluid
element.

Re = —P-
where L is the characteristic linear dimension for the flow system, u is the velocity,
p is the density and p is the viscosity of the fluid .
16. Schmidt number: It is the ratio of momentum diffusivity to mass diffusivity.

where
P ^ AB
is the mass diffusivity of a species A in a mixture of A and B.
17. Sherwood number: It is represents a dimensionless mass transfer coefficient and is
the ratio of concentration gradient in the fluid in contact with a solid wall to a reference
concentration gradient applicable to the entire fluid .

DAB
where kc is the mass transfer coefficient, L is the characteristic linear dimension for
the flow system, and is the mass diffusivity.
18. Stanton number: The Stanton number for heat transfer ( StH ) is the ratio of the
Nusselt number to the product of the Reynolds number and the Prandtl number while
the Stanton number for mass transfer ( StD ) is the ratio of the Sherwood number to
the product of the Reynolds number and the Schmidt number.
h
stH =
CPG
stD = C
U
where G is the mass velocity (pw), h is the heat transfer coefficient, CP is the heat
capacity, kc is the mass transfer coefficient and u is the velocity.
 Units and Dimensions 37

EXERCISES
Conversion of units
2.1 The viscosity of water is one centipoise . Express the viscosity of water in the following
units?
(a) Pa s
(b) lb/ (ft h)
2.2 Convert 1 bar into equivalent kgf/cm 2 and psi.
2.3 The thermal conductivity of an insulating brick is 0.15 Btu/(ft h °F). Express the
thermal conductivity in SI units.
2.4 The heat transfer coefficient of oil flowing through a pipe is 300 W/(m 2 K). Determine
the value of heat transfer coefficient expressed in
(a) kcal/ (h m 2 °C)
(b) Btu/ (h ft 2 °F)
2.5 Thermal conductivity of pure iron is 39 Btu/(ft h °F ) and that of steel containing 1% C
is 39 kcal/(m h °C) . Which one is a good conductor of heat, iron or steel?
2.6 The mass velocity of a gas through a duct is 1000 kg/m 2 h. Express the velocity into
lb/ft 2 s .
2.7 Mass flow rate is the product of volumetric flow rate and density. If the volumetric
flow rate of a liquid of specific gravity 0.78 is 100 ft3/min, find the flow rate in kg/s.
2.8 A man circling the earth in a spaceship weighed 300 N at a location where the local
gravitational acceleration was 4.5 m /s2. Calculate the mass of the man and his weight
on the earth where the gravitational acceleration is 9.81 m /s 2.
2.9 A man whose weight is 600 N takes 2 min for climbing up a staircase. What is the
power developed in him, if the staircase is made up of 20 stairs, each 0.18 m in height?
2.10 The potential energy of a body of mass 10.0 kg is 1.5 kJ. What is the height of the
body from the ground? If a body of mass 10 kg is moving at a velocity of 50 m /s,
what is its kinetic energy ?
2.11 Nitrogen gas is confined in a cylinder and the pressure of the gas is maintained by a
weight placed on the piston. The mass of the piston and the weight together is 50 kg.
The acceleration due to gravity is 9.81 m /s2 and the atmospheric pressure is 1.013 25
bar. Assume frictionless piston. Determine:
(a) The force exerted by the atmosphere, the piston and the weight on the gas if the
piston is 100 mm in diameter.
(b) The pressure of the gas.
( c ) If the gas is allowed to expand pushing up the piston and the weight by 400 mm,
what is the work done by the gas in kJ?
(d) What is the change in the potential energy of the piston and the weight after the
expansion in part (c)?
38 Stoichiometry and Process Calculations

2.12 The volume of a microbial culture is observed to increase according to the relation
V (cm 3) = e* where t is in seconds. Find the equivalent expression where V is in inch 3
and t is in hours.
Conversion of empirical equations
2.13 Stefan-Boltzmann law states that the emissive power is proportional to the fourth
power of absolute temperature . Stated mathematically,
Eb = oT 4
where Eb is the emissive power in Btu/(ft 2 h), o is the Stefan-Boltzmann constant, and
T is the temperature in °R. What is the value of o in W/(m 2 K 4), if its value in FPS
units is 0.171 x 10 8 Btu/(ft2 h °R 4)?
"

2.14 The following empirical equation was proposed to estimate the rate of heat loss from
the walls of a cylindrical pipe to the ambient air:
AT125
q = 0.5
D0 2 5
where q is the rate of heat loss in Btu/ft 2 h, AT is the temperature difference in °F
and D is the diameter in inches.
(a) Determine the units of the constant.
(b) Express the equation in SI units.
2.15 The van der Waals equation of state is given as
f a\
P+ (V - b ) = RT
\ V2/
where a and b are known as the van der Waals constants. For C02 the constants are
found to be a = 0.365 N m 4/mol 2 and b = 4.28 x 10-5 m 3/mol. If the pressure is given
in atm and the molar volume in L/mol, what are the values of the constants?
2.16 Rate of a gas phase reaction ( A B ) taking place at 298 K and 1 atm is given by

with kx= 17.3 and k 2 = 0.2, where CA is the concentration in kmol/m 3, t is the time
in minutes, and pA, pB are partial pressures in atm .
(a) Find the units of kx and k 2.
(b) If the rate is to be written in the form of

- £ EA - IC'C 2 2 - k' C 0 5

Note : Use the relation , C,

' = RT
what are the values of k\ and k 2
v
 Units and Dimensions 39

2.17 The pressure drop for a fluid flowing through a packed bed of solids is given by the
relation:
0.15
i/ p0 8 V 8 5
AP = 3.61
415
where AP is pressure drop in Pa, p is fluid viscosity in poise, H is the bed depth in
metres, p is fluid density in kg/m 3, v is fluid velocity in m /s and DP is packing diameter
in metres. Modify the relation such that the pressure drop is still in Pa, but other terms
are in FPS units.
2.18 The Antoine equation predicts the effect of temperature on vapour pressure by the
relation:
B
In Ps = A -
T -C
where A , B, and C are Antoine constants. For water, the values of the constants when
the vapour pressure is in kPa and temperature is in K are found to be A = 16.26205,
B = 3799.887 and C = 46.854. What are these values when
(a) Vapour pressure is in mm Hg and temperature in °C.
(b) Vapour pressure is in psia and temperature in °F.
2.19 The heat capacity of sulphuric acid in Btu/(lb-mol °R) is given by
CP = 23.06 + 2.071 x 10 "
2 r
where T is in °R. What is the equivalent expression if heat capacity is given in
(a) kJ / (kmol K ) and T is in K (b) kcal/(kmol °C) and temperature in °C.
2.20 The following equation relates the heat capacity of CO gas with temperature.
CP = 26.586 + 7.582 x 10 ~
3 r - 1.12 x 10^ T2
where CP is expressed in kJ/kmol K and T in K. Obtain equations which will express
(a) The heat capacity in cal/mol K, temperature in K.
(b) The heat capacity in cal/mol °C, temperature in °C.
(c) The heat capacity in J/kg K, temperature in K.
( d) The heat capacity in Btu/lb-mol °F, temperature in °F.
2.21 The heat capacity of carbon dioxide gas is given by
CP = 0.1978 + 1.059 x 10 - 2.395 x 10 ¥ "

where CP is in Btu/(lb°F) and t is in °F. Change the equation into the form in which
CP is given in kJ/(kmol K) and temperature is in K.
2.22 For fluids in turbulent motion through tubes, the heat transfer coefficient is given as
r \

h= a CPG 0.8
V D0.2 y

The numerical value of the constant a = 10.1, when h is measured in Btu/(ft 2 h °F),
CP is the specific heat of the fluid given in Btu /(lb °F), G is the mass velocity in
40 Stoichiometry and Process Calculations

lb/(ft 2 s) and the diameter is in ft. Determine the value of a (a) when h is measured
in W /(m 2 K), CP is the specific heat of the fluid given in kJ/(kg K), G is the mass
velocity in kg/(m 2 s) and (b) when h is measured in kcal/(m 2 h °C), CP is the specific
heat of the fluid given in kcal/(kg °C), G is the mass velocity in kg/(m 2 s) and the
diameter in m .
2.23 The diffusivity of a gas pair A-B is given by
r \l / 2
’3 / 2
1 1
1.8583 xl 0
"

37 +
M A MB J V
DAB ~
1
Pa Cl
in 2
where DAB is cm /s is the absolute temperature in K, MA and MB are molecular
, T
weights of species A and B , respectively, P is the pressure in atm , a is the
Lennard-Jones parameter in angstrom units and Q is a dimensionless parameter. If the
equation is written as
r \l / 2
3/ 2 1 1
CT +
V MA MB
DAB ~
Pa Cl 2

where is in m 2/s, T is in K, P is the pressure in Pa, a is the Lennard-Jones

parameter in nanometres, what is the value of C?
 Fundamental
3 Concepts of
Stoichiometry

The word “ stoichiometry ” has its origin in the Greek words stoicheion (elementary constituent)
and metrein (to measure). The conventional meaning of the word limits its application to
calculations involving the quantities of materials involved in chemical reactions. But in chemical
engineering the word stoichiometry is used in a broader sense; it is not just the application of
the law of combining proportions of chemical reactions. It includes calculations involving the
behaviour of gases and gas mixtures, the phase behaviour of liquids and solutions, the material
and energy balance of unit operations and unit processes, etc. The present chapter introduces
the reader to some basic concepts governing process calculations.

3.1 THE MOLE CONCEPT

A chemical element is made up of very minute, discrete and indivisible particles called atoms.
An atom is the smallest particle that can take part in a chemical change. It is extremely small
that the absolute mass of an atom cannot be determined easily. It is customary to indicate the
mass of an atom in relation to the mass of an arbitrarily chosen reference substance. The atomic
weight of an element is the mass of an atom based on a scale that assigns a mass of 12 for the
carbon isotope 12C. On this scale, the atomic weight of oxygen is 16 and that of hydrogen is
1.008. That is, the mass of an atom of oxygen is approximately 16 times the mass of an atom
of hydrogen. Atomic weight is a dimensionless number. The atomic weights of elements are
given in Table A. l (Appendix A).
A molecule of an element or a compound is made up of a number of atoms of the constituent
elements. The molecular weight is the sum of the atomic weights of the elements constituting
the molecule. Thus the molecular weight of a monatomic element is its atomic weight, while
that of a diatomic element such as hydrogen is twice its atomic weight. For hydrogen, the
molecular weight is 2 x 1.008 = 2.016. A molecule of water is made up of 2 atoms of hydrogen
and 1 atom of oxygen. The molecular weight of water is 2 x 1.008 + 16 = 18.016. Like atomic
weight, molecular weight is also a dimensionless number.
41
42 Stoichiometry and Process Calculations

A gram-atom of an element is the mass in grams that is numerically equal to the relative
atomic weight of the element. Thus the mass of one gram -atom of carbon is 12 g and the mass
of one gram -atom of oxygen is 16 g. A gram-molecule of a compound is the mass in grams of
the compound numerically equal to its molecular weight. Thus one gram -molecule of water is
18.016 g of water. Since an atom of oxygen is 16/12 times heavier than an atom of carbon, the
number of carbon atoms present in one gram -atom (12 g) of carbon and the number of oxygen
atoms present in one gram -atom (16 g) of oxygen are the same. This is true for all elements,
and in general, we can say that a gram -atom of any element contains the same number of atoms.
This number is equal to 6.023 x 1023, and is known as Avogadro s number. Similarly, a gram-
molecule of all compounds contains the same number of molecules and this number is 6.023 x 1023.
The number of gram -atoms of an element or the number of gram -molecules of a compound
can be determined from the mass of the element or the compound in grams.
the number of grams of the element
The number of gram -atoms of the element
atomic weight of the element
, , the number of grams of the compound
The number of gram -molecules of the compound = — —
molecular weight of the compound
—
The term gram -molecule is generally abbreviated into gram mole and is referred simply as
mole (symbol mol in SI units). In process calculations, for convenience, gram mole or mole
is used for referring gram -atom of an element as well as gram -molecule of a compound . Thus
one mole of aluminium represents 26.9815 g of aluminium and one mole of water means
18.016 g of water. A mole of 02 signifies 32 g of oxygen, while a mole of O would mean
16 g of oxygen. In short, we can designate a mole as the amount of the substance that contains
as many elementary entities as there are atoms in 12 g of carbon. The number of moles of a
substance can be determined by the following formula.
_ mass in grams
molecular weight
In engineering calculations a related quantity kilogram mole abbreviated as kilomole (symbol
kmot) is also commonly used .
, , mass in kilograms
kmol = 5 = 10
t
mol
molecular weight
In the FPS system, the quantity pound mole (abbreviated as Ib-mol ) is used to indicate the
quantity of substance that contains as many elementary entities (atoms or molecules) as there
are atoms in 12 pound of carbon. Thus the number of molecules contained by one pound mole
of any compound is the same for all substances. This number will not be equal to 6.023 x 1023
which is the number of molecules contained by a mole of the substance.
mass in lb
„
lb-mol =
,
—molecular rv- = 453.6 mol
weight

EXAMPLE 3.1 1000 pounds per minute of a gas (average molecular weight = 30.24) is being
sent to an absorption column. What is the molar flow rate of the gas in kmol/h?
 Fundamental Concepts of Stoichiometry 43

kg ^
Solution 1000 lb = 1000 (lb) x 0.4536
l J
lb
= 453.6 kg
27216
Mass flow rate = 453.6 kg/min = 453.6 x 60 = 27216 kg/h = = 900 kmol/h
30.24
EXAMPLE 3,2 How many molecules are present in 691 g K 2C03?
Solution The atomic weights of the elements are:
potassium = 39.1, carbon = 12.0, oxygen = 16.0
The molecular weight of K 2C03 is
39.1 x 2 + 12.0 + 16 x 3 = 138.2
691
691 g K 2C03 = — = 5 mol K 2C03
One mole of a substance contains 6.023 x 1023 molecules. Therefore, 5 mol K 2C03 contains
5 x 6.023 x 1023 = 30.115 x 1023 molecules.

EXAMPLE 3.3
(a) How many moles of sodium sulphate will contain 100 kg of sodium ?
(b) How many kilograms of sodium sulphate will contain 100 kg of sodium ?
Solution
(a) Since the atomic weight of sodium is 23,
100 xio3
100 kg sodium = = 4.348 x 103 g-atoms of sodium.
23
The molecular formula of sodium sulphate is Na2S04. One mole Na2S04 contains 2 g-atom
sodium . Therefore, the number of moles of Na 2S04 that contains 4.348 x 103 g-atom
sodium is
4.348 x 103
= 2.174 x 103 mol = 2.174 kmol
2
(b) 2.174 kmol sodium sulphate contains 100 kg sodium . The molecular weight of sodium
sulphate is
23 x 2 + 32.06 + 16 x 4 = 142.06
Therefore, 2.174 kmol sodium sulphate is
2.174 x 142.06 = 308.84 kg sodium sulphate.

3.2 CHEMICAL CALCULATIONS AND USE OF MOLAL QUANTITIES

The conventional application of stoichiometry is concerned with the mass relations involved in
chemical reactions between the reactants on the one hand and the products on the other. The
mole concept is found to be very much helpful in dealing with calculations involving chemical
reactions compared to those using ordinary mass units. Since a mole of a compound reacts
44 Stoichiometry and Process Calculations

with a simple multiple of moles of other reactants, it is easier to use molal quantities such as
mol, kmol or lb-mol in mass balance calculations of processes in which chemical reactions are
involved. This is particularly true when the desired change is brought about by several reactions
in series, each with varying degrees of completion. An alternative to the use of molal quantities in
stoichiometric calculations is the use of the combining weight ratios of the reactants and products.
But this method is cumbersome and is error prone as shown in Example 3.4.

EXAMPLE 3.4 Sulphur trioxide gas is obtained by the combustion of iron pyrites (FeS2)
according to the following reaction:
4FeS2 + 1502 -> 2Fe 203 + 8S03
How many kilograms of pyrites are burned to obtain 100 kg of sulphur trioxide ? How many
kilograms of oxygen are consumed in the production of 50 kg of S03?
Solution Molecular weight of FeS2 = 55.85 + 2 x 32.06 = 119.97
Molecular weight of Fe 203 = 2 x 55.85 + 3 x 16 = 159.7
Molecular weight of S03 = 32.06 + 3 x 16 = 80.06
Using molal quantities
100
100 kg of S03 = 1.2491 kmol.
80.06
Since 4 kmol FeS2 gives 8 kmol S03, pyrites needed to produce 100 kg of S03 (i.e., 1.2491
kmol) is

- X 1.2491 = 0.6246 kmol = 0.6246 x 119.97 = 74.93 kg

8
50
50 kg of S03 = —80.06
— = 0.6246 kmol
Since 15/8 kmol oxygen is required for the production of 1 kmol S03, oxygen consumed in the
production of 50 kg (0.6246 kmol) S03 is
15
— x 0.6246 = 1.1711 kmol = 1.1711 x 32 = 37.48 kg
8
Using the method of combining weight ratios
The relative weights of the reactants and products are calculated by multiplying the molecular
weight of the constituents by the respective stoichiometric coefficients. These are written along
with the chemical formula of the constituents taking part in the reaction:
4FeS2 + 1502 -> 2Fe203 + 8SOs
(4 x 119.97) (15 x 32) (2 x 159.7) (8 x 80.06)
479.88 480 319.4 640.48
479.88 kg of FeS2 gives 640.48 kg of S03. Therefore, the amount of pyrites needed to
produce 100 kg of S03 is
479.88
x 100 = 74.93 kg
640.48
 Fundamental Concepts of Stoichiometry 45

480 kg oxygen is needed to produce 640.88 kg S03. Therefore, oxygen consumed for the
production of 50 kg S03 is
480
x 50 = 37.47 kg
640.48

3.2.1 Molar Volume of Gaseous Substances

The volume occupied by one mole of a gaseous substance at a given set of temperature and
pressure is called the molar volume of the gas under those conditions. The molar volume of an
ideal gaseous substance is found to be a constant under standard conditions of temperature and
pressure (STP). The standard temperature is 273.15 K and standard pressure is 1 atm (101.325
kPa). The concept of ideal gases is discussed in detail later. It has been verified experimentally
that one mole of an ideal gas under standard conditions of temperature and pressure occupies
a volume of 22.4143 x 10-3 m 3. Accordingly, the molar volume at STP (also known as normal
molar volume ) is 22.4143 x 10-3 m 3/mol or 22.4143 m 3/kmol at STP. The molar volumes of real
gases at STP will be different from this value depending upon the extent to which the gases
depart from ideal behaviour. The constancy of normal molar volume is another concept which
is useful in the calculations involving gaseous substances.
EXAMPLE 3.5 Determine the volume of oxygen obtained under standard conditions, by the
decomposition of 100 kg of potassium chlorate.
Solution Consider the reaction
2KC103 -> 2KC1 + 302
The molecular weight of potassium chlorate is (39.10 + 35.46 + 3 x 16) = 122.56.
100 kg of potassium chlorate is equivalent to 0.816 kmol. When 2 mol of potassium chlorate
is decomposed, 3 mol oxygen is produced. So 0.816 kmol potassium chlorate will liberate
1.224 kmol oxygen. Since one kmol oxygen under STP occupies a volume of 22.4143 m 3, the
volume of oxygen produced at STP is 1.224 x 22.4143 = 27.43 m 3.

EXAMPLE 3.6 Iron reacts with steam according to the following reaction:
3Fe + 4H20 -> Fe304 + 4H 2
(a) How many kilograms of iron and steam are required to produce 100 kg of hydrogen?
(b) What volume will the hydrogen occupy at standard conditions?
Solution
100
(a) 100 kg of hydrogen = = 49.60 kmol
2.016
Since three moles of iron reacts giving 4 moles of hydrogen, the moles of iron required
to produce 49.6 kmol (i.e . 100 kg) hydrogen is

- x 49.6 = 37.2 kmol

4
37.2 kmol iron is equivalent to 37.2 x 55.85 = 2077.62 kg.
46 Stoichiometry and Process Calculations

As one mole steam reacts giving one mole hydrogen, the total steam required is 49.6
kmol = 893.6 kg.
(b) Since the normal molar volume of an ideal gas is 22.4143 m 3/kmol, the volume occupied
by 100 kg (49.6 kmol) hydrogen at STP is
49.6 x 22.4143 = 1111.7 m 3.

3.2.2 Equivalent Weight

The equivalent weight of an element is the number of parts by weight of the element which
can combine with or displace 1.008 parts by weight of hydrogen or the equivalent weight of
any other element. Equivalent weight is a dimensionless number like atomic weight and molecu-
lar weight. When equivalent weight is expressed in grams, it is known as the gram equivalent
weight. The equivalent weight of an element may be defined as the ratio of the atomic weight
of the element to its valency. For example, consider the reaction

H 2 + -O 2 -> H 2O

2.016 parts by weight of hydrogen combines with 16 parts by weight of oxygen to form 18.016
parts by weight of water. Therefore 1.008 parts by weight of hydrogen combines with 8 parts
by weight of oxygen. Hence the equivalent weight of oxygen is 8.
An element with more than one valency will have more than one equivalent weight. The
element iron (atomic weight 55.85) has a valency 2 in ferrous compounds and 3 in ferric
compounds. Thus iron has equivalent weights 27.925 and 18.617 respectively, in ferrous and
ferric compounds.
The equivalent weight of an acid is the number of parts by weight of the acid which
contains 1.008 parts by weight of replaceable hydrogen. The number of replaceable hydrogen
atoms in a molecule of acid is known as the basicity of the acid . Thus the equivalent weight
of an acid is the ratio of the molecular weight of the acid to its basicity. Since 36.46 parts by
weight of HC1 contains 1.008 parts by weight H +, the equivalent weight of HC1 is 36.46.
Similarly the equivalent weight of H 2S04 is half its molecular weight, that is 49.038, since one
molecular weight of H 2S04 contains 2 atomic weights of replaceable hydrogen.
The equivalent weight of a base is the ratio of its molecular weight to its acidity. The acidity
of the base is the number of -OH groups in one molecule of the base . Thus the equivalent
weight of a base is the number of parts by weight of the base that is required to react completely
with one equivalent weight of an acid . One molecule of NaOH contains one -OH group.
Therefore, the equivalent weight of NaOH is 40 which is the same as its molecular weight.
The equivalent weight of a salt is the number of parts by weight of the salt that is required
to react with one equivalent weight of an acid or base or any other substance. For example, in
the reaction
Na2C03 + 2HC1 2NaCl + C02 + H20
106 parts by weight of Na 2C03 reacts with 2 x 36.46 parts by weight of HC1 or two
equivalents of HC1. Therefore, the equivalent weight of Na 2C03 is (molecular weight of
Na2C03)/2 = 53.
 Fundamental Concepts of Stoichiometry 47

The equivalent weight of an oxidiser is the number of parts by weight of the substance
which would give 8 parts by weight of oxygen for oxidation purposes, or it is the ratio of the
molecular weight to the number of electrons gained per molecule of the oxidiser. The equivalent
weight of a reducer is the number of parts by weight of the reducer which requires 8 parts by
weight of oxygen for complete oxidation. Or it is the ratio of the molecular weight to the total
number of electrons lost per molecule of the reducer. Potassium permanganate is a good oxidiser
in acid medium
2KMn04 + 3H 2S04 -> K 2S04 + 2MnS04 + 3H 20 + 50
The molecular weight of KMn04 = 158.04. Thus, 316.08 parts by weight of KMn04
liberates 80 parts by weight of oxygen. The equivalent weight of KMn04 is

316.08 x —808 = 31.61

Now consider the oxidation of ferrous sulphate:
2FeS04 + H 2S04 + O -> Fe 2(S04)3 + H 20
2 x 151.91 parts by weight of FeS04 requires 16 parts by weight oxygen for complete oxidation.
Therefore, the equivalent weight which is the number of parts by weight of the sulphate
combining with 8 parts by weight of oxygen is 151.91.

EXAMPLE 3,7 Find the equivalent weight of CaC03

Solution
CaC03 + 2HC1 -> CaCl 2 + H 20 + C02
One mole of CaC03 reacts with 2 equivalents of hydrochloric acid . The weight of CaC03
reacting with one gram -equivalent of acid is
Molecular weight of CaC03
i = 100.08 = 50.04 g
2
—
Therefore, the equivalent weight of CaC03 is 50.04.

3.3 DENSITY AND SPECIFIC GRAVITY

The mass per unit volume of a substance is designated as the density of the substance. Since
the volume of a given mass of a substance varies with temperature, density is a function of the
temperature. The density of water at 277.2 K is 1000 kg/m 3 and that at 313.2 K is 992.25 kg/m 3.
The density of mercury at 313.2 K is 13 496.9 kg/m 3. The densities of liquids and solids are
considered to be independent of pressure for most calculations. However, the density of a gas
depends strongly on temperature as well as on pressure . The term specific gravity refers to the
relative density. It is a dimensionless ratio. For liquids and solids, it is defined as
t2 density of the substance at temperature t 2
Specific gravity sp gr (3.1)
t1 density of water at temperature tx
48 Stoichiometry and Process Calculations

288.8 K
v
^ SP 288lK
is the ratio of the density of the substance at 288.8 K (60°F) to the
density of water at the same temperature . Since the density of water at 277.2 K is 1 g/cm 3
in CGS units, the specific gravity of a substance with reference to water at 277.2 K is
numerically equal to its density expressed in CGS units. But, densities in SI units and in FPS
units are not numerically equal to the specific gravities. This is because, the density of water
in these units at 277.2 K is 1000 kg/m 3 and 62.43 lb/ft3, respectively. For gases, the reference
substance used for defining specific gravity is usually dry air at the same conditions as the gas.

Bulk density: For porous solid, the bulk volume of the solid includes the volumes of the
pores. Thus by dividing the mass of the solid in air by the volume of the solid what we get is
the bulk density or the apparent density of the solid . The true density of the solid depends on
the porosity of the solid. The porosity or the void fraction is defined as the fraction of the total
volume that is void . Let e be the porosity and pT and pB be the true density and bulk density
of the solid, respectively. Then

£ = 1 - PB (3.2)
pT

3.4 SPECIFIC GRAVITY SCALES

For liquid solutions, the specific gravity may vary appreciably with the concentration of the
solute. Therefore, many chemical process industries use specific gravity as a measure of the
concentration of their products. Industries dealing with sulphuric acid, hydrochloric acid, caustic
soda, etc. report the concentration in terms of specific gravity. These industries had been using
certain special specific gravity scales for this purpose . Some of the important specific gravity
scales in use are discussed as follows. Many of these scales are now being abandoned in favour
of the SI units of density.

API scale: Many important physical properties of petroleum products, like the boiling point,
molecular weight, viscosity, etc. depend strongly on their composition which in turn can be
conveniently related to their specific gravities. The petroleum industries had been using the API
(American Petroleum Institute) scale for this purpose. On this scale, one degree API is defined
as
141.5
°API = - 131.5 (3.3)
288.8 K
sp gr
288.8 K
For example, if the specific gravity of a liquid at 288.8 K with reference to water at the same
/ \
288.8 K
temperature is 0.934 sp gr = 0.934 it corresponds to 20 °API on this scale.
v 288.8 K

Baume scale: The mathematical definition of °Be (degree Baume) for liquids lighter than
water differs from that of liquids heavier than water. For liquids lighter than water,
 Fundamental Concepts of Stoichiometry 49

140
° Be = - 130 (3.4)
288.8 K
sp gr
288.8 K
/ \
288.8 K
A liquid of specific gravity 0.933 sp gr = 0.933 is 20 °Be on this scale . For liquids
v 288.8 K /

heavier than water, the definition of Baume degree is

145
°Be = 145 - (3.5)
288.8 K
sp gr
288.8 K
20 °Be on this scale refers to a liquid of specific gravity 1.16. This scale is used to represent
concentration of solutions heavier than water, like sulphuric acid, hydrochloric acid and caustic
soda. 20 °Be sulphuric acid represents a concentration of 22.25 % (weight) of H 2S04 in water.
/ \
288.8 K
50 °Be sulphuric acid sp gr = 1.5263 represents a concentration of 62.18 % (weight)
v 288.8 K /

H 2S04.
Twaddell scale: This scale is used for liquids heavier than water. One degree Twaddell ( °Tw)
is defined as
/ \
288.8 K ,
°Tw = 200 spgr 1.00 (3.6)
\
288.8 K /

A specific gravity of 1.1 according to this scale would correspond to 20 °Tw. A 40% (weight)
aqueous caustic soda solution has a specific gravity of 1.445 which is equivalent to 89 °Tw .

Brix scale: Degree Brix (°Brix) is used to indicate the strength of sugar solution. This scale
is defined in such a way that the density of 1.0 % (weight) aqueous sugar solution is equivalent
to one degree Brix.

“ Bris msK
" 400 <37>
SP 83
288.8 K

EXAMPLE 3, 8 A body weighs 1.0 kg in air, 0.90 kg in water and 0.82 kg in a liquid. What
is the specific gravity of the liquid?
Solution The loss in weight of a body in a liquid is equal to the weight of liquid displaced
by the body. Since the weight of liquid displaced is equal to the product of the volume of liquid
displaced and density of the liquid, the volume of liquid displaced is
loss in weight
density of the liquid
Loss in weight in water = 1.0 - 0.9 = 0.1 kg
Loss in weight in the given liquid = 1.0 - 0.82 = 0.18 kg
50 Stoichiometry and Process Calculations

Since the volume displaced by the solid is the same in water as well as in the liquid, we have
0.1 0.18
Pw Pi
where pw and p/ are, respectively, the density of water and the liquid.
The specific gravity of the liquid is the ratio of its density to the density of water. Here this
ratio is
pj_ _ 0 J 8 _ i s
Pw 0.1
EXAMPLE 3, 9 10 kg of liquid A of specific gravity 1.17 is mixed with 5 kg of liquid B of
specific gravity 0.83. Assuming that there is no volume change on mixing, what is the specific
gravity of the mixture? (Take density of water = 1000 kg/m 3.)
Solution Density of liquid A = 1.17 x 1000 = 1170 kg/m 3; density of liquid B = 0.83 x
1000 = 830 kg/m 3
Volume of 10 kg liquid A is

Volume of 5 kg liquid B is
-
^
1170
- = 8.547 xlO 3 m 3
"

— = 6.024 x 10 3 m 3
830
Assuming that there is no volume change on mixing, the volume of mixture is 14.571 x 10 3 m3.
"

mass of the mixture (10 + 5)

Density of the mixture = : 3 1029 kg/m 3
volume 14.571 x l O

EXAMPLE 3, 10 What is the specific gravity on the Baume scale for a 100°Tw solution?
Solution 200 (sp gr - 1.0) = 100

or sp gr = — + 1.0 = 1.50

On the Baume scale, this corresponds to

.. —1 4 -5 = 48.3 Be
145 -
1.50

EXAMPLE 3, 11 250 cubic meters of 30 °API gas oil is blended with 1000 cubic meters of
15 ° API fuel oil. What is the density of the resultant mixture in kg/m 3? The density of water
at 288.5 K = 999 kg/m 3. Assume no volume change on mixing.
Solution The API gravity scale is defined by
141.5
° API - 131.5
288.8 K
spgr
288.8 K
 Fundamental Concepts of Stoichiometry 51

For 30 ° API gas oil, the specific gravity is

141.5
131.5 + 30
= 0.8762
The density of gas oil is
0.8762 x 999 = 875.3 kg/m 3
Therefore, the mass of gas oil blended is
250 x 875.3 = 2.1883 x 105 kg
Similarly, the specific gravity of fuel oil is
141.5
131.5 + 15
= 0.9659
The density of fuel oil is
0.9659 x 999 = 964.9 kg
Therefore, the mass of fuel oil blended is
1000 x 964.9 = 9.649 x 105 kg
The density of the mixture after blending is
(2 1883 x 10s + 9 649 x 10s )
, ,

= 947 kg/m 3
(250 + 1000)

3.5 COMPOSITION OF SOLIDS, LIQUIDS AND GASES

3.5.1 Mass Fraction ( Weight Fraction )
Compositions of solid and liquid mixtures are usually expressed as mass fraction or weight
fraction. The mass fraction of a component in a mixture is the ratio of the mass of the component
to the total mass of the mixture. Consider a binary mixture made up of components A and B .
Let the mass of A and the mass of B in the mixture be mA and mB, respectively.
Then,
mA
wA , mass fraction of A = (3.8)
mA + mB
In a solution containing several components (multi-component solutions),
w4, mass fraction of A = —m (3.9)
E mi
i =1

where rrij is the mass of component / in the solution.

3.5. 2 Mass Percent (Weight Percent )

The weight (mass) percent of a component in a mixture is the number of parts by weight
(mass) of the constituent in 100 parts by weight (mass) of the mixture .
52 Stoichiometry and Process Calculations

YYl
weight percent of A = xlOO (3.10)
mA + mB
Thus, the weight per cent is the weight fraction multiplied by 100.

3.5.3 Mass Ratio

Another term used for expressing the concentration in binary mixtures is the mass ratio or
weight ratio. In a mixture made up of constituents A and B , the mass ratio of A is the mass of
A per unit mass of B. Thus,
mA
mass ratio of A = —mB (3.11)

We see that the mass ratio of A in a binary mixture of A and B is the mass fraction of A
on A -free basis. Concentration expressed as mass ratio is particularly convenient in calculations
involved in such operations where only certain of the constituents undergo a change in mass
while the quantities of the others remain unchanged. For example, in drying operation, a wet
solid is admitted to the dryer where the moisture content of the solid gets reduced where as the
dry weight, i.e . the weight of the moisture -free solid remains unchanged . When ammonia is
removed from an ammonia-air mixture by absorbing in water in an absorber, the quantities of
ammonia-free air entering and leaving the absorber are the same. In these operations it is more
convenient to carry out the mass balance calculations using mass ratios than the mass fractions.
For example, let the mass ratio of moisture in a wet solid entering the drier is 0.25 and that in
the solid leaving the drier is 0.05, and we are asked to determine the fraction of the original
water that is removed in the drying operation. Since 0.25 kg is the moisture associated with 1 kg
dry solid entering the drier and the solid leaving the drier contains only 0.05 kg moisture per
kg dry solid, the water removed in the drying operation is - 25 - 0.05
Q
0.25 ^ ^ ^ water

present in the feed. When we say that a wet material is being dried from an initial moisture
content of 0.2 mass fraction to a final value of 0.0476, though we refer to the same problem,
the calculation will not be as easy as we have illustrated with the mass ratio values.

3.5.4 Dry Basis and Wet Basis

— —
In the conventional method of expressing the concentration the wet basis the percentage of
water in the solid is the mass of moisture contained in 100 parts by weight of the wet material.
The water content of a wet material can be expressed on a moisture-free basis or dry basis also.
Percent moisture on a dry basis is the mass ratio of moisture to moisture-free solid expressed
as percentage. Thus, when the moisture content of the solid is 25% on a dry basis, there are
25 parts by weight of water associated with 100 parts by weight of dry solid. Or, 125 parts by
weight of the wet solid contains 25 parts by weight of water. Therefore, the percent water on
wet basis is 20.

EXAMPLE 3.12 250 kg wet ammonium sulphate containing 50 kg moisture is sent to a dryer
in order to remove 90% of the moisture in the feed. Calculate for the entrance and exit to the
dryer, the following:
 Fundamental Concepts of Stoichiometry 53

(a) The weight fraction of water

(b) The weight ratio of water
(c) The weight percentage of moisture on a wet basis
(d) The weight percentage of moisture on a dry basis.
Solution Basis: 250 kg wet charge.
Entrance to the dryer
Dry ammonium sulphate = 250 - 50 = 200 kg
Water in the charge = 50 kg
(a) The weight fraction of water is
mass of water _ 50 _
total mass 250
(b) The weight ratio of water is
mass of water _ 50 _
mass of dry solid 200 ^
The weight percent of moisture on wet basis is
maSSOfwaler
X 100 = x 100 = 20.00%
total mass 250
(c) The weight percent of moisture on dry basis is
mass of water
mass of dry solid
X 100 = —
200
X 100 = 25.00%

Exit of the dryer

Mass of dry ammonium sulphate = 200 kg.
Since 90% of water in the charge is removed, the mass of water present in the solid = 0.01
x 50 = 5 kg.
(a) The weight fraction of water is
mass of water
total mass
—205 = 0.0244
(b) The weight ratio of water is
mass of water
mass of dry solid 200
—
= 0.025
(c) The weight percent of moisture on a wet basis is
mass of water 5
total mass
x 100 =
205
—x 100 = 2.44%

(d) The weight percent of moisture on a dry basis is

x 100 = -A. x 100 = 2.50%

maSSOfWal<!r
mass of dry solid 200
54 Stoichiometry and Process Calculations

EXAMPLE 3.13 A wet stock of ammonium sulphate containing 25% water on dry basis is
sent to a drier. The material leaving the dryer contains 2.5% moisture on dry basis. Determine
the percentage of water removed in the drying operation.
Solution Basis: 100 kg of dry solids in the feed to the dryer
Water in the feed is 25 kg and that in the dried product is 2.5 kg. Therefore, the amount
of water removed = 25 - 2.5 = 22.5 kg.
The percentage of water removed in the dryer is

—22255 x 100 = 90%

EXAMPLE 3.14 A wet stock of ammonium sulphate containing 20% water1 is sent to a drier.
The material leaving the dryer contains 2.44% moisture . Determine how many kg of water is
removed per kg of wet material charged. Also find the percent of original water in the feed that
is removed by drying.
Solution Basis: 1 kg of wet ammonium sulphate
Weight of dry solid = 0.80 kg, weight of water = 0.20 kg
The material leaving the drier contains 0.80 kg dry solid which constitutes 100 - 2.44 =
97.56% of the total material leaving the dryer. Let x be the weight of total material. Then
x x 0.9756 = 0.8 => x = 0.82 kg
1 kg of material enters the dryer and 0.82 kg leaves. The amount of water removed is
1.00 - 0.82 = 0.18 kg.
The percent of water in the feed that is removed by drying is
0 18
100 = 90%
0.20

3.5.5 Mole Fraction and Mole Percent

If a mixture is made up of distinct chemical entities, the composition can conveniently be
expressed on a mole basis. The number of moles of a constituent is determined by dividing the
mass by its molecular weight. The mole fraction is the ratio of the moles of the constituent to
the total moles in the mixture . Consider a solution containing nA moles of A and nB moles of
B. Then
nA
xA, mole fraction of A = (3.12)
nA + nB
Let MA and MB be the molecular weights of A and B, respectively.

xAA , mole fraction of A = — mJMA

mA /MA + MB /MB
(V3.13)
'

1 Unless otherwise specified , the percentage composition of solids and liquids may be treated as percentages
on a wet basis.
 Fundamental Concepts of Stoichiometry 55

where mA and mB are the masses of the components A and B, respectively. Suppose that the
solution is made up of n constituents and nt is the number of moles of component / in the
solution. Then
nA
xA , mole fraction of A = (3.14)

The mole ratio of component A in a binary mixture of A and B is the ratio of moles of
A to moles of B in the mixture. The mole percent is the number of moles of a component
present in 100 moles of the total mixture. It is equal to the mole fraction multiplied by 100.
Composition of a gas mixture is generally expressed as mole percent or mole fraction.

3.5.6 Volume Fraction and Volume Percent

The volume fraction of a component in a solution is the ratio of its pure-component volume
to the total volume of solution both at the same temperature and pressure. By pure-component
volume, we mean the volume occupied by the component in its pure state. Thus if VA is the
pure-component volume of A and V is the volume of the solution, then

volume fraction = —VA

The volume fraction multiplied by 100 gives the volume percent of the component in
solution. The volume percent is usually used to represent the composition of gases. In rare
cases, the concentrations of liquids also are expressed on a volumetric basis, a typical example
being the alcohol-water solution, the alcohol content being represented on a volumetric basis.
It will be shown in later chapters that the volume occupied by an ideal gas at a given
temperature T and pressure P in the pure state is the same as the volume occupied by the gas
in mixtures with other ideal gases, provided the temperature and pressure are the same. This
property of ideal gases can be attributed to the absence of intermolecular forces in such gases.
Thus the total volume of the gas mixture F, is the sum of the pure-component volumes and
the volumetric percentages of the constituent gases which add up exactly to 100. This is
roughly true for real gases also, because at low pressures such as the atmospheric pressure
at which the gas analysis is usually made, all real gases behave almost like ideal gases. Thus
the volume percent and volume fraction are valid means for expressing the concentration of
the gas mixtures. Composition expressed on a volumetric basis does not change with change
in temperature, because both the pure -component volume and the total volume of the gas
mixture vary with temperature to the same extent. Furthermore, as will be shown later in
Chapter 4, the volume percent and mole percent are identical for gas mixtures. Unless otherwise
indicated, the percentage composition of a gas mixture means the composition by volume,
which also means the composition by mole as well.
A change in volume usually accompanies the formation of liquid solutions from its constituent
pure liquids. The volume that a unit mass of a liquid in a solution contributes to the total
solution volume is not the same as the volume occupied by the liquid in its pure state at the
same temperature and pressure as the solution. The volume percentage by our definition is the
ratio of the volume of the pure liquid to the volume of the solution expressed as a percentage.
56 Stoichiometry and Process Calculations

The volume percentage as defined earlier will not add up to exactly 100 in the case of liquids
because of the volume change accompanying the mixing. Therefore, the compositions of the
liquid solutions are generally expressed on a mass basis rather than on a volume basis.
Furthermore, the effect of temperature on the volumes of pure components vary from liquids
to liquids. Therefore, the volumes of the pure components and the solution vary differently with
changes in temperature . The volumetric composition of liquids is therefore a function of
temperature. Hence, it is imperative that when we represent, say, for example, the ethyl alcohol
content in an aqueous solution on a volumetric basis, the temperature be specified.

EXAMPLE 3.15 The solubility of sodium chloride in water at 290 K is 35.8 kg/100 kg of
water. Express the solubility as the following:
(a) Mass fraction and mass percent of NaCl
(b) Mole fraction and mole percent of NaCl
(c) kmol NaCl per 1000 kg of water
Solution Basis: 100 kg of water and the salt dissolved in it in a saturated solution at 290 K.
(a) Mass of NaCl = 35.8 kg
Mass of solution = mass of water + mass of NaCl = 100 + 35.8 = 135.8 kg
35.8
Mass fraction of NaCl = = 0.2636
135.8
Mass percent of NaCl = mass fraction x 100
= 0.2636 x 100 = 26.36%
mass of NaCl in kg 35.8
(b) kmol of NaCl = = 0.6125 kmol
molecular weight 58.45
mass of water in kilograms
kmol water =
molecular weight
100
= 5.5494 kmol
18.016
moles of NaCl
Mole fraction =
moles of solution
0.6125
(5.5506 + 0.6125)
= 0.0994

Mole percent = mole fraction x 100 = 9.94%

( c ) 100 kg of water dissolves 0.6125 kmol NaCl. Therefore, kmol NaCl per 1000 kg of
water is 6.125 kmol.

EXAMPLE 3.16 The absolute humidity of air is 0.015 kg water vapour/kg dry air. Assuming
the average molecular weight of air to be 29, calculate the following:
 Fundamental Concepts of Stoichiometry 57

(a) The mole percent of water vapour in the air

(b) The molal absolute humidity, which is same as the mole ratio of water vapour to dry
air
Solution When the humidity is 0.015 kg water vapour/kg dry air, air contains
0.015
18.016
= 8.326 xl (T4 kmol water vapour in association with — = 0.0345 kmol dry air
(a) Mole per cent of water vapour is
8.326 xl (T4
x 100 = 2.36%
(8.326 x 10^ + .0345)
(b) Molal absolute humidity is
8.326 x 10 4
= 0.0241 kmol water/kmol dryJ air
(0.0345)

3.6 OTHER EXPRESSIONS FOR CONCENTRATIONS

— —
A solution is a homogeneous medium gas, liquid or solid made up of two or more compo-
nents. In process calculations, the term solution is generally used to refer to liquids and gases
made up of solutes and a solvent. The component present in larger proportions in the solution
is the solvent and that present in smaller proportions is called the solute . In addition to the
different methods of expressing compositions as discussed above, the concentration of solute
in a solution can be expressed as parts per million, molarity, molality and normality.
Parts per million (ppm): It is used to represent extremely small amounts of solutes present
in solutions. It is the ratio of the number of parts by weight of the solute to 106 parts by weight
of solution. For very dilute aqueous solutions, the density of the solution being the same as
density of pure water,
1g lg 1 mg
1 ppm = = mg/L
106 g solution »6
10° mL solution v3
^
10 mL solution
ppm is the measure used to represent concentration of impurities present in trace quantities,
such as hardness of water, BOD (biochemical oxygen demand) of effluents, etc .

Molarity: It is defined as the number of moles of the solute per litre (10 3 m 3) of solution.
Molality: It is the number of moles of the solute present per 1 kg of solvent.

Normality: It is the ratio of the number of gram equivalents of the solute per litre of solution.
The product of normality and equivalent weight is equal to the weight in grams per litre of
solution.
EXAMPLE 3.17 An aqueous solution of K 2C03 contains 50% salt and the specific gravity of
the solution is 1.53. Determine the following:
58 Stoichiometry and Process Calculations

(a) The mole percent of the salt in the solution

(b) The volume percent of water assuming density of water is 1000 kg/m 3 and there is no
volume change on mixing
(c) The molality of the solution
(d) The molarity of the solution
(e) The normality of the solution
Solution Basis: 100 g of solution
Molecular weight of K 2C03 = 138.20
50
(a) Mass of K 2C03 = 50 g
138.20
= 0.3618 mol
50
Mass of water = 50 g
18.016
= 2.7753 mol
0.3618
Mole percent of salt x 100 = 11.53%
0.3618 + 2.7753
mass
(b) Volume of the solution
density
100
= 65.36 mL
L 53
mass
Volume of water in the solution =
density
50
3 = 50 mL
1000 xl 0
“

volume of water , _ _
Volume percent of water = x 100
solution volume

( c ) 50
^
= - - x 100 = 76.50% .
65.36
x 10-3 kg water contains 0.3618 mol K 2C03.
mol solute
Molality =
kg solvent
_ 0.3618
50 x 10-3 = 7.236 mol/
kg
(d) 65.36 mL solution contains 0.3618 mol K 2C03.
mol solute
Molarity = 7 : :——
litre solution
0.3618
T
3 = 5.536 mol/L
65.36 x 10
 Fundamental Concepts of Stoichiometry 59

(e) Equivalent weight of K 2C03 = molecular weight/2 = 138.20/2 = 69.10

mass in grams
Number of gram equivalents of K 2C03 = :— : rv-
equivalent weight
50
= 0.7236 gram equivalents
69.10
gram equivalents
Normality =
litre solution
_ 0.7236
65.36 x 10 3
= 11.07 gram equivalents/L or 11.07 N
EXAMPLE 3J 8 Pure water and alcohol are mixed to get a 60% (weight) alcohol solution.
The densities (kg/m 3) of water, alcohol and the solution may be taken to be 998, 798 and 895
respectively at 293 K. Calculate the following:
(a) The volume percent of ethanol in the solution at 293 K
(b) The molarity
(c) The molality
Solution Basis: 100 kg of 60% (weight) alcohol-water solution
(a) Volume of 100 kg of solution is

-5!2!L = = 0.1117 m 3
density 895
The volume of pure alcohol mixed to get the above solution is
60
60 kg =
798
= 0.0752 m3
Volume percent of ethanol in the solution is
0 0752
x 100 = 67.3%
0.1117
( Note : The volume of the solution resulting on mixing two pure liquids need not be
equal to the sum of the volumes of the liquids. Therefore, the volume percent of the
individual constituents will not add to give 100.)

moles of ethanol
(b) Molarity of the solution = —volume
: — :— : :—
or solution litres
in

60
Moles of ethanol in 100 kg& solution = . , = 1.303 kmol = 1303 mol
46.048
Volume of solution is 0.1117 m 3 = 111.7 L. Therefore,
1303
molarity = 11.67 mol/L
111.7
60 Stoichiometry and Process Calculations

(c ) Molality of the solution = —moles of alcohol

kilograms of water
Mass of water in 100 kg solution is 40 kg. Hence,
1303
molality = = 32.575 mol/(kg of water)
^
3.7 CHEMICAL REACTIONS AND PROCESS CALCULATIONS
The conversion of raw materials into useful products in most cases is brought about by means
of chemical reactions. For solving material balance and energy balance problems involving
chemical reactions, it is essential that a balanced chemical equation be written for the reaction
under consideration. The chemical equation provides us with a variety of qualitative and
quantitative information essential for solving material balance problems. For example, consider
the determination of the quantity of iron pyrites (FeS2) that is to be fed to the burner to produce
say, 100 kg of sulphur dioxide by oxidation with air. The relevant chemical reaction is represented
by the equation
4FeS2 + 1102 -> 2Fe 203 + 8S02
The coefficients of the chemical formulae of the different chemical species in the equation are
called the stoichiometric coefficients. The ratio of the stoichiometric coefficients of any two
substances involved in the reaction is the stoichiometric ratio of the substances. The stoichio-
metric ratio helps us to calculate the number of moles of one substance involved in a chemical
reaction with a given number of moles of another substance . According to the equation, 4 mol
of FeS2 combines with 11 mol of oxygen to produce 2 mol of Fe 203 and 8 mol of S02.The
molecular weights of the reactants and products of the reaction can be calculated from the
atomic weights of the constituent elements. Thus
Molecular weight of FeS2 = 55.847 + 2 x 32.065 = 119.977
Molecular weight of Fe 203 = 2 x 55.847 + 3 x 16.00 = 159.694
Molecular weight of S02 = 32.064 + 2 x 16.00 = 64.065
Accordingly, 479.9 kg (= 4 x 119.977) FeS2 combines with 352 kg (= 11 x 32) oxygen
producing 319.388 kg (= 2 x 159.694) Fe 203 and 512.512 kg (= 8 x 64.065) S02. When the
ratio of the pyrites charged to the oxygen supplied is 4:11 on a mole basis or 479.9: 352 on
a weight basis, we say that the reactants are supplied in stoichiometric proportions.

3.7.1 Excess and Limiting Reactant

In industrial processes one would rarely come across the use of exact stoichiometric quantities
for chemical conversion. Frequently, one of the reactants is supplied in excess to ensure completion
of the reaction. Excess reactants may be necessary in certain cases to prevent the occurrence
of undesired side reactions or to ensure the complete use of costly reactants. When the reactants
are not in stoichiometric quantities, the reactant present in excess of the stoichiometric quantities
is termed the excess reactant and the material that is not present in excess of that required to
react with any of the other materials or the material that is present in least stoichiometric
 Fundamental Concepts of Stoichiometry 61

proportions is termed the limiting reactant . The limiting reactant is present in the smallest
stoichiometric amount and if the reaction is allowed to go to completion, it would disappear
first from the reaction mixture. It is the quantity of the limiting reactant present that determines
the amount of the product obtained using the given feed mixture.
The synthesis of ammonia is represented by the equation
N 2 + 3H 2 2NH3
If the ammonia converter is charged with a mixture of nitrogen and hydrogen containing 20%
nitrogen by volume, which one is the limiting reactant? If the reactants were in stoichiometric
quantities, the ratio of moles of hydrogen to moles of nitrogen = 3/1 = 3.0. In the feed mixture,
there is 20 moles of nitrogen for 80 moles of hydrogen. The ratio of moles of hydrogen to moles
of nitrogen = 80/20 = 4.0. It means that for every mole of nitrogen, 4 moles of hydrogen is
supplied which is one mole in excess of the stoichiometric requirement. Therefore, nitrogen is
the limiting reactant and hydrogen is present in excess.
If more than two reactants are present one of the reactants may be chosen as the reference
and the ratio of the moles of each reactant to the moles of the reference substance may be
calculated . These are then compared with the respective stoichiometric quantities for finding out
the limiting reactant. The excess of a reactant over that theoretically required to react with the
limiting reactant is usually expressed as percent excess. It is defined as
excess amount
percent excess = — :— :—
theoretically required amount
xlOO

The quantity of the desired substance formed by the reaction is determined from the quantity
of the limiting reactant. Its consumption in a reaction will limit the extent to which the reaction
can proceed . Frequently the limiting reactant may enter into many side reactions leading to the
formation of undesired by -products. It may also form intermediates which are not completely
decomposed and hence may be present in the reactor effluents.
Suppose that 500 kg of pyrites is oxidized in a supply of 400 kg of oxygen. The stoichiometric
requirement of oxygen to combine with 500 kg of pyrites is (352/479.9) x 500 = 366.7 kg.
Since oxygen supplied is greater than this amount, oxygen is the excess reactant and pyrites is
the limiting reactant. The percent excess oxygen supplied for burning pyrites can be calculated
as follows:
Pyrites charged = 500 kg = 500/119.975 = 4.17 kmol
Oxygen theoretically required = (11/4) x 4.17 = 11.47 kmol
Oxygen supplied = 400 kg = 400/32 = 12.5 kmol
Excess of oxygen = 12.5-11.47 = 1.03 kmol
Percent excess = (1.03/11.47) x 100 = 9.0%
Oxygen theoretically required for the above reaction is 11.47 kmol. The term theoretical
requirement in certain situations needs some clarification. Even if only part of the limiting
reactant actually undergoes reaction, the theoretical requirement of other substances are calculated
based on the complete conversion of the limiting reactant. Consider the combustion of one
kilogram -atom of carbon. Assume that only 90% of the carbon charged is undergoing combustion
and of the carbon converted, 80% is burned to C02 and the rest forms CO. The theoretical
requirement of oxygen is to be calculated based on the complete conversion of carbon to C02.
62 Stoichiometry and Process Calculations

Thus the theoretical requirement of oxygen is one kilomole. In some cases, as for example, in
the combustion of a fuel containing oxygen, the theoretical requirement is based on net oxygen
demand. That is, when the theoretically required quantity of oxygen by a given amount of the
fuel is calculated, it is necessary to subtract the amount of oxygen already present in the fuel
from the quantity of oxygen that is required by all the combustible components of the fuel.
Suppose that one hundred kilogram coal containing 66.0% carbon, 12.0% hydrogen, 15.0%
oxygen and 7.0% ash by weight is burned in air. How many moles of air are theoretically
required by 100 kg coal? Assume a basis of 100 kg coal charged. The number of moles of
—
carbon present in coal = 66/12 = 5.5 kmol. Since C + 02 > C02, one mol of carbon requires
one of mol oxygen for complete combustion. Therefore, the amount of oxygen required by
carbon = 5.5 kmol.
The number of moles of hydrogen present in coal = 12/2.016 = 5.95 kmol. Since H 2 +
—
l /202 > H 20, one mol of hydrogen requires 0.5 mol of oxygen for complete combustion.
Therefore, oxygen required by hydrogen in the fuel is 2.98 kmol. The total oxygen required
is
5.5 + 2.98 = 8.48 kmol
Oxygen present in the fuel = 15/32 = 0.47 kmol. Therefore, net oxygen demand = 8.48
-0.47 = 8.01 kmol. Since this oxygen should come from air which contains only 21% oxygen,
the number of moles of air required theoretically for the combustion of 100 kg coal is 8.01 x
(100/21) = 38.14 kmol.

3.7.2 Conversion
Chemical reactions never go to completion. Reactions occur within a given system till equilibrium
— —
between various constituents reactants and products is established. The extent of the reaction
corresponding to this equilibrium condition is measured by the equilibrium conversion for the
reaction. Reactions can never be carried out to a conversion beyond this equilibrium value. The
actual conversion will be less than the equilibrium value due to such reasons as insufficient time
allowed for the reaction. The conversion is the fraction of the feed or fraction of certain
constituents of the feed that is converted into products.
. moles of the feed reacted , _ _
Percent conversion = —
^
— — -— —
moles of the feed charged
- xlOO

Closely related to the percent conversion is the degree of completion of a reaction. Degree
of completion is, in fact, the conversion of the limiting reactant and may be defined as the ratio
of the amount of the limiting reactant that has undergone chemical transformation to the amount
that was available for the reaction. In the oxidation of iron pyrites we have considered earlier,
the charge consisted of 4.17 mol of pyrites. If the percent conversion of iron pyrites was 90%,
only (90/100) x 4.17 = 3.75 mol of pyrites would undergo reaction. If the reactant takes part
in more than one reaction, the percent conversion should consider the quantities involved in all
the steps.
Frequently the limiting reactant may enter into many side reactions leading to the formation
of undesired by -products. It may also form intermediates which are not completely decom -
posed and hence may be present in the reactor effluents.
 Fundamental Concepts of Stoichiometry 63

3.7. 3 Yield and Selectivity

Frequently, the reactants may enter into many side reactions, leading to the formation of
undesired by -products. These may also form intermediates which are not completely decom -
posed, and hence, may be present in the reactor effluents. The terms yield and selectivity are
used to indicate the degree to which the reactants are converted into desired products.
Yield is the ratio of the actual moles of the desired product to the moles which would have
been resulted if the reactant was converted entirely to form the desired products. In other
words,

moles of the reactant converted to the desired product

Percent yield x 100 (3.15)
total moles of the reactant converted
The yield defined by Eq. (3.15) is also called the reactor yield to distinguish it from the overall
yield or plant yield, which is defined as

Plant yield. % =
moles f '
° ^ convened to the desired product Q
total moles of the reactant fed to the process
x 1 0 (3 [6)

Plant yield is a measure of the overall performance of the plant and includes all chemical and
physical losses.
Selectivity is another term used to indicate the relative prominence of side reactions over
the desired reactions. It is defined as
_ , . . moles of the reactant converted to the desired product
Selectivity =
moles of the reactant converted to undesired products

Consider that 60% of the reactant fed is converted in a reaction and 50% of that converted
gives the desired product A and the rest undesired by -product B . Then, of the 100 moles of
the reactant fed, 60 moles are converted of which 30 moles form desired product A and
30 moles form by -product B . Then
30 30 30
Yield = — x 100 = 50 %, Plant yield = x 100 = 30 % and selectivity = — = 1.0
60 100 30
The difference between conversion and yield must be clear before attempting to solve any
problem involving chemical reaction. It is clear that conversion refers to the reactants and yield
to the products. Consider the production of methanol by the reaction of carbon monoxide and
hydrogen. The reaction of CO with H 2 may also result in the formation of formaldehyde.
CO + 2H 2 -> CH3OH
CO + H 2 -> HCHO
Starting with a mixture of 1 mol CO and 3 mol H 2, let 0.18 mol formaldehyde and 0.72 mol
of methanol be present in the product mixture . 0.90 mol CO (the limiting reactant) has reacted
or the conversion of CO is 90%. However, only 72% of the CO charged has been converted
to the desired product (methanol). The yield of methanol is the ratio of the moles of CO
64 Stoichiometry and Process Calculations

converted to methanol to the moles of CO converted in any way. That is, the yield is
( 0.72/ 0.9) x 100 = 80%. However, the plant yield would be only (0.72/1.0) x 100 = 72%.
Consider another reaction. In the nitration of benzene to nitrobenzene, it is found that some
dinitrobenzene is also formed as a by -product.
C6H 6 + HN03 C6H 5N02 + H 20
C6H6 + 2HN03 C 6H 4N 204 + 2H 20
The yield in this process would be based on the nitrobenzene produced.
moles of benzene converted to nitrobenzene , ..
Percent yield = —
total moles of benzene converted
x 100 (3.17)

The conversion of benzene is given by

moles of benzene consumed in the reaction , _ _
Percent conversion = —
total moles of benzene charged
x 100 (3.18)

3.7. 4 Extent of Reaction

The extent of reaction, also called reaction coordinate measures the progress of a reaction and
is defined as the degree to which a reaction has advanced. Let us denote the extent of reaction
by e. The extent of reaction and the number of moles taking part in the reaction are related as
dn , = v , d£ (3.19)
The change in the extent of reaction d£ is the same for each component whereas the
changes in the number of moles are different for different species taking part in the reaction.
In Eq. (3.19) v , is the stoichiometric number of species / . The stoichiometric numbers are
'

positive for products, negative for reactants and zero for inert species. Consider the reaction
2A + 3B — > L + 2M
Here vL = 1, vM = 2, vA = -2 and vB = -3. Let ni0 be the number of moles of the species
initially present in the system and n , the number of moles present after the reaction. Then
n , = nl0 + An , where An , is the change in the number of moles of / due to the reaction.
An , = v ,£ (3.20)
Therefore,
n , = n ,o + v, £ (3.21)
Let us examine how the extent of reaction is related to the conversion of reactants. Let
the fraction of the limiting reactant converted be z ,. In terms of conversion, the number of
moles of the reactant unconverted = n ,0 - z , n ,0 whereas in terms of extent of reaction this is
ni0 + v, £. Comparing these two results we see that the conversion and the extent of reaction
are related as
v, £
z (3.22)
n/ 0
 Fundamental Concepts of Stoichiometry 65

Since v, is negative for reactants, the above equation may be written as

—I —
V,. | £
z= (3.23)

EXAMPLE 3.19 Carbon monoxide combines with chlorine in the presence of a suitable
catalyst to form phosgene according to the following reaction.
CO(g) + Cl 2(g) -> COCl 2(g)
After reaction, the products contained 12 moles of phosgene, 3 moles of chlorine and
8 moles of carbon monoxide . Assuming that the original reactant mixture is free of phosgene,
calculate the following:
(a) The percent excess reactant used
(b) The percent conversion of the limiting reactant
(c) The moles of the total product per mole of the reactant mixture fed to the reactor

Solution The reaction product consisting of 12 moles of phosgene, 3 moles of chlorine,

and 8 moles of carbon monoxide is considered . 12 moles of phosgene is produced by the
reaction between 12 moles of CO and 12 moles of Cl 2. Therefore, the original reactant mixture
contained 12 + 3 = 15 moles of Cl 2 and 12 + 8 moles = 20 moles of CO. Since the
stoichiometric ratio between CO and Cl 2 is 1, and the reactant mixture contained CO and Cl2
in the ratio 20:15, chlorine is the limiting reactant and CO is present in excess.
excess amount
(a) Percent excess of CO = x 100
theoretically required amount
20 15
X 100 = 33.33%
15
(b) Chlorine is the limiting reactant.
moles of Cl 2 reacted
Percent conversion =
moles of Cl 2 charged
xl 00 =
15
—
x 100 = 80%

(c) Total products = 12 + 3 + 8 = 23 mol

Total reactants = 20 + 15 = 35 mol
Moles of total products per mole of total reactants are
23
— = 0.657
35
EXAMPLE 3.20 A gas mixture containing 2 moles of nitrogen, 7 moles of hydrogen and
1 mole of ammonia initially, is undergoing the following reaction.
N 2 + 3H 2 -> 2NH 3
Derive expressions for the mole fractions of various components in the reaction mixture
in terms of the extent of reaction.
Solution The total number of moles initially present is n0 = X ni0= 2 + 7 + 1 = 10 and
the sum of the stoichiometric numbers is v = E vi = 2 - 1 - 3 = - 2. The number of moles
66 Stoichiometry and Process Calculations

of various components after the reaction is related to the extent of reaction by Eq. (3.23) and
the ratio of the number of moles to the total moles gives the mole fraction y of the component.
nN 2 ,0 + vN 2 e 2-£
TN 2 -
n0 + ev 10 - 2e
%2 , o + vH 2 e 7 - 3e
TH2 - n0 + ev
~
10 - 2e
%H 3 , O + VNH 3 £ l -\- 2e
TNH3 - n0 + ev 10 - 2e

EXAMPLE 3.21 In the vapour -phase hydration of ethylene to ethanol, diethyl ether is obtained
as a by -product.
C 2H 4 + H 20 -> C 2H 5OH
2C 2H 4 + H 20 -> (C 2H 5) 20
A feed mixture consisting of 60% ethylene, 3% inerts and 37% water is sent to the reactor.
The products analyzed 53.89% ethylene, 14.37% ethanol, 1.80% ether, 26.35% water, and
3.59% inerts. Calculate the conversion of ethylene, yield of ethanol and ether based on ethylene.
Solution Basis: 100 mol of feed mixture
Products, P mol
Reactants = 100 mol Ethanol = 14.37%
Ethylene = 60 mol
> Reactor >. Ether = 1.80%
Water = 37 mol Ethylene = 53.89%
Inerts = 3 mol Water = 26.35%
Inerts = 3.59%
Figure. 3.1 Chemical process in Example 3.21.

Since the amount of inert materials does not change during reaction, inerts may be treated
as the key component (for a detailed discussion on key components see Chapter 9) for making
material balances. Let P mol of products are formed . Then inert balance gives
3 = 0.0359 xP
Therefore, P = 83.57 mol. The product contains
53.89 x
Ethylene = 83.57 = 45.04 mol
100
14.37 x
Ethanol = 83.57 = 12.01 mol
100
1.8 x
Ether = 83.57 = 1.5 mol
100
23.35 x
Water = 83.57 = 22.02 mol
100
Inerts = 3 mol
 Fundamental Concepts of Stoichiometry 67

moles of ethylene reacted

Conversion of ethylene = x 100
moles of ethylene charged
60 - 45.04
x 100 = 24.93%
60
moles of ethylene converted to ethanol
Yield of ethanol = x 100
total moles of ethylene converted
12.01
x 100 = 80.0%
60 - 45.04
(The number of moles of ethylene converted to ethanol is equal to the number of moles
of ethanol in the products because one mole of ethanol requires one mole of ethylene.)
moles of ethylene converted to ether
Yield of ether = x 100
total moles of ethylene converted
15x2
= 60 - 45.04 x 100 = 20.0%
(The number of moles of ethylene converted to ether is equal to twice the number of moles
of ether in the products as two moles of ethylene is needed for 1 mole of ether.)

EXERCISES
The mole concept
3.1 How many grams of NH 4C1 are there in 5 mol?
3.2 Convert 750 g CuS04.5H20 into moles. Find equivalent mol of CuS04 in the crystals.
3.3 How many kilogram of CS2 will contain 3.5 kg-atom carbon?
3.4 How many grams of carbon are present in 264 g of C02?
3.5 The molecular formula of an organic compound is C10H 7Br. Find the weight percentage
of carbon, hydrogen and bromine in the solid .
3.6 Find the equivalents of 3 kmol of FeCl3.
3.7 What is the equivalent weight of A12(S04)3?
3.8 How many equivalents are there in 500 g KMn04?
3.9 Calculate the equivalent weight of H3P04 in the reaction
Ca(OH)2 + H 3P04 -> CaHP04 + 2H 20
3.10 A certain organic compound is found to contain 81.5% C, 4.9% H, and 13.6% N by
weight. If the molecular weight of the compound is 103, determine the molecular
formula of the compound.
68 Stoichiometry and Process Calculations

3.11 Aluminium chloride is made by the chlorination of molten aluminium metal in a furnace:
2A1(/) + 3C12( g ) -> 2AlCl 3(g)
(a) How many kilograms of A1C13 can be made from 100 kg of chlorine?
(b) How many grams of A1 will react with 50 g of chlorine?
3.12 Sodium hydroxide is made by the electrolysis of brine solution. The overall reaction
may be written as:
2NaCl + 2H20 -> 2NaOH + H 2 + Cl 2
(a) How much NaOH can be made from 1000 kg NaCl?
(b) How much water is consumed in the production of 500 kg Cl2?
3.13 Sulphur trioxide gas is obtained by the combustion of pyrites (FeS2) according to the
following reaction:
4FeS2 + 1502 -> 2Fe 203 + 8S03
The reaction is accompanied by the following side reaction:
4FeS2 + 1102 -> 2Fe 203 + 8S02
Assume that 80% (weight) of the pyrites charged reacts to give sulphur trioxide and
20% reacts giving sulphur dioxide .
(a) How many kilograms of pyrites charged will give 100 kg of S03?
(b) How many kilograms of oxygen will be consumed in the reaction?
3.14 Barium chloride reacts with sodium sulphate to precipitate barium sulphate:
—
BaCl 2 + Na 2S04 ^ 2NaCl + BaS04
(a) How many grams of barium chloride are needed to react with 100 g of sodium
sulphate ?
(b) For precipitating 50 g of barium sulphate, how many grams of the reactants are
consumed?
(c) How many grams of sodium chloride would be obtained when 50 g of barium
sulphate is precipitated?
3.15 Chromite ore analyzed 30.4% Cr 203. Determine the theoretical amount of lead chromate
(PbCr04) that can be obtained from 1000 kg of the ore.
3.16 The alloy brass contains lead as an impurity in the form of lead sulphate (PbS04). By
dissolving brass in nitric acid, lead sulphate is precipitated . A sample of brass weighing
5.0 g is dissolved in nitric acid and 0.03 g of precipitate is formed. Calculate the
percentage of lead present in the brass sample.
3.17 How many kilograms of C02 are obtained by the decomposition of 100 kg of limestone
containing 94.5% CaC03, 4.2% MgC03 and 1.3% inert materials? What is the volume
of C02 obtained at STP?
3.18 Sulphur dioxide is obtained by the following reaction
Cu + 2H 2S04 -> CuS04 + 2H 20 + S02
(a) When 50 kg Cu dissolves in sulphuric acid what volume of sulphur dioxide is
produced at standard conditions?
 Fundamental Concepts of Stoichiometry 69

(b) How many kilograms of 94% sulphuric acid will be required for the above
reaction?
3.19 Crude calcium carbide, CaC 2, is made in an electric furnace by the following reaction.
CaO + 3C -> CaC 2 + CO
The product contains 85% CaC 2 and 15% unreacted CaO.
(a) How much CaO is to be added to the furnace charge for each 1000 kg CaC 2?
(b) How much of CaO is to be added to the furnace charge for each 1000 kg of crude
product?
Specific gravity and specific gravity scales
3.20 A 1-kg lead ball of density 11.34 x 103 kg/m 3 is immersed in water. The density of
water is 1000 kg/m 3. Calculate the buoyant force on the body.
3.21 A body weighs 1.0 kg in air, 0.90 kg in water and 0.85 kg in a liquid . What is the
specific gravity of the liquid?
3.22 10 kg of liquid A of specific gravity 1.2 is mixed with 3 kg of liquid B of specific
gravity 0.8. Assuming that there is no volume change on mixing, what is the specific
gravity of the mixture ?
3.23 An alloy contains metal A and B in the ratio 5 :3. If metal A has a specific gravity 10
and metal B has a specific gravity 5 in the pure state, what would be the specific gravity
of the alloy ?
3.24 An aqueous solution of a valuable chemical (molecular weight = 180) leaves the
reactor at a rate of 60 x 10 3 m 3/h. The solution concentration is 40% (weight) and its
~

specific gravity is 1.05. Determine (a) the concentration of the solution in kg/m 3 and
(b) the flow rate in kmol/h.
3.25 A certain solution has a specific gravity of 1.15 at 288.8 K referred to water at 288.8 K.
Express the specific gravity as ° Be and °Tw.
3.26 What is the specific gravity on Baume scale for a 90 °Tw solution?
3.27 The specific gravity of a hydrocarbon oil is 0.88 at 288.8 K. What are the corresponding
values in the Baume and API scales?
3.28 The bulk density of a solid is 1.125 g/mL and the true density is 1.5 g/mL. What is
the porosity of the solid?
3.29 500 cubic meters of 30 °API gas oil is blended with 2000 cubic meters of 15 °API
fuel oil. What is the density of the resultant mixture in kg/m 3? The density of water
at 288.5 K = 0.999 g/ml. Assume no volume change on mixing.
3.30 100 litres each of gasoline (55°API), kerosene (40°API), gas oil (31°API), and isopentane
(96° API) are mixed . The density of water at 288.5 K = 0.999 g/mL.
(a) Determine the density of the mixture in kg/m 3.
(b) What is the specific gravity in °API?
( c ) Express the composition of the mixture in weight percent.
70 Stoichiometry and Process Calculations

288.5 K
3.31 The specific gravity of an ammonia-water solution is 0.9180. What would
288.5 K
288.5 K
be the specific gravity if the density of water at 288.5 K and 300 K are
300 K
respectively, 0.998 g/mL and 0.989 g/mL?
3.32 An analysis of sea water showed 2.8% NaCl, 0.5% MgCl 2 and 0.0085% NaBr by
weight. The average specific gravity of the water is 1.03. What mass of magnesium,
sodium and chlorine can be obtained from 100 m 3 of sea water?
Composition of solids, liquids and gases
3.33 What is the weight percentage of CaO in Ca(OH) 2?
3.34 Determine the weight percentage of the constituent elements of potassium sulphate?
3.35 What is the percentage of water in A12(S04)317H 20?
3.36 Compare the percentages of iron in ferrous chloride and ferric chloride?
3.37 An aqueous solution contains 40% by weight NaN03. Determine the composition in
mole percent.
3.38 How many kg of Glauber’s salt (Na2SO 410H 2O) will be obtained from 250 kg Na2S04?
3.39 A sample of urea (NH 2CONH 2) contains 42.0% nitrogen by weight. What is the percent
purity of the sample?
3.40 Determine the mass fraction and mole fraction of chlorine in the substance Ca(C10)2.
3.41 The strength of phosphoric acid is usually represented as weight percent of P205. A
sample of phosphoric acid analyzed 40% P205. What is the percent by weight of
H3P04 in the sample ?
3.42 A blast furnace treats 106 kg per day hematite ore which contains 50% pure ferric
oxide. Determine the weight of pig iron produced per day. Pig iron contains 94% iron.
3.43 A liquid mixture contains three components A ( MW = 72) , B (MW = 58 ) and
C (MW = 56) in which A and B are present in the mole ratio 1.5:1 and the weight
percent of B is 25%. A sample of the mixture is found to contain 10 kg of C. Calculate
the total number of moles of the mixture.
3.44 A portland cement sample contained 20% Si02 by weight derived from two silicate
compounds, Si02 2CaO and Si02 3CaO that are present in the cement in the mole ratio
3:4. Determine the percent by weight of each silicate compound in the cement.
3.45 An ethanol-water mixture forms an azeotrope* at 89.43 mole percent ethanol at 101.3 kPa
and 351.4 K. What is the composition of the azeotrope in weight percent?
3.46 A 20% (weight) aqueous solution of monoethanolamine (MEA, NH 2CH 2CH 2OH) is
used as a solvent for absorbing C02 from a gas stream . The solution leaving contains
0.25 mol C02 per mol MEA. Determine
(a) The mole percent of C02 in the solution leaving the absorber.
(b) The mass percent of C02 in the solution.
*Azeotropes are constant boiling mixtures that boil without a change in composition till the entire liquid is
vaporized .
 Fundamental Concepts of Stoichiometry 71

3.47 A water soaked cloth is dried from 45% to 9% moisture on dry basis. Find the weight
of water removed from 2000 kg of dry fabric.
3.48 A solution of sodium chloride is saturated in water at 289 K . Calculate the weight of
salt in kg that can be dissolved in 100 kg of this solution if it is heated to a temperature
of 343 K. The solubility of sodium chloride at 289 K = 6.14 kmol/1000 kg water. The
solubility at 343 K = 6.39 kmol/1000 kg of water.
3.49 The solubility of benzoic acid (C6H 5COOH) is found out to be 66 parts in 100 parts
by weight of ether (C 2H 5OC 2H 5). Find the mole fraction of benzoic acid in the saturated
solution with ether.
3.50 The solubility of benzoic acid (C6H 5COOH) in ether (C 2H 5OC2H 5) is found to be
28.59% (by mole). What is the solubility in weight percent? What is the weight ratio
of acid to ether in the saturated solution?
3.51 Hydrogen chloride is made by the action of sulphuric acid on sodium chloride. Hydrogen
chloride being readily soluble in water forms hydrochloric acid. Calculate the following:
(a) The weight in grams of HC1 formed by the action of excess sulphuric acid on 1 kg
of salt which is 99.5% pure
(b) The volume of hydrochloric acid solution (specific gravity 1.2) containing 40% by
weight HC1 that can be produced
( c ) The weight in kilograms of sodium sulphate obtained
3.52 An excess of NaN03 is treated with 25 kg sulphuric acid solution which contains
93.2% by weight of pure H 2S04. Calculate the following:
(a) The number of kilomoles of pure nitric acid obtained
(b) The mass of nitric acid containing 70% by weight HN03 obtained
(c) The number of kilograms of Na 2S04 produced
3.53 A liquid mixture contains three components A ( MW = 72) , B (MW = 58) and
C (MW = 56) in which A and B are present in the mole ratio 1.5:1 and the weight
percent of B is 25%. The specific gravities of the pure liquids are 0.67, 0.60 and 0.58
respectively, for A , B and C and there is no volume change on mixing. Calculate the
following:
(a) The analysis of the mixture in mole percent
(b) The molecular weight of the mixture
(c) The volume percent of C on a 5-free basis
( d) The specific gravity of the mixture
3.54 An alcohol-water solution contains 20% (volume) ethanol at 300 K. The densities of
ethanol and water at 300 K are 0.798 g/mL and 0.998 g/mL respectively. What is the
weight percent of alcohol?
3.55 Calculate the concentration in mol/L of pure methanol at 298 K if the density of
methanol at 298 K is 0.9842 g/mL.
3.56 A company has a contract to buy NaCl of 98 percent purity for ? 300 per 1000 kg
salt delivered. Its last shipment of 1000 kg was only of 90% purity. How much they
should pay for the shipment?
72 Stoichiometry and Process Calculations

3.57 A compound is found to contain 62.4% Ca and 37.6% C.

(a) How many gram atoms of Ca and C are present in 100 g of the compound?
(b) Suggest an empirical formula for the compound.
3.58 It is desired to prepare a 40% solution of NaCl in water at 300 K .
(a) How many kg of anhydrous sodium chloride should be added to 0.05 cubic metres
of pure water having a density of 0.998 g/mL at 300 K?
(b) If the salt contains 10% water, how many kg of salt is required?
3.59 Absolute humidity of air is 0.02 kg water vapour/kg dry air. Assuming the average
molecular weight of air to be 29, calculate the following:
(a) The mole percent of water vapour in the air
(b) The molal absolute humidity, which is same as the mole ratio of water vapour to
dry air.
3.60 Assuming that dry air contains 21% oxygen and 79% nitrogen, calculate the following:
(a) The composition in weight percent
(b) The average molecular weight of dry air
3.61 By electrolysing brine, a mixture of gases is obtained at the cathode having the following
composition by weight: chlorine 67%, bromine 28% and oxygen 5 %. Calculate
composition of gases by volume .

Other expressions for concentrations

3.62 Determine the weight percent of NaOH in an aqueous solution of molality 2.
3.63 Calculate the molality of a solution of 93% H 2S04 (W/V). The density of the solution
is 1840 kg/m 3.
3.64 A 6.9 molar solution of KOH in water contains 30% by weight of KOH. Calculate the
density of the solution.
3.65 The concentration of S02 in the flue gases from a boiler is found to be 0.2 kg/m 3 at
STP. Determine the concentration of S02 in parts per million by volume at STP.
Assume that the gases are perfect.
3.66 A benzene solution of an organic compound A analyses 10% of A . The molality of the
solution is reported to be 0.62. Calculate the following:
(a) The molecular weight of the compound
(b) The mole fraction of the compound in the solution
3.67 An aqueous solution of NaCl contains 20% NaCl. The density of the solution is 1.16 g/mL.
500 ml water of density 1 g/mL is added to 1 litre of the solution. What will be the
molality and molarity of the resulting solution?
3.68 A solution of ZnBr 2 in water contains 130 g salt per 100 mL solution at 293 K . The
specific gravity of the solution is 2.00. Calculate the following:
(a) The concentration of ZnBr2 in mole percent
(b) The concentration of ZnBr2 in weight percent
(c ) The molarity
(d ) The molality
 Fundamental Concepts of Stoichiometry 73

3.69 The molality of an aqueous solution of LiCl in water is 10. The density of the solution
is 1.16 g/mL at 350 K. Determine the following:
(a) The weight percent of LiCl in the solution
(b) The molarity of the solution at 350 K
(c) The normality of the solution at 350 K
(d) The composition of the solution in mole percent
3.70 The molarity of an aqueous solution of MgCl 2 at 300 K is 4.0. The specific gravity
of the solution is 1.3 at 300 K. Determine the following:
(a) The concentration of MgCl 2 in weight fraction
(b) The concentration of MgCl 2 in mole fraction
(c ) The molality of the solution
(d) The normality of the solution at 300 K
3.71 Pure water and alcohol are mixed to get a 50% alcohol solution. The density (g/mL)
of water, alcohol and the solution may be taken to be 0.998, 0.780 and 0.914, respectively
at 293 K. Calculate the following:
(a) The volume percent of ethanol in the solution at 293 K
(b) The molarity
(c ) The molality
3.72 A solution of potassium chloride in water contains 384 g KC1 per litre of the solution
at 300 K. The specific gravity of the solution is 1.6. Determine the following:
(a) The concentration in weight percent
(b) The mole fraction of KC1
(c) The molarity of the solution
(d) The molality of the solution
3.73 Silver nitrate reacts with metallic Zn depositing silver according to the reaction
Zn + 2AgN03 — > 2Ag + Zn(N03) 2

With 0.05 kg metallic Zn is added to 10 3 m 3 of silver nitrate solution, it was found

~

that after all silver in the solution is deposited in metallic form some Zn metal is left
unreacted . The total weight of the unreacted Zn and deposited silver was found to be
0.07 kg. Determine the following:
(a) The mass of silver deposited
(b) The molarity of the silver nitrate solution
Chemical reactions and process calculations
3.74 1 kg nitrogen is mixed with 3.5 m 3 of hydrogen at 300 K and 101.3 kPa and sent to
the ammonia converter. The product leaving the converter analyzed 13.7% ammonia,
70.32% hydrogen and 15.98% nitrogen.
(a) Identify the limiting reactant.
(b) What is the percent excess of the excess reactant?
( c ) What is the percent conversion of the limiting reactant?
3.75 In the chlorination of ethylene to dichloroethane, the conversion of ethylene is 99.0%.
If 94 mol of dichloroethane is produced per 100 mol of ethylene fed, calculate the
overall yield and the reactor yield based on ethylene .
C2H 4 + Cl 2 C 2H 4C12
74 Stoichiometry and Process Calculations

3.76 In the manufacture of methanol by the reaction of carbon monoxide and hydrogen,
some formaldehyde is also formed as a by -product.
CO + 2H 2 -> CH3OH
CO + H 2 -> HCHO
A mixture consisting of CO and H 2 is allowed to react and the product analyzed 2.92%
CO, 19.71% methanol, 6.57% formaldehyde and 70.80% hydrogen. Calculate the
following:
(a) The percent conversion of limiting reactant
(b) The percent excess of any reactant
( c ) Percent yield of methanol
3.77 Water vapour decomposes according to the following reaction
H2O -> H2 +|o2
What is the mole fraction of oxygen in the reaction mixture in terms of the extent of
reaction if the system contained n0 moles of water vapour initially ?
3.78 The following reaction occurs in a mixture consisting of 2 mol methane, 1 mol water,
1 mol carbon monoxide and 4 mol hydrogen initially.
CH 4 + H 20 -> CO + 3H 2
What is the mole fraction of hydrogen in the reaction mixture in terms of the extent
of reaction.
3.79 A system consisting of 2 mol methane and 3 mol water is undergoing the following
reaction:
CH 4 + H 20 -> CO + 3H 2
CH 4 + 2 H20 -> C02 + 4H 2
Derive expressions for the mole fraction of hydrogen in terms of the extent of reac -
tions.
3.80 The following gas-phase reactions occur in a mixture initially containing 3 mol ethyl-
ene and 2 mol oxygen.
C 2 H4 + }02 -> (CH2)20
C 2H 4 + 302 -4 2C02 + 2H20
Derive an expression for the mole fraction of ethylene in terms of the extent of
reactions.
3.81 In the vapour-phase hydration of ethylene to ethanol, diethyl ether is obtained as a
by -product.
C 2H 4 + H 20 C 2H 5OH
2C 2H 4 + H 20 -> (C 2H 5)20
A feed mixture consisting of 55% ethylene, 5% inerts and 40% water is sent to the
reactor. The products analyzed 52.26% ethylene, 5.49% ethanol, 0.16% ether, 36.81%
 Fundamental Concepts of Stoichiometry 75

water, and 5.28% inerts. Calculate the conversion of ethylene, yield of ethanol and
ether based on ethylene.
3.82 Elemental phosphorous is produced from phosphate rock in an electric furnace by the
following reaction:
2Ca3(P04)2 + IOC + 6Si02 —> P 4 + 6CaSi03 + 10CO
The furnace is fed with 1000 kg phosphate. Carbon charged is 25% in excess and
silica charged is 50% in excess. The reaction goes to 95% completion. The uncon-
verted reactants along with the calcium silicate formed constitute the slag. Calculate the
following:
(a) The mass of carbon and silica charged (in kilograms)
(b) The amount of phosphorous obtained (in kilograms)
(c ) The mass of slag produced (in kilograms)
3.83 Iron pyrites is burned in 50% excess air. The following reaction occurs:
4FeS2 + 1102 -> 2Fe 203 + 8S02
For 100 kg of iron pyrites charged, calculate the following:
(a) The amount of air supplied (in kilograms)
(b) The composition of exit gases if the percent conversion of iron pyrites is 80%
3.84 Ammonia reacts with sulphuric acid giving ammonium sulphate :
2NH 3 + H 2S04 (NH 4)2S04
(a) 20 m 3 of ammonia at 1.2 bar and 300 K reacts with 40 kg of sulphuric acid.
Which is the excess reactant and what is the percent excess?
(b) How much ammonium sulphate is obtained?
3.85 Sulphur dioxide reacts with oxygen producing sulphur trioxide :
so2 + \02 -> so3
In order to ensure complete reaction, twice as much oxygen is supplied than that
required theoretically. However, only 60% conversion is obtained. The pressure was
500 kPa and temperature 800 K. 100 kg of S02 is charged to the converter. Determine
the following:
(a) The volume of pure oxygen supplied at 1.5 bar and 300 K
(b) The volume of sulphur trioxide produced
(c) The volume of gases leaving the converter
(d) The composition of gases leaving the converter
(e) The average molecular weight of the gas leaving the converter
3.86 Nitrogen dioxide shows a tendency to associate and form nitrogen tetroxide .
2N02 N 204
One cubic metre nitrogen dioxide at 100 kPa and 300 K is taken in a closed rigid
container and allowed to attain equilibrium at constant temperature and volume. The
pressure inside the container has fallen to 85 kPa at equilibrium .
76 Stoichiometry and Process Calculations

(a) What is the degree of association?

(b) What is the partial pressure of N 204 in the final mixture?
3.87 Ammonium chloride in the vapour phase dissociates into ammonia and hydrogen chloride
according to
NH 4C1 NH3 + HC1
10.7 g of ammonium chloride is taken in a container. When dissociation is complete
and equilibrium is attained the pressure, the volume and temperature of the gas mixture
were measured to be 1.2 bar, 7.764 x 10-3 m 3 and 400 K, respectively. Determine the
following:
(a) The fraction of ammonium chloride dissociated
(b) The partial pressure of HC1 in the products
3.88 A gaseous mixture consisting of 50% hydrogen and 50% acetaldehyde (C 2H 40) is
initially contained in a rigid vessel at a total pressure of 1.0 bar. Methanol is formed
according to
C 2H 4O + H 2 -> C 2H6O
After a time it was found that the total pressure in the vessel has fallen to 0.9 bar while
the temperature was the same as that of the initial mixture. Assuming that the products
are still in the vapour phase, calculate the degree of completion of the reaction.
3.89 Ammonia is made by the reaction between hydrogen and nitrogen according to the
following reaction:
N 2 + 3H 2 -> 2NH3
(a) For complete conversion of 100 cubic metres of nitrogen at 20 bar and 350 K,
what volume of hydrogen at the same conditions of temperature and pressure is
theoretically required?
(b) If hydrogen is available at 5 bar and 290 K, what is the volume required which
is stoichiometrically equivalent to 100 m 3 of nitrogen at 20 bar and 350 K ?
(c ) If the reaction is carried out at 50 bar and 600 K, what volumes of nitrogen and
hydrogen at these conditions are theoretically required for producing 1000 kg
ammonia and what will be the volume of ammonia produced at the reactor
conditions?
3.90 Carbon dioxide dissociates into carbon monoxide and oxygen at 1 bar and 3500 K .
C02 -» CO + \o2
25 L of C02 at 1 bar and 300 K is heated to 3500 K at constant pressure. If all gases
behave ideally, determine the following:
(a) The final volume of the gas if no dissociation is occurred
(b) The fraction of C02 is dissociated if the final volume is found to be 0.35 m 3.
 4 Ideal Gases and
Gas Mixtures

Operations in which gases and gas mixtures are to be handled are quite numerous in chemical
process industries. Chemical conversions involving gases are quite common, the synthesis of
ammonia from a mixture of nitrogen and hydrogen, combustion of gaseous fuels in air being
two typical examples. Unit operations such as absorption, distillation, drying, adsorption, gas
cooling, humidification, etc., transportation and storage of gases are some of the important areas
where gases undergo a change of state. The calculations involving the quantities of the material
and energy required in such processes as well as the effect of operating parameters on such
processes are frequently encountered by chemical engineers.
—
The gaseous state is the most simple form of matter among the three states solids, liquids
and gas. The general characteristics of a gas are the following:
• Gases do not have a definite shape or volume. These are determined by the shape and
volume of the container in which the gas is taken.
• Compared to solids and liquids, gases have very low densities. Consequently, the
molecules in a gas are far removed from one another.
• Even a small increase in pressure will compress the gas to a very great extent. In
contrast, the effect of pressure on solids and liquids is negligible.

4.1 IDEAL GAS

On a molecular level, an ideal gas may be treated as the one for which (a) the size of the
molecules is very small compared to the distance between them so that the volume of the
molecules is negligible in comparison with the total volume of the gas and (b) the intermole -
cular forces are negligibly small. The concept of ideal behaviour coupled with a mechanism to
estimate the extent of deviation from ideality is very useful in predicting the behaviour of real
systems which are either very complex or are not mathematically amenable. Though no gas is
ideal in the true sense of the term, experiments have shown that at low pressures and fairly
high temperatures, all ordinary gases behave ideally. A pressure -volume-temperature relationship
77
78 Stoichiometry and Process Calculations

for a real fluid is not easily explained mathematically. However, for an ideal gas such a
relationship is easily established as described by a series of laws such as Boyle’s law, Charles’
law and Avogadro’s hypothesis.

Boyle’s law: Boyle in 1662 proposed that for a fixed quantity of a gas the volume is inversely
proportional to pressure at constant temperature .
PV = constant (at fixed T and n ) (4.1)
where P = pressure, V = volume, T = temperature and n is the number of moles of the gas.

Charles’ law: The dependence of the volume of a gas on temperature was reported by Charles
in 1787. A quantitative relationship between volume and temperature was proposed by
Gay-Lussac in 1802. The laws of Gay-Lussac and Charles state that the volume of a fixed
quantity of gas at constant pressure varies directly with temperature.
V
—= constant (at fixed P and n ) (4.2)

Avogadro’ s principle: According to Avogadro’s hypothesis equimolal quantities of all gases

at the same temperature and pressure occupy the same volume .

4.1.1 Ideal Gas Equation

The ideal gas equation is obtained by combining Boyle ’s law and Charle’s law. Assume that one
mole of a gas is initially at temperature T0 , and pressure P0 and let the volume occupied by the
gas under these conditions be V0 . Now let the gas be brought to the final state where the
pressure, volume and temperature are, respectively, P , V and T . Let this change be accomplished
in two steps. First, an isothermal process in which the temperature is kept constant at T0 , and
pressure is changed to P . In the second step, the gas pressure is kept constant at P and the
temperature is changed from T0 to T.
In the first step the volume of the gas changes from V0 to V' at constant temperature T0 and
Boyle’s law is applicable.
P0V0 = PV = constant ( 4.3)
Rearranging this equation, we get
PQVQ
V' = (4.4)
p
In the second step, the volume changes from V to V at constant pressure P and therefore,
Charles’ law is applicable.
V' V
= constant (4.5)
1

Substituting Eqs. (4.4) into Eq. (4.5) and rearranging, we get

PV _ P0V0
The state of the gas as given by its pressure P volume V and temperature T may be thought
9

of as attained through the two successive steps, one isothermal and the other isobaric, from
 Ideal Gases and Gas Mixtures 79

an arbitrarily chosen reference state at which pressure is P0 and temperature is T0. Assigning
standard values for the reference conditions P0 and T0 , the volume occupied by any gas at the
reference state V0 would be constant according to Avogadro’s principle, so that we can take the
quantity P 0V0/ T0 on the right hand side of Eq. (4.6) to be a universal constant which is denoted
by R.
PV PV0VV0 n
= - - -= R (4.7)
T To
or PV = RT (4.8)
R is known as the gas constant and its magnitude depends on the units of standard pressure
P0 > standard volume V0 and standard temperature T0 . As pointed out in Chapter 2, experi-
ments have shown that the volume occupied by one mole of an ideal gas at standard
temperature T0 = 273.15 K and standard pressure P0 = 1.01325 x 105 N/m2 is 22.4143 x 10 3
m 3/mol. In the FPS system, the molar volume at standard conditions (P0 = 14.7 psia, T0 = 492°R)
is 359 ft3/(lb-mol). In SI units the ideal gas constant is equal to 8.314 J/(mol K) or 8.314 kJ/
(kmol K). The values of R in other units are given in Table 4.1. Equation (4.8) gives the volume
of one mole of an ideal gas at pressure P and temperature T . For n moles of the gas, the total
volume V is n times the molar volume, and Eq. (4.8) can be generalized as
PV = nRT ( 4.9)

Table 4.1 Ideal gas constant in various units

P T V n R Units of R
N/m 2 (Pa) K m3 mol 8.314 J/( mol K )
103 N/m 2 (kPa ) K m3 kmol 8.314 kJ/( kmol K )
atm K L mol 8.206 x 10-2 L atm/(mol K )
atm K m3 mol 8.206 x 10 5
“
m3 atm/( mol K )
atm K m3 kmol 8.206 x 10-2 m3 atm/(kmol K )
atm K cm 3 mol 82.06 cm 3 atm /(mol K )
atm °R ft3 lb mol 0.73 ft3 atm/(lb- mol °R)
psia ( pounds
per square inch) °R ft3 lb mol 10.73 ft3 psia /(lb-mol °R)

Gases such as hydrogen, helium, nitrogen and oxygen at room temperatures follow the
perfect gas law very closely and they can be treated as ideal gases for engineering calculations.
However, the only state at which the real gases follow ideal behaviour is at zero pressure. For
engineering purposes all gases at pressures in the neighbourhood of atmospheric pressure are
treated as ideal.

m mmHg
EXAMPLE 4.1 (a) Find the value of the gas constant R in
mol K
jn
^ ^MKS

system energy is usually expressed as calories or kilocalories. What will be the value of R when
cal
it is expressed in ?
mol K
80 Stoichiometry and Process Calculations

Solution
P0V0
(a) For one mole of ideal gas at the standard conditions, R =
. The standard conditions
T0

R
_
are P0 = 760 mm Hg, T0 = 273.15 K and V0 = 22.4143 x 10-3 m 3/mol. Substituting
these values in the above equation, we get
760 x 22.4143 x 10 ~3
273.15
= x ]0-2
mWlg
mol K
(b) When P0 = 1.01325 X 105 N/m 2, T0 = 273.15 K and V0 = 22.4143 X 10 3 m 3/mol,
we get
1 01325 x 10s (22 4143 x 10 3 )
*= 273.15
,

= R_
N
^
mol K
= g 3H
_ _
molK
±
8.314 cal
Since 1 cal (thermo-chemical calorie1) = 4.184 J, R = = 1.987
4.184 mol K

4.1 .2 Calculations for Ideal Gas

In the application of ideal gas equations, two types of problems are generally encountered . In
the first type, the pressure ( Pi ) , temperature ( Tx ) and volume ( V {) at an initial state will be
known. The gas is undergoing a change of state and the conditions in the final state are pressure
( P 2), temperature ( F2) and volume ( V 2 ). You are required to calculate any one of the three
quantities in the final state P2, T 2 or V 2 for the same mass of the gas. Using Eq. (4.9), we can
write for both states,
P 1V 1 = nRTi
P 2V 2 = nRT2
Dividing the first equation by the second and rearranging the result, we get
pyi p2 v2
(4.10)
Ti T2
Equation (4.10) may be used for the solution of the problems of this type.
In the second class of problems, the mass of the gas is also involved . It would be required
to find the pressure, volume or temperature of a given mass (that is, given number of moles)
of a gas. Alternatively, for given conditions of pressure, volume and temperature, the mass is
to be determined. Equation (4.9) can be used to solve such problems. However, in using
Eq. (4.9), care should be taken to use the appropriate value of R depending upon the units of
the four variables P, V , T and n . Otherwise, the units of P, V , T and n have to be converted
into appropriate units so that they are consistent with the units of R chosen for calculations.
This difficulty can be circumvented by using the following relation

1 In older tables of thermodynamic properties of substances, the calorie known as the thermo-chemical calorie
is equivalent to 4.184 J, whereas in the International Steam Table it is equivalent to 4.1868 J.
 Ideal Gases and Gas Mixtures 81

PV PQVQ
(4.11)
T T0
and calculating the volume V0 occupied by the gas at standard conditions P0 and T0

V0 = V x —P, x —T
0
(4.12)

In Eq. (4.12), V0 is the volume occupied by a given quantity of an ideal gas in the standard
state. Any units of pressure, volume, or temperature may be used in this equation, provided the
units in both the given state and the standard state are the same. In the second step, the volume
V0 SO calculated is converted to moles by dividing it by the normal molal volume. In the usual
standard state (the one corresponding to P0 = 1 at1*1 and T0 = 273.15 K), the normal molal
volume is 22.4143 x 10-3 m 3/mol or 359 ft3/(lb-mol).
EXAMPLE 4.2 Assuming air to behave as an ideal gas, calculate the molar volume of air at
350 K and 1 bar.
Solution One mole of a gas at STP (standard conditions of temperature and pressure )
occupies 22.4143 x 10 3 m 3 (That is P 0 = 1.01325 bar, T0 = 273.15 K, and V0 = 22.4143
“

x 10-3 m 3) . Now we can use Eq . ( 4.11) to calculate the volume ( V ) at 1 bar ( P ) and
350 K ( 7).
T
v = v0 x
^P
x
To
/
1.01325 \ 350
= 22.4143 x 10 3 = 2.91 x 10 2 m 3
“ “

V / 273.15 1
Thus the molar volume of air at 350 K and 1 bar = 2.91 x 10-2 m 3/mol.
[Alternatively, Eq. (4.9) can be used with temperature T = 350 K and pressure P = 1 bar
= 105 N /m 2. Accordingly, one mole of air at the stated conditions will have a volume F, where
RT
V=
P
8.314 x 350 2
= 2.91 x 10 m3
"

1 x 105

EXAMPLE 4.3 A 150 L oxygen cylinder contains gas at 300 K and 10 bar. What is the mass
of oxygen in the cylinder?
Solution Here P =10 bar, T = 300 K and V 150 L —
The volume at STP is found out using Eq. (4.12):

v0 = F x —
P0
r
x
^
T
10 V 273.15
= 150
v 1.01325 / v 300 /
= 1347.9 L ^
82 Stoichiometry and Process Calculations

As the normal molal volume is 22.4143 L/mol, the number of moles of oxygen = 60.14
mol. Thus, the mass of oxygen in the cylinder = 60.14 x 32 = 1924.36 g = 1.9244 kg.

EXAMPLE 4.4 An automobile tyre is inflated to a pressure of 195 kPa at 273 K. If the
pressure inside the tyre is not to exceed 250 kPa, what is the maximum temperature to which
the tyre may be heated?
Solution Using Eq. (4.10), we can write
r \( p

UJ^
rr
V- r2
T2 = T\ 2
V i /

It is assumed that the volume of air inside the tyre remains constant, so that V 2/ Vl =1.
Therefore,
250
T2 = 273 x 1 x = 350 K
195
EXAMPLE 4.5 Carbon dioxide is contained in a 250 L cylinder at a temperature of 300 K.
The gas from the cylinder is allowed to enter an evacuated chamber of capacity 750 L by
opening a valve. The flow of gas into the chamber stops when the pressures inside the chamber
and the cylinder equal 100 kPa. The temperature of the gas is uniform throughout and it is equal
to 310 K. What was the original pressure inside the cylinder?
Solution After C02 is admitted into the chamber, the total volume of the gas ( V 2 ) =
1000 L ( T2 = 310 K, P 2 = 100 kPa). Initial volume ( Vx ) = 250 L ( Tx = 300 K, Px = ?). Eq. (4.10)
can be rearranged to give
/ \ /

px V
= p2 2 - Ty
\

Substituting the values, we get

4.2 MIXTURES OF IDEAL GASES

Px = 100
f

v 250— ooo / 300 V

J UioJ =
387.1 kPa

Consider a mixture of different gases A, B, C, etc . at temperature T and pressure P and let
the total volume of the mixture be V . Let nA, nB , nc , etc. be the number of moles of the different
components. If all the component gases are ideal, then the behaviour of the individual species
is not influenced in the presence of other gases in the mixture . This is because of the absence
of intermolecular forces in an ideal gas. The pressure exerted by nA moles of A in the mixture
will be the same as the pressure exerted when nA moles of A alone occupy a volume V at
temperature T . This is true for the other constituents B, C, etc. as well. The pressure exerted by
a constituent in a mixture of gases when it alone occupies the total volume at a given
temperature is called the partial pressure of that constituent in the mixture. The partial
 Ideal Gases and Gas Mixtures 83

pressure of constituent / is denoted by pv In the case of ideal gases this is also equal to the
pressure exerted by the constituent / in the mixture.
Pure -component volume is defined as the volume occupied by a component if it alone were
present at the total pressure and temperature of the mixture. The volume V! occupied by the pure
component / at T and P the temperature and pressure of the mixture, is the pure-component
9

volume of / in the mixture. This is in fact a fictitious volume as the constituents cannot have
individual volumes in the mixture as they get distributed throughout the container. However, it
can be viewed as the contribution of individual constituents to the total volume of the mixture,
in which case it is also known as the partial volume . Even this is strictly true only for ideal
gases. The partial volume of a component in the mixture is the increase in the volume of the
mixture resulting by the addition of a given number of moles of the constituent at the temperature
and pressure of the mixture . For ideal gases, this increase in volume will be the same as the
pure-component volume because the intermolecular forces are negligible. For real gases, however,
there may be volume change on mixing and the partial volume and pure-component volume will
be different.

4.2.1 Dalton’ s Law

Dalton proposed the law of additive pressures in 1805 which states that the total pressure of
a mixture of gases is equal to the sum of the partial pressures of the individual components.
Stated mathematically,
P = PA + PB + Pc + - = 2 P,
Dalton’s law is strictly true only for ideal gases. For real gases, the partial pressure of a
component as defined above and the pressure exerted by it in the mixture may be different
because of the differences arising due to the change in intermolecular forces in the new
environment in the mixture as compared to those in the pure state.
If the constituent gases are ideal, the mixture also will be ideal so that
PV = nRT (4.13)
where
n = nA + nB + nc + ... = Z ni

n is the total number of moles in the mixture. Also, by the definition of partial pressures,
PAV nART
=
pBV =nBRT (4.14)
pcV = ncRT
Adding the terms on both sides of Eq. (4.14), we get
(PA + PB + Pc + -W = (PA + nB + nc + ...)RT (4.15)
or
( - '• ! ' ( - » ) RT = nRT (4.16)
84 Stoichiometry and Process Calculations

Comparing Eq. (4.13) with Eq. (4.16), we see that

p = Pi
*
thus verifying the applicability of Dalton’s law for ideal gases.
Another useful result that follows from Dalton’s law is that the partial pressure of a
component gas in an ideal gas mixture is the product of its mole fraction and the total pressure .
Divide Eq. (4.14) by Eq. (4.13).
Pi_ — = y, (4.17)
P n
where / = A , B , C, ... and yi is the mole fraction of i in the mixture . Equation (4.17) can be
written as
Pi = yf (4.18)

4.2.2 Amagat’ s Law of Additive Volumes

Amagat’s law states that the total volume of a mixture of gases at a given temperature and
pressure is equal to the sum of the pure component volumes of the constituents at the same
temperature and pressure. This law is strictly true only for ideal gases. It can be stated
mathematically as
v = VA + VB + Vc + ... = Z v t (4.19)

Using the definition of pure component volume and assuming the gases are ideal, we can
write
PV 4 = nART
PVB = nBRT (4.20)
PVC = ncRT

Adding the terms on both sides of Eq. (4.20), we get

P( PA + VB + Vc + ...) = ( nA + nB + nc + ...)RT (4.21)
That is
P
H-H RT = nRT

Since Eq. (4.13) is applicable for the mixture as a whole, we see that
(4.22)

V = 'LVi

which shows that Amagat’s law is applicable for ideal gases. Also, by dividing Eq. (4.20) by
Eq. (4.13), we get
K = y, (for z = A , B , C , ... ) (4.23)
v n
 Ideal Gases and Gas Mixtures 85

where y, is the mole fraction of gas / in the mixture. Equation (4.23) means that the volume
fraction and mole fraction in an ideal gas mixture are identical, the result we have used in
Chapter 3. Combining Eqs. (4.17) and (4.23) the following general result of great applicability
is deduced :
mole fraction = volume fraction = pressure fraction

4.2.3 Average Molecular Weight

Through the use of average molecular weight, a complex gas mixture can be treated as though
it is a pure gas. If m is the mass of a mixture of gases and Mav its average molecular weight,
then the number of moles of the mixture n is given by
m = n Mav (4.24)
We can calculate the average molecular weight of a mixture of gases knowing its molal
composition. Assume a suitable basis, say 100 moles of the mixture, and evaluate the number
of moles of each constituent in the mixture. The mass of each constituent in the mixture is
obtained by multiplying the number of moles by the respective molecular weight.
rrij = rijMj (4.25)
where mi is the mass and n , is the number of moles of constituent / in the mixture and Mi its
molecular weight. The total mass of the mixture is the sum of the individual masses.
= = X ri' Mi (4.26)
The average molecular weight is calculated as

^ av =-
n
(4.27)

4.2.4 Density and Specific Gravity

The density of a mixture of gases is the mass per unit volume of the mixture at the specified
conditions of temperature and pressure. It is expressed in kg/m 3, g/ L, lb/ft3, etc. From the molal
composition of the mixture, the mass of n moles of the mixture can be evaluated by the method
outlined above. The volume of n moles of the gas mixture at the specified temperature and
pressure is determined by using Eq. (4.9) or Eq. (4.11). The density is now evaluated as the ratio
of mass to volume.
Let Mav be the average molecular weight of the gas mixture . Then, the mass of n moles of

the gas is m = nMav. Volume is obtained from the ideal gas equation V = . Therefore,

m PMav
density = f = (4.28)

As volume of gas depends strongly on temperature and pressure, the density is very much
dependent on the temperature and pressure of the gas . When the standard temperature and
pressure are used in the computation, the value so calculated is the density of the gas at STP.
86 Stoichiometry and Process Calculations

The specific gravity of a gas is the ratio of the density of the gas to the density of dry
air at the same temperature and pressure. Using Eq. (4.28) we can show that the specific
gravity of a gas is the ratio of the average molecular weight of the gas to that of dry air.

EXAMPLE 4.6 An analysis of the vent gases from the chlorinator in a plant for making
chlorinated rubber showed 70% by volume HC1, 20% by volume Cl 2 and the rest CC14. Determine
the following:
(a) The percent composition by weight
(b) The average molecular weight of the gas
(c) The density at standard conditions (in kg/m 3)
Solution For gas mixtures, the volume percent and mole percent are the same. Therefore,
the gas contains 70% (mole) HC1, 20% (mole) Cl 2 and 100 - 70 - 20 = 10% (mole) CC14.
Basis: 100 kmol gas mixture
(a) The calculations are presented as follows:

Component No. of kmol Molecular Mass in kg Weight

weight percent
HC1 70 36.453 2551.71 46.33
C12 20 70.906 1418.12 25.75
CC14 10 153.812 1538.12 27.92
Total 5507.95 100.00

Mass in kg is obtained by multiplying the number of kmol of each constituent by its

molecular weight. Weight percent is calculated by dividing the mass in kg of each
component by the total mass and by multiplying by 100. For example, for chlorine, the
1418 12
mass is 1418.12 kg and the mass percent is x 100 = 25.75% .
5507.95
(b) Average molecular weight of the gas is obtained by dividing the total mass by the
number of moles. Here, 100 kmol has a mass = 5507.95 kg. Therefore,
5507.95
average molecular weight = —— — = 55.08

( c ) 100 kmol of an ideal gas occupies a volume of 100 x 22.414 m 3 at STP. We have already
found out that the mass of 100 kmol is 5507.95 kg. Since density is mass/volume,
5507.95
density at standard conditions = = 2.4574 kg/m 3
100 x 22.414

EXAMPLE 4.7 Natural gas is piped from the well at 300 K and 400 kPa. The gas is found
to contain 93.0% methane, 4.5% ethane and the rest nitrogen. Calculate the following:
(a) The partial pressure of nitrogen
(b) The pure-component volume of ethane in 10 m 3 of the gas
(c) The density at standard conditions in kg/m 3
( d) The density of the gas as piped in kg/m 3
 Ideal Gases and Gas Mixtures 87

(e) The average molecular weight of the gas

(f ) The composition in weight percent
Solution
(a) Mole percent of nitrogen = 100 - 93.0 - 4.5 = 2.5. Therefore,
mole fraction of nitrogen = 2.5/100 = 0.025
Using Eq. (4.18),
partial pressure of nitrogen = mole fraction of nitrogen x total pressure
= 0.025 x 400 = 10 kPa
(b) Using Eq. (4.23),
pure-component volume of ethane = mole fraction of ethane x total volume
= (4.5/100) x 10 = 0.45 m 3
(c) Basis: 100 mol natural gas
The calculation are presented as follows:

Component Molecular No. of Weight (g ) Weight fraction

weight moles

Methane 16.032 93.0 16.032 x 93.0 = 1490.98 1490.98/1696.24 = 0.8790

Ethane 30.048 4.5 30.048 x 4.5 = 135.22 135.22/1696.24 = 0.0797
Nitrogen 28.014 2.5 28.014 x 2.5 = 70.04 (1 -- 0.8790 - 0.0797) = 0.0413
:

Total 100.0 1696.24 1.00

mass
density =
volume
The mass of 100 moles = 1696.24 g = 1.696 kg.
The volume of 100 moles at STP is
100(22.414 x 10 3) = 2.2414 m 3
-

Therefore,
1.696
= 0.7567 kg/m 3
density =
2.2414
(d) The volume at 300 K and 400 kPa is
/i
Pn T 101.325 300 \
A I

F0 x — —
P Tr0
x
V
= 2.2414
400 / v 273.15 /
= 0.6236 m 3
Therefore, the density at 300 K and 400 kPa is
1.696
2.7197 kg/m 3
0.6236
(e) The mass of 100 moles of the gas = 1696 g. Therefore,
average molecular weight = 1696.0/100 =16.96
(f ) Composition in weight percent is obtained by multiplying the weight fraction by 100.
Thus
Methane = 87.90%, Ethane = 7.97%, and Nitrogen = 4.13%
88 Stoichiometry and Process Calculations

4.2.5 Calculations Involving Change in the Mass

Material and energy balance calculations usually deal with physical operations in which a gas
stream undergoes change in mass. This change in mass results due to condensation of certain
constituents in the mixture, due to absorption of certain soluble constituents in a liquid solvent,
due to evaporation of liquids into a gas stream, or due to the adsorption of certain constituents
on a solid adsorbent surface. Separation techniques such as humidification, dehumidification,
gas absorption, drying and adsorption are some examples of such operations. Chapter 9 gives
brief explanation of the principle behind these operations. In all these operations it can be seen
that even when the total mass of the mixture changes, the mass of certain components in the
gas remains unchanged . For example, in the removal of water vapour present in an inert gas
stream by adsorbing the vapour on silica gel, the amount of inert gas in the stream entering
the adsorber as well as in the stream leaving the adsorber will be the same . Only the amount
of water vapour is reduced due to adsorption. In such operations where the amount of one of
the components in the mixture remains unchanged, it will be convenient to base the calculations
on such components. Such materials are known as tie elements or key components. If the
temperature and pressure of the gases entering and leaving the unit are the same, the change
in the volume of the gas directly gives the change in the mass of the non-tie elements. If the
conditions at the entrance and the exit are different, appropriate corrections are necessary.
There are several methods for solving the problems involving the changes in the mass of the
gas mixture . The choice of a suitable method depends largely on the type of data available.
Example 4.8 illustrates the different techniques used for solving such problems.

EXAMPLE 4.8 100 m 3/h of an ammonia-air mixture containing 20% ammonia by volume is
admitted to an absorption column at 120 kPa and 300 K in order to recover ammonia by
absorbing in water. 90 percent of ammonia in the entering gas is absorbed and the gas leaves
the column at 100 kPa and 280 K. What is the volume of gas leaving in one hour?
Solution Basis: 1 hour operation
Calculation on a mole basis: The number of moles of the gas entering is determined using
the ideal gas equation. Since volume percent and mole percent are the same, moles of ammonia
and air in the gas entering the column and the moles of ammonia absorbed can be calculated.
The moles of air entering will be equal to the moles of air leaving as air is not absorbed. The
sum of the moles of air leaving and the moles of ammonia that is left unabsorbed gives the total
moles of the gas leaving. This is converted to volume at the desired temperature and pressure
using the ideal gas equation.
Gas entering = 100 m 3 at 120 kPa and 300 K.
Using Eq. (4.12), the volume at standard conditions is determined which is divided by
22.414 to give the number of moles of the gas entering.
V P T0
Moles of gas entering Xy Xy
22.4143 P0 T

100 120 273.15

= 4.8108 kmol
22.4143 101.325 300
 Ideal Gases and Gas Mixtures 89

Moles of air entering = moles of air leaving = 0.80 x 4.8108 = 3.8486 kmol
Moles of ammonia entering = 0.20 x 4.8108 = 0.9622 kmol
Moles of ammonia absorbed = 0.90 x 0.9622 = 0.8659 kmol
Moles of ammonia leaving = 0.9622 - 0.8659 = 0.0963 kmol
Total gas leaving = 3.8486 + 0.0963 = 3.9449 kmol
Volume of gas leaving at standard conditions = 3.9449 x 22.4143 = 88.422 m 3
Using Eq. (4.11), the volume of gas leaving at 100 kPa and 280 K is

V0 x
^
P
-x
—r
0
= 88.422 X
101.325
100
X
280
273.15
= 91.84 m 3

Calculation on a pure- component volume basis: It is assumed that the absorption of ammonia
(that results in the reduction in the number of moles of ammonia in the gas) occurs at the
temperature and pressure of the entering gas. As there is no change in the number of moles of
air, the pure component volume of air remains the same as that before absorption. The total
volume of the gas decreases by the pure -component volume of ammonia absorbed, which is
determined directly from the given data. The sum of the pure component volume of ammonia
remaining unabsorbed and the pure-component volume of air makes up the total volume of the
gas after absorption at the initial temperature and pressure . This is then converted to the volume
at the final temperature and pressure.
Gas entering (120 kPa, 300 K):
Pure -component volume of air = 80 m 3
Pure -component volume of ammonia = 20 m 3
Gas after absorption (120 kPa, 300 K):
Pure -component volume of air = 80 m 3
Pure component volume of ammonia absorbed = 0.90 x 20 = 18 m 3
Pure-component volume of ammonia remaining = 20 - 18 = 2 m 3
Total volume after absorption (120 kPa, 300 K) = 80 + 2 = 82 m 3
Equation (4.10) gives

V2 = Vlx —Pi x —Tx

Therefore, the volume of gas leaving (100 kPa, 280 K) is
120 280
82 x = 91.84 m 3
ioox 300
Calculation on a partial pressure basis: Assume that the absorption is taking place at the
temperature of the gas entering without any change in the total volume. Therefore the reduction
in the number of moles due to absorption will lead to the reduction in the partial pressure of
ammonia in direct proportion to the decrease in its number of moles. However, the partial
90 Stoichiometry and Process Calculations

pressure of the tie element— the air— remains the same as that before absorption. At this
pressure, the volume occupied by air is equal to the total volume of the gas. The total volume
of the gas leaving at the specified temperature and pressure can now be computed using
Eq. (4.10). Alternatively, the total pressure after absorption can be found out as the sum of the
partial pressures of the air and the partial pressure of ammonia that is not absorbed . This can
be used to calculate the total volume of the gas leaving the absorber.
Since the partial pressure is given by the product of mole fraction (or, volume fraction) and
the total pressure, we have for the gas entering the absorber,
Partial pressure of air = 0.80 x 120 = 96 kPa
Partial pressure of ammonia = 0.20 x 120 =24 kPa
Partial pressure of ammonia after absorption = 24 x 0.10 = 2.4 kPa
Total pressure after absorption = 96 + 2.4 = 98.4 kPa
We have 100 m 3 of the gas at 98.4 kPa and 300 K after absorption. Therefore using Eq. (4.10),
the volume of gas leaving the absorber at 100 kPa and 280 K

K x —PP x —Ti = 100 x 98.4

2
x
100 300
280
= 91.84 m 3

EXAMPLE 4, 9 Air is to be dehumidified by condensing the water vapour present in it by

cooling at constant pressure. 100 m 3 of air at 100 kPa and 300 K contains water vapour which
exerts a partial pressure of 4 kPa. Keeping the pressure constant, this air is cooled to 275 K
and the condensed water is removed. The partial pressure of water in the air after cooling is
found to be 1.8 kPa. Calculate the following:
(a) The volume of air after dehumidification in m 3
(b) The mass of water removed in kg
Solution Basis: 100 m 3 air entering
(a) In the partial pressure method, the change in the number of moles is taken into account
by a corresponding change in the pressure :
Partial pressure of dry air entering = 100 - 4 = 96 kPa
Partial pressure of dry air leaving = 100 - 1.8 = 98.2 kPa
Dry air at 96 kPa and 300 K occupies a volume 100 m 3. Therefore, the volume
occupied by the dry air at 98.2 kPa and 275 K is

v1 X AxZl = i 0 0 x -
P2 ^ -x
98.2
—300 = 89.61 m 3

-
This will be the volume occupied by the air water vapour mixture after condensation.
(b) The volume of water vapour entering at its partial pressure is the same as the volume
of total gas entering. Therefore,
, . volume of water vapour at STP
moles of water vapour entering =
normal molal volume
——
Vp V P T
22.414
= 22.414 *y P *y T0
0
 Ideal Gases and Gas Mixtures 91

100 4 273 15
X — = 0.1604 kmol
X
22.414 101.325 300
Similarly, the volume of water vapour leaving at its partial pressure is the volume of
total mixture leaving. Therefore, the moles of water vapour leaving is
Vp V P Tf0
X X
22.414 22.414 Pi0 T
89.61 1.8 273.15
X X = 0.0705 kmol
22.414 101.325 275
Mass of water vapour removed = moles x molecular weight of water
= (0.1604 - 0.0705)18.02 = 1.619 kg
EXAMPLE 4.10 The feed to an absorption column consists of 20% H 2S and the balance
inerts. Only H 2S is removed from the gas by absorbing in an alkaline solution. The gas enters
the absorber at 600 kPa and 310 K and leaves at 500 kPa and 290 K containing 2% H 2S. If H 2S
is removed at a rate of 100 kg/h, calculate the following:
(a) The volume of gas (in m 3) entering per hour
(b) The volume of gas (in m 3) leaving per hour
(c) Percentage recovery of H 2S

Solution Basis: 100 m 3 gas entering

The volume of gas entering at STP is
600 273.15
F0 = F x —P x —T = 100 x 101.325 X
310
= 521.76 m 3
0
Moles of gas entering is
Vp
521.76
= 23.28 kmolt
22.414 22.414
Mole fraction of H 2S in the gas = volume fraction = 0.20
Moles of H 2S entering = 0.20 x 23.28 = 4.656 kmol
Moles of inerts entering = 23.28 - 4.656 = 18.624 kmol
Moles of inerts leaving will be the same as those entering. But inerts constitute 98% of the
gas leaving. Therefore,
18.624
Moles of total gas leaving = 19.00 kmol
0.98
Moles of H 2S in the gas leaving = 0.02 x 19.00 = 0.38 kmol
Mass of H 2S absorbed = moles absorbed x molecular weight
= (4.656 - 0.38)34.08 = 145.726 kg
92 Stoichiometry and Process Calculations

(a) 145.726 kg of H 2S is absorbed per 100 m3 of gas entering. For the removal of 100 kg/h
of H 2S, gas entering per hour is
100 3
X 100 = 68.622 m /h
145.726
(b) 19 kmol gas leaves per 100 m 3 of gas entering, moles of gas leaving per 68.622 m 3/h
of gas entering is

— X 68.622 = 13.038 kmol/h

100
The volume of gas leaving at STP is
13.038 x 22.414 = 292.23 m 3/h
The volume of gas leaving at 500 kPa and 290 K is
R T 101.325 290
V0 x o x = 292.05 x x = 62.87 m 3/h
P Tro 500 273.15
( c ) For 4.656 kmol H 2S in the gas entering, 0.38 kmol is present in the gas leaving.
Therefore, the percent recovery of H 2S is
(4.656 - 0.38)
x 100 = 91.84%
4.656

4.3 REACTIONS INVOLVING GASES

Gases take part in chemical reactions as reactants, products or as both. The law of combining
proportions indicates that the number moles of the substances taking part in a chemical
reaction bears a simple ratio of whole numbers. For example, the ratio of moles of nitrogen
to hydrogen reacting to form ammonia is 1:3. If both nitrogen and hydrogen are at the same
conditions of temperature and pressure, the ratio of their volumes will also be 1:3. This is
because of Avogadro's law which means that equal volumes of all gases contain the same
number of molecules. Thus, 1 m 3 of nitrogen reacts with 3 m 3 of hydrogen forming 2 m 3
of ammonia if the temperature and pressure are constant. If the temperature and pressure of
the reactants and products are not the same, the volumes may be corrected using the ideal
gas equation .
The use of molal quantities is recommended for performing these calculations. The
advantage is that for calculations carried out in molal quantities, the complications arising due
to the change in volumes accompanying the changes in temperature and pressure can be
avoided . Once the results are obtained in molal quantities, they may be converted to the
volumetric basis, using the normal molal volume constant and the ideal gas law. The choice
of a suitable basis for the calculation depends on the type of data available. A unit weight
or unit mole (a basis of 100 moles is preferred for gas mixtures) of a substance may be chosen
as the basis depending upon whether the given data for the substance is in weight units or
volume units. The following examples will illustrate the calculations involving ideal gases in
chemical reactions.
 Ideal Gases and Gas Mixtures 93

EXAMPLE 4.11 Ammonia is made by the reaction between hydrogen and nitrogen according
to the following reaction:
N 2 + 3H 2 -> 2NH 3
(a) For complete conversion of 100 cubic metres of nitrogen at 20 bar and 350 K, what
volume of hydrogen at the same conditions of temperature and pressure is theoretically
required?
(b) What is the volume of hydrogen at 5 bar and 290 K required which is stoichiometrically
equivalent to 100 m 3 of nitrogen at 20 bar and 350 K ?
(c) If the reaction is carried out at 50 bar and 600 K, what volumes of nitrogen and
hydrogen at these conditions are theoretically required for producing 1000 kg of ammonia
and what will be the volume of ammonia produced at the reactor conditions?
Solution
(a) According to Avogadro’s principle, equal volumes of all gases under similar conditions
of temperature and pressure contain the same number of moles. Since one mole nitrogen
requires three moles hydrogen, 100 m 3 of nitrogen at 20 bar and 350 K requires 300
m 3 hydrogen at the same temperature and pressure.
(b) The volume of hydrogen that is stoichiometrically equivalent to 100 m 3 of nitrogen at
20 bar and 350 K is 300 m 3 at 20 bar and 350 K . Therefore, at 5 bar and 290 K the
equivalent volume is

F1 x
^ ^Tx =
-x
P2
- 300 x —
5
x — = 994.29 m 3
350
(c) Basis: 1000 kg ammonia
Moles of ammonia = 1000/17.03 = 58.72 kmol
2 moles of ammonia requires 1 mole of nitrogen and 3 moles of hydrogen. Therefore,
58.72 kmol requires 29.36 kmol nitrogen and 88.08 kmol hydrogen.
29.36 kmol nitrogen will have a volume 29.36 x 22.414 m 3 at STP. At 50 bar and
600 K, the volume of nitrogen is
P T (1.01325 V 600 \
3
fT r0 x —0 x — = 29.36 x 22.414 = 29.29 m
P Tro V 50 y v 273.15 y
Volume of hydrogen = 29.29 x 3 = 87.88 m 3
Volume of ammonia = 29.29 x 2 = 58.59 m 3

EXAMPLE 4.12 Producer gas has the following composition by volume: Carbon monoxide
= 25.0%, carbon dioxide = 4.0%, oxygen = 3.0% and nitrogen = 68.0%.
(a) Determine the volume of the gas at 1 bar and 290 K per kg carbon.
(b) 100 m 3 of the gas at 1 bar and 290 K is to be burned with air 20% in excess of
that is theoretically required for complete combustion . What volume of air is
required at 1 bar and 290 K ? ( Assume that air is a mixture of 21.0% oxygen and
79.0% nitrogen .)
(c) For the conditions in part (b), what would be the composition of the gas after complete
combustion?
94 Stoichiometry and Process Calculations

Solution Basis: 100 kmol producer gas

(a) The gas contains 25.0 kmol C02 and 4.0 kmol CO. Moles of carbon present = 25.0
+ 4.0 = 29.0 kmol.
Therefore, the mass of carbon per 100 kmol gas is
29.0 x 12 = 348.0 kg
Moles of producer gas that contains 1 kg of carbon is

—348 = 0.2874 kmol

The volume of 0.2874 kmol gas at STP is
0.2874 x 22.414 = 6.44 m 3
The volume of gas at 1 bar and 290 K is
B T
V Q X o x = 6.44
f 1.01355 V 290 \ 6.93 m 3
=
P Tro V 1 / v 273.15 /

(b) CO +
V_ > C02
100 kmol gas contains 25.0 kmol CO which requires 12.5 kmol oxygen for complete
combustion. 3.0 kmol oxygen is already present in the gas mixture. Therefore, the
theoretical requirement of oxygen is 12.5 - 3.0 = 9.5 kmol.
Oxygen supplied is 20% in excess of the theoretical requirement. Hence,
oxygen supplied = 1.2 x 9.5 = 11.4 kmol
Since air contains 21.0% oxygen, air supplied is

11.4 x —21 = 54.286 kmol

100 kmol gas requires 54.286 kmol air. Since air and the fuel are at the same conditions
of temperature and pressure, 100 m 3 of the fuel gas will require 54.286 m 3 of air.
(c) After complete combustion, the products contain:
Carbon dioxide = carbon dioxide present in the fuel
+ carbon dioxide produced by combustion of CO
= 4.0 + 25.0 = 29.0 kmol
Oxygen = oxygen supplied + oxygen present in the fuel - oxygen consumed
= 11.4 + 3.0 - 12.5 = 1.9 kmol
Nitrogen = nitrogen present in the fuel + nitrogen in the air supplied
= 68.0 + (54.286 - 11.4) = 110.886 kmol
Total products = 29.0 + 1.9 + 110.886 = 141.786 kmol
Percent composition (mole ):
29.0
Carbon dioxide = x 100 = 20.45%
141.786
 Ideal Gases and Gas Mixtures 95

1.9
Oxygen = x 100 = 1.34%
141.786
110.886
Nitrogen = x 100 = 78.21%
141.786
Percent composition by volume and percent composition by mole are identical.

EXAMPLE 4.13 Chlorine is produced by the oxidation of hydrogen chloride gas with air
4HC1 + 02 -> 2C12 + 2H 20
The reaction is carried out at 1.2 x 105 N/m 2and 400 K . 50 percent excess air is used
and the reaction is only 80 percent complete . Calculate the following:
(a) The volume of air admitted per 100 m 3 of HC1 if both air and HC1 enter the reactor
at 1.0 bar and 290 K
(b) The volume of gases leaving the reactor per 100 m 3 of HC1 entering
(c) Kilograms of chlorine produced per 100 m 3 of HC1 entering
(d) The percent composition by volume of the exit gas on a dry basis
Solution Basis: 1 mol HC1 entering the reactor
(a) Oxygen required = 0.25 mol
Oxygen supplied = 1.5 X 0.25 = 0.375 mol

Air supplied = x 0.375 = 1.786 mol

1 mol HC1 requires 1.786 mol air. Since air and HC1 enter at same temperature and
pressure, the volumes of HC1 and air bear the same ratio 1 : 1.786. Therefore, for 100
m 3 of HC1, the air admitted is

100 = 178.6 m 3
1
(b) Only 80% of the HC1 is converted . HC1 converted is 0.8 mol.
Oxygen consumed = 0.8/4 = 0.2 mol, chlorine produced = 0.8/2 = 0.4 mol, and water
produced = 0.4 mol. Therefore, the gases leaving the reactor are as follows:

Compound No. of moles

HCl 1 - 0.8 = 0.20
Oxygen 0.375 - 0.20 = 0.175
Chlorine 0.40
Water 0.40
Nitrogen 1.786 - 0.375 = 1.411
Total 2.586

Moles of gas leaving per mol HC1 entering is 2.586 mol.

96 Stoichiometry and Process Calculations

For 100 m 3 of HC1 entering at 1 bar and 290 K, the volume of gas leaving will be 2.586
x 100 = 258.6 m 3 at 1 bar and 290 K. Therefore, volume of gas leaving at 1.2 bar
and 400 K is

v1, X
^ ^i
P2
-X
7
- = 258.6 X — —290 = 297.24 m
1.2
X

( c ) Per mol HC1 entering, chlorine produced is 0.4 mol. That is, per 100 m 3 of HC1
3

entering, chlorine produced will be 40 m 3 at 1 bar and 290 kPa .

This is equivalent to
?7 1 5
40 x
1
x ^:— = 37.18 m 3 at STP
1.01325 290
or 37.18/22.414 = 1.66 kmol
Therefore, the mass of chlorine produced = 1.66 x 70.90 = 117.62 kg
(d) The percent composition on a dry basis does take into account the water present in the
-
mixture. On a water free basis, the composition is evaluated as follows:

Compound No. of moles Mole percent

HC1 1 - 0.8 = 0.20 (0.2/2.186) x 100 = 9.15
Oxygen 0.375 - 0.20 = 0.175 (0.175/2.186) x 100 = 8.00
Chlorine 0.40 (0.40/2.186) x 100 = 18.30
Nitrogen 1.786 - 0.375 = 1.411 (1.411 /2.186) x 100 = 64.55
Total 2.186 100.00

EXAMPLE 4.14 Carbon dioxide dissociates into carbon monoxide and oxygen at 1 bar and
3500 K.

C02 CO + |o 2

25 L of C02 at 1 bar and 300 K is heated to 3500 K at constant pressure. If all gases behave
ideally, determine the following:
(a) The final volume of the gas if no dissociation had occurred .
(b) If the final volume is found to be 0.35 m 3 what fraction of C02 is dissociated?
Solution
(a) If no dissociation had occurred, the final volume is given by the ideal gas equation
' lV 3500 N
V, x —P 2
x —
7)
= 25 x 1(T3
1 Jt 300 /
= 0.292 m3

(b) Moles of C02 initially taken is

Vp V P T0
= *y *y
22.414 22.414 P0 T
 Ideal Gases and Gas Mixtures 97

25 1 273.15
X
22.414 1.01325
X
300
= 1.00 mol
Let z be fraction of C02 dissociated . Then after dissociation the mixture contains:
C02 = 1.00 - z mol, CO = z mol, 02 = z mol
Therefore, the total moles after decomposition = (1.00 + 0.5 z) mol. (A)
Since the gas mixture occupies 0.35 m 3 at 1 bar and 3500 K, the number of moles present
is
VQ V P To
X
22.414 22.414 PQX T
350 1 273
X
22.414 1.01325
X
3500
= 1.20 mol (B)

Comparing (A) and (B), we get

(1.0 + 0.5z) = 1.2
Solving this, we get z = 0.40, which means 40% of C02 is converted .

EXERCISES
Ideal gas
4.1 How many kilograms of nitrogen will occupy a volume of 1000 m 3 at a pressure of
1.2 bar and a temperature of 400 K?
4.2 A gas occupies a volume of 100 m 3 at 375 K and 1.25 x 105 N/m 2. What volume will
the gas occupy at 275 K and 1 bar?
4.3 20 kg of chlorine is to be stored in a container at 0.9 bar and 295 K . What should be
the volume of the container?
4.4 (a) How many kilograms of liquid water will be obtained by the complete condensation
of 5 m 3 water vapour at 200 kPa and 1000 K ?
(b) The steam tables give the specific volume of water vapour to be 2.937 m 3/kg. Using
this data calculate the mass of water vapour obtained and compare with the results
in part (a).
4.5 Steam tables give the specific volume of superheated steam at 1200 kPa and 925 K to
be 0.3534 m 3/kg. How does it compare with the value obtained by the ideal gas
equation?
4.6 It is desired to compress 7.00 kg of nitrogen gas to a volume of 0.5 m 3 at 305 K.
Calculate the pressure required.
4.7 A fire-extinguisher tank can hold 1 m 3 of gas. The tank contains 10 kg of C02 at 300 K.
What will be the pressure of the gas in N/m 2?
4.8 A 20 L glass vessel contains 28 g nitrogen. If the vessel cannot withstand a pressure
exceeding 120 kPa, up to what temperature the gas in the vessel can be heated?
98 Stoichiometry and Process Calculations

4.9 Calculate the density at standard temperature and pressure of (a) methane (b) sulphur
dioxide .
4.10 A 50 m diameter spherical balloon contains air at 300 K and 1 bar. How many kilograms
of air is present in the balloon? Take the molecular weight of air to be 29.
4.11 Find the mass of methane in a 100 m 3 gas holder at 293 K if the pressure on the holder
is 20 kPa gauge . The barometric pressure is 100 kPa.
4.12 How many kilograms of hydrogen can be stored at 325 K and 100 bar in a compressed
gas cylinder that normally holds 0.5 kg hydrogen at 300 K and 130 bar?
4.13 A tank contains oxygen gas at 1.40 x 107 N /m 2. On withdrawing 140 L of oxygen
measured at 1.01 x 105 N /m 2, the pressure in the tank is observed to fall to 1.30 x 105
N /m 2. Assume that there is no change in the temperature of the gas. What is the volume
of the tank in m 3?
4.14 A cooking gas cylinder can withstand a pressure of 15.0 atm . The pressure inside the
cylinder is 12 atm at 300 K. During a sudden fire in the building the temperature starts
rising. At what temperature will the cylinder explode ?
4.15 Calculate the volume occupied at 400 K and 2 atm pressure by the gas evolved from
2 ml of solid C02. The density of solid C02 = 1500 kg/m 3.

Mixtures of ideal gases

4.16 A vessel of volume 0.02 m 3 contains a mixture of hydrogen and helium at 320.15 K
and 4.15 x 105 N /m 2 pressure. The mass of the mixture is 10 g . Calculate the
individual masses of hydrogen and helium in the mixture.
4.17 The flow rate of a gas mixture consisting of 60% ethane , 25 % hydrogen and
15 % carbon dioxide is found to be 200 m 3/h at 300 K and 1.2 bar.
(a) Determine the composition of the gas in weight percent
(b) Express the composition in mol/L.
( c) What is the flow rate in kg/h?
4.18 2.0 cubic metres of oxygen at 200 kPa and 280 K is mixed with 10 kg of nitrogen
at 95 kPa and 300 K and the resulting mixture is brought to 110 kPa and 290 K.
(a) What is the partial pressure of oxygen in the final mixture ?
(b) What is the final volume of the mixture ?
4.19 In an air-naphthalene (C10H8) mixture at 70 kPa and 350 K, the partial pressure of
naphthalene is found to be 7 kPa. What volume of this mixture will contain 1 kg of
naphthalene?
4.20 15 kg each of nitrogen and hydrogen are mixed together at 300 kPa and 298 K.
Determine the following:
(a) The partial pressure of nitrogen
(b) The pure -component volume of nitrogen
( c ) The specific volume of the mixture (m 3/kg)
4.21 0.66 g of a gas containing 81.8% C and 18.2% H by weight measures 0.369 L at
100 kPa and 295 K . What is the formula of the hydrocarbon?
 Ideal Gases and Gas Mixtures 99

4.22 N 204 decomposes to N02 at high temperatures. 20 g of N 204 when heated to 373 K
at 96 kPa, is found to occupy a volume of 0.0125 m 3. Assuming the applicability of
ideal gas law, calculate the percent dissociation of N 204 to N02.
4.23 In the manufacture of formaldehyde by the Monsanto process, air, methyl alcohol, and
steam are used in the ratio 4:2:1 by weight at 800 kPa and 380 K. Calculate the partial
pressure of the gases in N/m 2.
4.24 What is the average molecular weight of a flue gas having the following composition
by volume?
C02: 13.0%, CO: 3.0%, 02: 4.0% and N 2: 80.0%
4.25 Assuming that air contains 78.1% nitrogen, 21.0% oxygen and 0.9% argon, calculate
the average molecular weight and density of air at 298 K and 1.01325 x 105 N/m 2.
4.26 A natural gas has the following composition by volume : C02: 0.8%, N 2: 3.2%, and CH 4:
96.0%. Calculate
(a) The composition in weight percent
(b) The average molecular weight
( c ) The density at standard conditions in kg/m 3
4.27 The average molecular weight of a gas mixture containing oxygen and other gases is
40. A student evaluated the average molecular weight as 36.8. He got the wrong result
because he used an incorrect value of 16 as the molecular weight of oxygen in the
calculation. What is the mole percentage of oxygen in the mixture?
4.28 A flue gas has the following percent composition by volume :
C02 = 14.00, S02 = 0.50, CO = 2.00, 02 = 2.5 and N 2 = 81.00.
Determine
(a) The average molecular weight of the gas
(b) The composition of gas in weight percent
( c ) The density of the gas at 320 K and 1.5 bar
(d) The specific gravity at 320 K and 1.5 bar
4.29 A gas mixture contains 10.0% C02, 15.0% Cl 2, 12.5% N 2 and the rest hydrogen.
Calculate the following:
(a) The average molecular weight of the gas
(b) The gas composition in weight percent
4.30 200 kg of a gas mixture containing 20% S02, 20% N02 and 60% N 2 is contained in
a gas cylinder. Determine the average molecular weight of the mixture
(a) If the analysis is on a mass basis
(b) If the analysis is on a volume basis
4.31 A sample withdrawn from a gas mixture at 120 kPa and 300 K gave the following
results when separated into its constituents: C 2H6 17.93 g, H 2 0.50 g, C02 6.57 g.
Determine the following:
(a) The average molecular weight
(b) The density of the gas mixture
100 Stoichiometry and Process Calculations

4.32 In a gas mixture consisting of hydrogen, nitrogen and carbon dioxide, the partial
pressures are 25 kPa for hydrogen, 35 kPa for nitrogen and 140 kPa for C02. For
50 m 3 of the gas mixture at 400 K, determine
(a) The number of moles of the mixture
(b) The number of moles and mole fraction of hydrogen
( c ) The mass and mass fraction of hydrogen
(d) The pure-component volume of hydrogen
(e) The average molecular weight of the mixture
4.33 The average molecular weight of a mixture of oxygen and sulphur dioxide is found to
be 44.8. For 5 kg of this mixture at 298 K and 200 kPa calculate
(a) The partial pressure of oxygen
(b) The volume of the mixture
( c ) The density at the standard conditions
4.34 An ammonia converter is charged with a 1:3 mixture of nitrogen and hydrogen at
1000 bar and 500 K. Calculate the following:
(a) The partial pressures of nitrogen and hydrogen
(b) The average molecular weight
( c ) The density of the mixture
4.35 A blue gas has the following composition by volume percent: CO: 34.8, H 2: 42.0,
CH 4: 0.4, C02: 5.5, 02: 0.2, and N 2: 17.1. Calculate
(a) The composition in weight percent
(b) The average molecular weight
( c ) The density at standard conditions in kg/m 3
4.36 A gas mixture has the following composition by volume: ethylene: 30.6%, benzene:
24.5%, oxygen: 1.3%, methane : 15.5%, ethane : 25%, and nitrogen: 3.1%. Calculate the
following:
(a) The average molecular weight
(b) The composition by weight
( c ) The density of the mixture at STP in kg/m 3
4.37 Air is dried from a partial pressure of 7 kPa of water vapour to a partial pressure of
1.5 kPa . The temperature of the entering air is 475 K. The pressure remains constant
at 1 bar at inlet and outlet. How much water in kilograms is removed per cubic metre
of entering gas?
4.38 An ammonia-air mixture containing 10% ammonia is sent to an absorber in which 90%
of ammonia is absorbed.
(a) What is the mole fraction of ammonia in the gas leaving?
(b) Express the composition of the exit gas from the absorber in weight percent.
(c) What is the average molecular weight of the gas entering and leaving the column?
(Average molecular weight of air is 29.)
 Ideal Gases and Gas Mixtures 101

Calculations involving change in the mass of the gas

4.39 Flue gas analysing 80.0% nitrogen, 7.0% oxygen and 13.0% carbon dioxide is sent to
a dryer at 500 K and 95 kPa. In the dryer it picks up moisture from the wet material
and leaves at 90 kPa and 360 K with the following composition: N 2 = 50%, 02 = 4.5%,
C02 = 8.0% and H 20 = 37.5%. Per 100 m 3 of gas entering the dryer, determine the
following:
(a) The volume of gas leaving the dryer
(b) The weight of water evaporated
4.40 Hydrochloric acid is obtained by absorbing HC1 gas in water. A gas mixture analyzing
30% HC1 and 70% air enters the absorber at 95 kPa and 320 K and leaves at 90 kPa
and 300 K. 95% of HC1 present in the entering gas is absorbed . For 100 m 3 of gas
entering the absorber, determine the following:
(a) The volume of gas leaving in m 3
(b) The mass of HC1 absorbed in kg
(c) The percent composition by volume of the gas leaving
4.41 Hydrochloric acid is obtained by absorbing HC1 gas in water. A gas mixture
consisting of HC1 and air enters the absorber at 95 kPa and 320 K with a partial
pressure of HC1 of 28.5 kPa and leaves at 90 kPa and 300 K with a partial
pressure of HC1 of 2 kPa . For 100 m 3 of gas entering the absorber determine the
following :
(a) The volume of gas leaving in m 3
(b) The mass of HC1 absorbed in kg
4.42 Air is to be dehumidified by cooling and condensation of water vapour present in it.
100 m 3 of air at 100 kPa and 305 K contains water vapour which exerts a partial
pressure of 3 kPa . Keeping the pressure constant, this air is cooled to 285 K and the
condensed water is removed. The partial pressure of water in the air after cooling is
found to be 1.5 kPa. Calculate the following:
(a) The volume of air after dehumidification in m 3
(b) The mass of water removed in kg
4.43 The feed to an absorption column consists of 30% H 2S and 70% inerts. Only H 2S is
removed from the gas by absorbing in an alkaline solution. The gas enters the absorber
at 700 kPa and 350 K and leaves at 600 kPa and 300 K containing 5% H 2S. If H 2S
is removed at a rate of 100 kg/h, calculate the following:
(a) Cubic meters of gas entering per hour
(b) Cubic meters of gas leaving per hour
( c) Percentage recovery of H 2S
4.44 A flue gas containing 18% C02 enters an absorber at 120 kPa and 400 K . Only C02
is absorbed and the gas leaves the unit at 95 kPa and 310 K containing 2% C02.
Assuming that 100 m 3 of gas is admitted to the unit, calculate
(a) The volume of gas leaving in m 3
(b) The weight of C02 absorbed in kg
102 Stoichiometry and Process Calculations

4.45 100 m 3 of a gas mixture in which benzene and nitrogen are present in the weight ratio
1 : 3 is sent to an absorption column to recover benzene. The gas enters the column
at 120 kPa and 350 K. The gas leaving the absorber measures 95 m 3 at 101.3 kPa and
300 K. Determine the following:
(a) The average molecular weight of the gas entering
(b) The average molecular weight of the gas leaving
(c) Weight in kilograms of benzene absorbed
(d) The percent recovery of benzene
4.46 50 cubic metres per minute of a gas containing 5% oxygen is flowing through a pipe.
It is desired to increase the oxygen content in the stream to 10% by (a) the addition
of pure oxygen and (b) the addition of air containing 21% oxygen and 79% nitrogen.
Determine the volumetric rate of addition (m 3/min) in both cases.
4.47 100 m 3/h of an ammonia-air mixture containing 20% ammonia by volume is admitted
to an absorption column at 120 kPa and 300 K in order to recover ammonia by
absorbing it in water. The gas leaves the column at 100 kPa and 280 K with a partial
pressure of ammonia of 2 kPa.
(a) What is the volume of gas leaving in one hour?
(b) How many kilograms of ammonia are recovered in one hour?
(c) What is the percent recovery ?
4.48 100 m 3 per hour of a mixture of toluene and air at 120 kPa and 375 K is passed
through a cooler where some of the toluene is condensed. Toluene exerts a partial
pressure of 50 kPa in the entering stream . The gases leaving the cooler measured
70 m 3 at 100 kPa and 325 K. Assuming an average molecular weight of 29 for air,
determine the following:
(a) The average molecular weight of gas leaving the cooler
(b) The amount of toluene (C 7H 8) condensed (in kilograms).
4.49 Two tanks are initially sealed off from one another by means of a valve. Tank I initially
contains 1 m 3 of air at 7 bar and 340 K. Tank II initially contains a mixture of oxygen
and nitrogen containing 95% nitrogen at 14 bar and 360 K. The valve is then opened
allowing the contents of the tank to mix. After complete mixing had been done, the gas
was found to contain 85% nitrogen. Calculate the volume of Tank II.
Reactions involving gases
4.50 Ammonia reacts with sulphuric acid giving ammonium sulphate
2NH 3 + H 2S04 (NH 4)2S04
(a) 20 m 3 of ammonia at 1.2 bar and 300 K reacts with 40 kg of sulphuric acid.
Which is the excess reactant and what is the percent excess?
(b) How many kilograms of ammonium sulphate will be obtained?
4.51 Sulphur dioxide reacts with oxygen producing sulphur trioxide.

so2 + \o2 -> so3

 Ideal Gases and Gas Mixtures 103

In order to ensure complete reaction, twice as much oxygen is supplied than that
required theoretically. However, only 60% conversion is obtained. The pressure was
500 kPa and temperature 800 K. 100 kg of S02 is charged to the converter. Determine
the following:
(a) The volume of pure oxygen supplied at 1.5 bar and 300 K
(b) The volume of sulphur trioxide produced
(c) The volume of gases leaving the converter
(d) The composition of gases leaving the converter
(e) The average molecular weight of the gas leaving the converter
4.52 Nitrogen dioxide shows a tendency to associate and form nitrogen tetroxide.
2N02 N 204
One cubic metre nitrogen dioxide at 100 kPa and 300 K is taken in a closed rigid
container and allowed to attain equilibrium at constant temperature and volume. The
pressure inside the container has fallen to 85 kPa at equilibrium .
(a) What is the degree of association?
(b) What is the partial pressure of N 204 in the final mixture ?
4.53 Ammonium chloride in the vapour phase dissociates into ammonia and hydrogen chloride
according to
NH 4C1 -4 NH 3 + HC1
10.7 g ammonium chloride is taken in a container. When dissociation is complete and
equilibrium is attained the pressure, volume and temperature of the gas mixture were
measured to be 1.2 bar, 7.764 x 10-3 m 3 and 400 K, respectively. Determine the
following:
(a) The fraction of ammonium chloride dissociated
(b) The partial pressure of HC1 in the products
4.54 One kilomole of methane is completely burnt to form C02 and water vapour using 10%
excess air than that required for complete combustion. The resulting gas mixture is
treated to remove all the water content.
(a) What will be the volume of dry gas leaving the burner at 110.3 kPa and 275 K ?
(b) What mass of water is removed from the products of combustion?
4.55 Pure sulphur is burned with excess air to give sulphur trioxide . Due to incomplete
oxidation some sulphur dioxide is also formed. The analysis of the burner gases
showed 0.8% S03, 7.8% S02, 12.2% 02 and 79.2% N 2. Determine the following:
(a) The percent excess air supplied
(b) The volume of burner gases at 1.2 bar and 600 K per kg sulphur burned
(c) The volume of air supplied at 1.013 bar and 288 K per kg sulphur burned
4.56 An organic ester of formula C19H3602 is to be hydrogenated at a rate of 100 kg/h to
yield C19H3802. The hydrogen required for the plant which runs continuously, is available
as 50 L cylinders in which the gas is contained at 70 bar and 300 K. How many
cylinders the company should order per week?
104 Stoichiometry and Process Calculations

4.57 Formaldehyde is produced by the gas phase oxidation of methanol with air over a
catalyst
CH3OH + \02 -> HCHO + H 20
100 m 3 of methanol vapour at 1.013 x 105 N /m 2 and 550 K is to be treated. If 10%
excess air is supplied and the reaction is only 80% complete, calculate
(a) The composition of the product gas
(b) The volume of product gases at 1.5 x 105 N/m 2 and 800 K
4.58 A gaseous mixture consisting of 50% hydrogen and 50% acetaldehyde (C 2H 40) is
initially contained in a rigid vessel at a total pressure of 1.0 bar. Methanol is formed
according to
C 2H 40 + H 2 C 2H60
After a time it was found that the total pressure in the vessel has fallen to 0.9 bar
while the temperature was the same as that of the initial mixture. Assuming that the
products are still in the vapour phase, calculate the degree of completion of the
reaction .
4.59 A sample of a gas mixture containing NO and N02 is contained in a standard cell of
volume 10 L at 170 kPa and 300 K. If the mixture weighed 28.087 g, what percent of
the gas mixture is NO?
4.60 A mixture of ethane (C 2H6) and ethylene (C 2H 4) occupies 4.0 x 10-2 m 3 at latm and
400 K. The mixture reacts completely with 0.130 kg of 02 to produce C02 and H 20.
Assuming ideal gas behaviour, calculate the mole fractions of C 2H 4 and C 2H6 in the
mixture .
4.61 Pure methane is completely burned with air. The gas leaving the burner which contain
no oxygen is passed through a cooler where some of the water is removed by
condensation. The mole fraction of nitrogen in the gas leaving the cooler was 0.8335.
Calculate the following:
(a) The analysis of the gas leaving the cooler
(b) Water condensed in kg per kmol of methane burned
(c) The partial pressure of water in the gas leaving the cooler at 325 K and 1.5 bar.
4.62 In the nitric acid manufacture, 100 m 3/h of ammonia at 290 K and 1 bar is mixed with
air and passed over a catalyst in a converter and the following reaction takes place :
4NH 3 + 502 -> 6H20 + 4NO
The gases from the converter are passed into an oxidizing tower where the oxidation
completed according to the following reaction:
2NO + 02 -> 2N02
The gases from the oxidizing tower are passed into a cooling tower where N02 is
absorbed in 50 kg/h of water and forms nitric acid according to the reaction
3N02 + H 20 -> 2HN03 + NO
 Ideal Gases and Gas Mixtures 105

The overall reaction for the process is given by

NH3 + 202 -> HN03 + H20
Air supplied is 20% in excess of that required for complete oxidation of the ammonia
to nitric acid and water. The degree of completion of the reaction in the converter is
85% and 90% of the nitric oxide entering the oxidising tower is converted to nitrogen
peroxide. Assume that the cooling tower exit gases contain no water vapour. Calculate
the following:
(a) The amount of air to be used in m 3/h at 1 bar and 290 K
(b) The amount of gases leaving the converter in m 3/h at 0.95 bar and 1000 K
(c ) The amount in kg/h and concentration in weight % of nitric acid produced
 5 Properties of
Real Gases

The significance of process calculations in which the change in quantity and state of the gases
are involved was pointed out in Chapter 4, while discussing the behaviour of ideal gases. Since
an ideal gas model provides a very simple equation of state, those calculations were quite
simple. But in practice, very few gases can be approximated as ideal gases. The assumption
of ideal gas behaviour in other cases leads to erroneous results depending upon the extent of
deviation of the gases from ideal behaviour. Instead of ideal gas equation, realistic models—
equations of state — which predict the actual behaviour of gases should be used in dealing with
real gases.

5.1 REAL GASES

At very low pressures and at very high temperatures, the molal volume of a gas becomes so
large that the molecules exist far removed from one another and the intermolecular forces
become negligibly small. These are the requirements for a gas to behave as an ideal gas. Thus
at very low pressures and at high temperatures real gases tend to exhibit ideal behaviour.
However, under ordinary pressures the molecules possess appreciable volume in comparison
with the volume of the gas as a whole . Also, the intermolecular forces existing in the gas will
not be negligible as in an ideal gas. Therefore, ideal gas equations will be inadequate to represent
the behaviour of real gases. For example, the volumes calculated by the ideal gas law is too
large, sometimes even five times the actual volume. The following methods are generally used
for calculations involving real gases:
1. Experimental P -V-T data
2. Equation of state
3. Generalized compressibility charts.

106
 Properties of Real Gases 107

Before we consider these various options, a brief discussion on the critical conditions of
a pure substance is quite in order, as the critical state is important in the development of the
equations of state.

5.2 CRITICAL PROPERTIES

The thermodynamic state of a pure fluid such as water can be represented as a function of
pressure and volume as shown in Figure 5.1. The figure shows the variation in molar volume
with pressure at various constant temperatures. Assume that the initial state of the system is
represented by point p. The change in volume of water with pressure at a constant temperature
Tx is along the isotherm p-q-r-s. In the region from p to q , the change in volume of the liquid
with change in pressure is negligibly small as the liquid is incompressible . At point q, the liquid
begins to vaporize and the volume of the system increases sharply. The pressure remains
constant till the entire liquid is vaporized . This pressure is known as the saturation pressure .
At point r the liquid is completely transformed into vapour. At point q the system is in the
saturated liquid state and at point r it is in the saturated vapour state. Between points q and r
the system consists of saturated liquid and saturated vapour in equilibrium . The volumes
corresponding to point q and r are, respectively, the specific volumes of saturated liquid and
saturated vapour. In the region between points q and r (the two-phase region), the volume of
the two-phase mixture depends upon the quality of the mixture, which is the fraction of the
mixture that is liquid. On further reduction of pressure from point r , the vapour becomes
superheated and the volume increases along the isotherm r-s.

c 72
Pc Gas
-a
3 T3
3T
2
3<
/)
-J Liquid
Tc
<L> and
CU Vapour
r

Ti
s
>
Volume
--
Figure 5.1 P V T diagram of a pure fluid .

If the liquid were at a temperature greater than Th the saturation pressure at which the two
phases coexist in equilibrium would be above that corresponding to Tx and the length of the
horizontal section joining the saturated liquid and vapour phases would be smaller. The locus
of the saturated phases is represented by the dome -shaped curve q-c-r . The area under this dome
represents the two-phase region, the area to the left of the curve q-c the liquid region and the
area to the right of the curve c-r the vapour region.
108 Stoichiometry and Process Calculations

At temperature Tc known as the critical temperature the length of the two-phase region is
so short that the PV isotherm passes through a point of inflection at point C, which is called
the critical point. The pressure at the critical point is Pc, the critical pressure . At the critical
point, the liquid and vapour phases have identical properties and are therefore indistinguishable.
A liquid at a temperature above its critical temperature cannot be vaporized by reducing the
pressure at constant temperature. The isotherms at T2 and T3 in the figure are above the critical
temperature. The two-phase region can be approached from the liquid state by increasing the
temperature at constant pressure as well, provided the pressure is below the critical pressure Pc .
The critical properties of water are Tc = 647.3 K, Pc = 221.2 bar and Vc = 57.1 x 10 6 m 3/mol.
-

The critical temperature and critical pressure represent the highest temperature and pressure
respectively, at which a pure material can exist in vapour-liquid equilibrium . If the temperature
is less than the critical temperature, the substance to the right of the saturated vapour line is
called a vapour and if the temperature is above the critical temperature the substance is called
a gas. A vapour can be condensed to a liquid by compression at constant temperature or by
cooling at constant pressure whereas a gas can be condensed only by the reduction of temperature
at constant pressure. It can not be condensed by compression at constant temperature. If the
temperature and the pressure of the substance are greater than Tc and Pc respectively, it is in
the fluid region and it can neither be condensed by any of the above methods nor can it be
vaporized by reduction in pressure as is possible with liquids. The substance in this state is
neither a gas nor a liquid. Table 5.1 gives the critical constants of a few substances.
Table 5.1 Critical properties of some typical materials

Substance Tc (K) Pc (bar) Vc x 106 (m 3/mol)

Oxygen, 02 154.6 50.4 73.4
Nitrogen , N2 126.2 33.9 89.8
Hydrogen , H2 33 12.9 64.3
Carbon dioxide, C02 304.1 73.8 93.9
Water, H2Q 647.3 221.2 57.1

5.3 EQUATIONS OF STATE

The thermodynamic state of a pure fluid may be specified by specifying properties such as
pressure, temperature and volume. An equation of state is a functional relationship between
these three variables and it may be written as
f (P, K T) = 0 (5.1)
The simplest equation of state is the perfect gas law given by Eq. (4.9), i.e . PV = nRT . But it
is applicable only to ideal gases and is inadequate to explain the behaviour of real gases. For
real gases to behave ideally, the molecular interactions should be negligible. At low molar
volumes or high pressures, molecules come very close to each other and molecular interactions
cannot be neglected. The perfect gas law may be viewed as an approximation describing the
behaviour of real gases at ordinary pressures or as describing the limiting behaviour of real
gases at low pressures. Many equations of state have been proposed to explain the actual
 Properties of Real Gases 109

behaviour of gases. An equation of state, in general, should satisfy certain limiting conditions.
For example, all equations reduce to the ideal gas equation at low pressures. That is,
PV = RT as P -> 0
Also the P-V curve at constant temperature should exhibit a point of inflection at the critical
point. Stated mathematically, this means
f dP~
=0 (5.2)
K dv JTc
\
d2P
2 =0 (5.3)
v dV JTC
In the following sections we describe some important equations of state.

5.3.1 The van der Waals Equation

The perfect gas equation fails to explain the P-V-T behaviour of real gases. The van der Waals
equation is a powerful equation of state that represents the behaviour of actual gases reasonably
accurately. The perfect gas equation was developed on the premise that the molecular interactive
forces are negligible and the molecules of the gas occupy a negligibly small volume in comparison
to the total volume of the gas. The van der Waals equation takes into account these two non-
ideal features of real gases by incorporating certain correction factors in the pressure and
volume terms of the ideal gas equation.
The pressure exerted by the molecules of a gas will be less than the ideal gas pressure
because of the attractive forces between molecules. This attractive force is proportional to 1IV 2
where V is the molar volume of the gas. The actual pressure is thus proposed to be less than
the ideal gas pressure by a/ V 2, a fact verified to be true by the kinetic theory. In using the ideal
gas equation, the pressure term should be replaced by p + a!V 2 . In an ideal gas, a molecule is
treated as point mass occupying no volume on its own. But in reality the molecules have a finite
volume, though it is only a small fraction of the total volume of the gas. The actual volume of
a gas is thus greater than the volume occupied by the gas if it were ideal. The volume term in
the ideal gas equation is to be replaced by V - b , where b indicates the excluded volume per
mole of the gas. Incorporating these corrections in the ideal gas equation, van der Waals
proposed the following equation for the P-V-T behaviour of real gases :
/
a
P+ (V - b ) = RT (5.4)
v V 2,
where a and b are called van der Waals constants. The van der Waals equation is cubic in
volume and at temperatures below the critical temperature, there are three real roots. When P
is the saturation pressure, the smallest and largest roots correspond to the molar volumes of
saturated liquid and saturated vapour respectively. The intermediate root has no physical
significance.
The constants in the van der Waals equation can be evaluated utilising the limiting conditions
which are obeyed by any equation of state. Equation (5.4) can be written as
110 Stoichiometry and Process Calculations

a RT
P= (5.5)
V2 V -b
The limiting conditions, Eqs. (5.2) and (5.3) can be applied by finding the first and second
derivatives of P with respect to V at constant T. These are as follows:
( dP } 2a RTC
=0=
V dV )Tc v/ ( Vc - bf
( d2 p ) 2 RTC 6a
=0=
JTC -
V dV
’
2
(K -bf v;
Solving these two equations simultaneously, we get
vc = 3b (5.6)
8a
Tc = 27 Rb (5.7)

c (5.8)
9b 2 2b
The last two of the above identities can be solved to get the van der Waals constants as
2
27 R 2T
a= (5 9)

b= PP (5.10)
% Pc
where Tc and Pc are, respectively the critical temperature and pressure of the fluid .

EXAMPLE 5.1 Calculate the pressure developed by one kmol gaseous ammonia contained in
a vessel of 0.6 m 3 capacity at a constant temperature of 473 K by the following methods:
(a) Using the ideal gas equation
(b) Using the van der Waals equation given that a = 0.4233 N m 4/mol2; b = 3.73 x 10-5
m 3/mol
Solution
RT
(a) Use the ideal gas equation, p = —V
, where V is the molar volume of the gas. Here,

V = 0.6 x 10-3 m 3/mol. Therefore, the pressure given by the ideal gas equation is
8.314 X 473
P=
0.6 xl 0 3 =
“
— I A6 X T /
6.554 x 10 N /m 2 = 65.54
s c c si u
bar

(b) The van der Waals equation may be rearranged as

V -b V2
 Properties of Real Gases 111

Substituting of the values gives

8.314 (473) 0.4233
P= = 5.8128 X 106 N /m 2 = 58.13 bar
(0.6 x 10 3 ) - (3.73 x 10 5 ) (0.6 x 10 3) 2
~ ~ ~

EXAMPLE 5.2 Estimate the molar volume of C02 at 500 K and 100 bar using the (a) ideal
gas equation and (b) the van der Waals equation. The van der Waals constants are 0.364 N m 4/mol2
and 4.267 x 10-5 m 3/mol.
Solution
(a) Using the ideal gas equation,
RT 8.314 (500) _ _3
Tr
V = P
= — z—
(l x l O 7 )
— — 0.4157 x 10
A
.
1C 1A
m 35

(b) Volume can be determined using the van der Waals equation by trial and error. Here,
a = 0.364 N m 4/(mol)2 and b = 4.267 x 10-5 m 3/mol. The van der Waals equation gives
/
a\
P+ (V - b ) = RT
v V2/
Substituting the values, we get

flOOxlO
v
+ -
0 364
V
5
^ (V - 4.267
.
2
y
X 10
“ 5
O
-
= 8.314 x 500
This can be simplified as
V3 - 4.5837 x 10 -4 F2 + 3.64 x 10 8 F - 1.5582 x 10
- “ 12
= 0
Solving this, the molar volume of C02 in the present case is found to be
4
V = 3.717 x 10 "

m 3/mol .

5.3.2 Other Equations of State

A number of equations of state have been proposed by various researchers such as the Redlich-
Kwong equation, the Soave’s modification for the Redlich-Kwong equation, the Peng-Robinson
equation, etc. The Benedict-Webb-Rubin equation and the virial equations are prominent among
them . A review of these equations of state can be found in books on thermodynamics.
Redlich-Kwong equation: This is a two-parameter equation of state widely used in engineer-
ing calculations.
„ RT a
P= XT (5.11)
V - b T SV (V + b)
0

The constants a and b are related to the critical properties as given below :
5
0.4278i? 2r£ 2 0.08677 7;
*
'
,
a= — ; b= - (5.12)
*Pc *Pc
112 Stoichiometry and Process Calculations

Redlich-Kwong-Soave equation: Soave’s modification of the Redlich-Kwong equation is as

follows:
RT a\T )
(5.13)
V - b V (V + b )
where a' ( T ) = aa where a depends on the temperature. The constant b is given by Eq. (5.12),
whereas the constant a is evaluated using Eq. (5.12) with the exponent of Tc changed to 2.

Peng-Robinson equation: It is written as

p _ RT aa
~ ~
(5.14)
V -b V (V + b ) + b ( V -b)

where a and b are constants, and a depends on reduced temperature T .

Benedict-Webb-Rubin equation: This equation contains a more number of parameters

compared to the equations given above and hence is more complex. Being more accurate than
the cubic equations of state discussed above , it is widely used for estimating the properties of
light hydrocarbons and their mixtures in petroleum and natural gas industries.

BaRT - A - CJT 2
/ \
„ RT bRT - a aa C 7 exp 7
P= +
V
— V2
+ r
V3
+ + — 1 +
V 6 y 2> j 2 V V 2 V2
(5.15)

where A0, B0, C0, a, b, c, a and y are constants.

Virial equations: Virial equations express the compressibility factor Z (= PV/ RT ) as functions
of pressure or volume. The compressibility factor is the ratio of the volume of a real gas ( V )
to the volume if the gas behaved ideally at the stated temperature and pressure { RHP ). Virial
equations are available in the following two forms :
PV ,
= 1 + B’ P + CP 2 + D' Pi + • ••
7
Z= (5.16)
RT
PV C B
D
Z — RT —
1
V
H
2
H
V3
V
+1 — — * * * (5.17)

Equations (5.16) and (5.17) are known as virial equations and the constants B, C, D and B\
C', Df are known as virial coefficients . These equations find greatest application in predicting
P-V-T behaviour at low to moderate pressures.
EXAMPLE 5.3 Assume that gaseous ammonia follows the Redlich-Kwong equation of state .
Calculate the pressure developed by one mole of NH3 contained in a vessel of volume
0.6 x 10-3 m 3 at 473 K given that the critical pressure and temperature are 112.8 bar and
405.5 K .
Solution The constants a and b in the Redlich-Kwong equation are evaluated using
Eq. (5.12), i.e.
0.42787? 2 r 25 (0.4278)(8.314) 2 ( 405.5) 2 5 '
, N m4 K0 5
a= = = 8.68
0 0

Pc 112.8 xl 05 mol 2
 Properties of Real Gases 113

_,
ft = ° 0867Pc ?7; = (° 0867112.8
j )(8.314X 405.5)
x 10s = ^ x 10
3

Equation (5.11) gives the pressure developed by the gas.

RT
P
V - ft T 0 SV (V + ft )

_ (8, 314) (473)

(0.6 xlO 3 ) - (2.59 xlO 5 )
- “

84>8
( 473° )(0.6 x 10 )(0.6 X 10 3 + 2.59 x 10 5 )
5 3
" “ “

= 5.787 x 106 N/m 2 = 57.87 bar

EXAMPLE 5.4 Calculate the molar volume of gaseous ammonia at 373 K and 10 bar using
the Redlich-Kwong equation given that the critical pressure and temperature are 112.8 bar and
405.5 K.
Solution The constants in the Redlich-Kwong equation were evaluated in Example 5.3.
Now the molar volume is given by Eq. (5.11).
p _ RT
V -b T 05V (V + ft )

(8.314)(373) 8 68
106 ,

V - 2.59 x 10 5
373 - F(F + 2.59 X 10 5 )
° 5
“ ~

3
Solving this equation, we get V = 3.0 x 10 “

m 3/mol.
EXAMPLE 5.5 Using the virial equation of state, calculate the molar volume of methanol
vapour at 500 K and 10 bar. The virial coefficients are, B = -2.19 x 10 4 m3/mol; C = -1.73 “

x 10 8 m6/mol2.
“

Solution The virial equation truncated to three terms is

PV c_
which can be rearranged as
Z=
jRT
=l+
^
V
+
V2

RT , B c
/ \

V = ~ 1+ — +
~

P V V V2 /
4 \
1.73 x 10-8
~

-3 2.19 x!0
= 4.157 x 10 (A)
V V2 /

Assume a value for V and calculate the right-hand side of this equation. The assumed value
will be equal to the molar volume if the right-hand side so evaluated and the volume assumed
114 Stoichiometry and Process Calculations

are equal. Otherwise repeat the calculation with a new value for V . The volume calculated using
the ideal gas equation can be taken as the initial guess value for V . The ideal gas volume is
V = RT/ P = 4.157 x 10-3 m 3
The results of these calculations are:
Assumed V (m 3) : 4.157 x 10 3 3.934 x 10 3 3.921 x 10 3 3.920 x 10 3
" " " "

RHS (m )3 3.934 x 10 3 3.921 x 10 3 3.920 x 10 3 3.920 x 10 3

: " " " "

Since the assumed and calculated values are equal at V = 3.92 x 10-3 m 3, it may be accepted
as the molar volume of methanol.

5.4 COMPRESSIBILITY CHARTS

5.4. 1 Compressibility Factor
The compressibility factor measures the deviation of a gas from ideal behaviour. It is defined
as Z = PV /RT . It can be interpreted as the ratio of the actual volume of a gas ( V ) to the volume
that the gas will occupy if it were an ideal gas ( RT/ P ) at the given temperature and pressure.
Compressibility charts are plots of the compressibility factor against pressure with temperature
as parameter as shown in Figure 5.2. For a perfect gas, the compressibility factor is unity and
the curve of Z versus P is a straight horizontal line at Z = 1.0. The shape of the curve for a real
gas depends on the nature of the gas. However, since a real gas behaves ideally as pressure
is reduced, the compressibility factor of a real gas approaches unity as the pressure is reduced
to zero. This is clear from Figure 5.2. At other conditions, the compressibility factor may be
less than or more than unity depending on the temperature and pressure of the gas.

Ethane
Methane

N
s-T
o
-> Hydrogen
'S3

E '

'
Ideal gas
K/i
Vl
u
PH
£
o
u
Ammonia

0.0
0 200 400 600 800 1000
Pressure, bar
Figure 5.2 Compressibility factor.
 Properties of Real Gases 115

5.4.2 Principle of Corresponding States

The principle of corresponding states can be stated as that all gases when compared at the same
reduced temperature and reduced pressure , have approximately the same compressibility factor
and all deviate from the ideal behaviour to the same extent. The reduced variables are obtained
by dividing the actual variables by the corresponding critical constants . Thus the reduced
pressure Pr = P / Pc , the reduced temperature Tr = T / Tc,, and reduced volume Vr = VI Vc.
According to the principle of corresponding states, the compressibility factor of any substance
is a function of the reduced temperature and reduced pressure alone. For example, consider the
compressibility factors of methane with the critical properties Tc = 191 K, Pc = 46 bar and
nitrogen with the critical properties Tc = 126 K, Pc = 34 bar. Methane at 382 K and 69 bar
and nitrogen at 252 K and 51 bar have identical reduced properties Tr = 2, Pr = 1.5. Then
according to the law of corresponding states, nitrogen at 252 K and 51 bar and methane at 382 K
and 69 bar should have the same compressibility factors. Thus the principle of corresponding
states enables one to coordinate the properties of a range of gases to a single diagram such
as the generalised compressibility chart.

5.4.3 Generalized Compressibility Charts

These charts enable engineering calculations to be made with considerable ease and also permit
the development of thermodynamic functions of gases for which no experimental data are
available. The generalised compressibility chart (Figure 5.3) is constructed based on the principle
of corresponding states. Based on experimental P-V-T data on 30 gases, Nelson and Obert*
prepared these charts which give the compressibility factors with an average deviation of less
than 5% from the experimental results.

Tr =
1.00 5.00
2.00
1.60
0.90 Go\ oc 1.40
o o
1.30
N 0.80 1.20
-T
j
o T = 0.70 0.90 1.15
o
C3
0.70 1.10
SJ
o .05
w
co
0.60 o 0 0
o - ii 'r

u
Q»

§ 0.50
o
_-
o
DC X

o
o o
0.40 1.00

0.30
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Reduced pressure, Pr

Figure 5.3(a) Generalized compressibility chart (lower pressures) .

116 Stoichiometry and Process Calculations

ci
3.50
2.50
o 2.00
N 1.80
Cv
V = 1.0
o /
1.60
o
C3
00
1.50
O 1.40
-
O
%
50
1.30
u sC
Q
S -o 1.20
o 1.15
O V

1.10
^r
o
1.05
7

Cl
T /? .00

1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
Reduced pressure, Pr
Figure 5.3(b) Generalized compressibility chart .

On these charts, the compressibility factor Z is plotted as a function of reduced tempera-

ture and reduced pressure. The generalized compressibility charts provide one of the best
means of expressing the deviation from ideal behaviour. When precise equations of state are
not available to represent the P -V-T behaviour, these charts provide a convenient method for
the evaluation of compressibility factor.

5.4.4 Methods Based on the Generalized Compressibility Charts

The principle of corresponding state can be mathematically expressed as
Z = f (P n T r) (5.18)
Though the generalized charts and correlations based on the above equations provide better
results than the ideal gas equation, significant deviations from experimental results exist for
many fluids. Considerable improvement can be made when a third parameter is introduced into
. PcVc
Eq. (5.18). Lyderson et al. T used the critical compressibility factor, Zc- as the third
RTC
parameter. Pitzer + used the acentric factor co as the third parameter.
Lydersen et al. method: The method assumes that Z = f( Tn Pn Zc ). Assume that there are
different, but unique, functions Z = fiPn T1.) for each group of pure substances with the same

*Nelson, L .E. and E.F. Obert , Chem. Eng., 61(7), 203 208 (1954). -

tSee Hougen, O.A ., K .M. Watson and R .A . Ragatz, Chemical Process Principles, vol . 2, Asia Publishing
House ( 1963).
iPitzer, K .S., J. Am. Chem. Soc. , 77, 3427 (1955).
 Properties of Real Gases 117

Zc. Then, for each Zc we have a different set of compressibility charts such as the one shown
in Figure 5.3. All fluids with the same Zc values then follow the Z-Tr-Pr behaviour shown on
charts drawn for that particular Zc. The generalized charts were drawn for Zc = 0.27 as most
materials fell in the range of 0.26 to 0.28 and correction tables were developed to correct
for values of Zc different from 0.27. The generalized charts for compressibility is given in
Figure 5.4.

2.00
1 70 1.80
60

1 35 1.40 1.45 1.50

o
Tr 0.80
1.25 1.30

\
0.85
X
1.15
.20
oc
o
X
\
N 0.90
cv

O 1 0
o
S3
\
0.92
1.08
O '

•
53
73
1.06
u 0.94
Cu Saturation line
S 1.04
o
O
0.95 N
1.02
o
o
0.96 1.00
\ 0.98
\ \
0.97
I/ I

O '

o
0.2 0.4 0.6 0.8
Reduced pressure, Pr

Figure 5.4(a) Generalized compressibility factor, low pressure range, Zc = 0.27 .

118 Stoichiometry and Process Calculations
r 1.2

1.1
5.00
10.00 '
5.00
3.0C 1.0
2.00
. 80
JO 0.9
- =* 1.60 /

1.50
.40 —
: t 0.8
N
c-
i T

o
C3
Saturated gas
^ AN§§ X\1.25
\
\
\
\
^ \
1.20
1 5
,I35

1.30
\ \ .25 J' 1
7
0.7

0.6
'
53 V /
/
OJ 1.20
r. i 5 0.5
E
c
0.80 0.85 0.90 0.95
U 1.10 /
.08 ^ 0.4

1.04
1.02
0.3

0.2
Saturated liquid
0.60
0.5 0.960 0.1

0.2 0.3 0.4 0.5 1.0 2.0 3.0 4.0 5.0 10.0 20.0 30.0
Reduced pressure , Pr
Figure 5.4(b) Generalized compressibility factor, Zc = 0.27 .

The values given in Figure 5.4 can be corrected for values of Zc different from 0.27
according to the following equation.
Z' = Z + D( ZC - 0.27) (5.19)
where Z' is the compressibility factor of the given fluid, Z is the compressibility factor at Zc =
0.27 and D is the deviation term . Generalized charts for deviation of the compressibility factor
are given in Figue 5.5.
Pitzer method: The acentric factors measure the deviation of the intermolecular potential
function of a substance from that of simple spherical molecules. For simple fluids it has been
observed that at a temperature equal to 7/10 of the critical temperature , the reduced vapour
pressure closely follows the following empirical result:
Ps
— =—
1 T n ,
at — = 0.7
Pc 10 Tc
where Ps is the vapour pressure. Pitzer defined the acentric factor ( co ) in terms of the reduced
vapour pressure at a reduced temperature of 0.7 as
 Properties of Real Gases 119

© © © o
o
'
O
©
00
1.2
©
© t
© ©
a © © /
© Z > 0.27 NO
NO OO
©
©
z < 0.27
1.0
O
'
1.0
©-
©

©
/ / / ©
I --
I
IJ

D 0.6 77
/
/
©
D 0.6 25 /
a
’
©
/
© O
O
0.4 ' 0.4
© © ©
© 30
©

0.2 tsJ
0.2 © -
© to
©

© © ©
o ©
0.0
0.2 0.3 0.4 0.6 0.8 1.0 1.2 0.2 0.3 0.4 0.6 0.8 1.0 1.2
Reduced pressure, Pr Reduced pressure , Pr
Figure 5.5 Generalized deviation D for compressibility factor at Zc = 0.27 .

r
co = - 1.00 - log
PS \
(5.20)
V Pc Jrr = o.7
For simple fluids the acentric factor = 0; for more complex fluids the acentric factor > 0. The
acentric factors are listed in standard references. [See , for example , Prausnitz, J. M ., Molecular
Thermodynamics of Fluid Phase Equilibria, Prentice-Hall Inc. (1986).] Table 5.2 gives the
acentric factors of some common substances.
Table 5.2 Acentric factors
Molecule c0 Molecule CO

CH 4 0.008 /7-C 4H10 0.193

o2 0.021 C 6HS 0.212
N2 0.040 co2 0.225
CO 0.049 NH3 0.250
C 2H4 0.085 -C 6Hi 4
A7 0.296
C 2H6 0.098 H2O 0.344

Pitzer proposed the following functional form for the compressibility factor.
Pn co)
Z = f( Tn (5.21)
It was suggested that instead of preparing separate Z-Tr-Pr charts for different values of m, a
linear relation could be used
Z = Z<0) ( Tn Pr ) + eoZ(1) ( Tn Pr ) (5.22)
(0) ( 1)
Here, the function Z would apply to spherical molecules, and the Z term is a deviation
function. Pitzer presented tabular and graphical values of the function Z(0 ) and the Z(1). Figures 5.6
and 5.7 give these plots incorporating the Lee-Kessler* modifications.
*Lee, B.L. and M.G. Kessler, AlChE J. , 21, 510 (1975).
120 Stoichiometry and Process Calculations

L
A
2.50
1.1 = 400

Compresiblty
3. /
.80
1.0 /
2.00
1 /70 ' /
0.9 7
.60
0.8 .51
0.7
0.85
s
\
S
s
\
>
1.30
1.40
, factor
0.6 S V
\

1.15
1.20
. 25 9 simple
0.5
\

\ V 1.10 fluid
0.4
0.3
Saturation line
.05 term
Z
/
1.00
0.2
T = 3.9
r

0.1
0.3 0.4 0.5 0.6 0.8 1.0 2.0 3.0 4.0 5.0 6.0 8.0 10.0
Reduced pressure, Pr
Figure 5.6 Generalized compressibility factor for simple fluid .

0.3 0.5 0.7 1.0 2.0

0.35

. 40 Tr =

0.23 1.30
\ 1.50
1.80
2.00
N 1.60 2.50
s 3.00
& 0.13 3.50
c
o 4.00
-Po
D
bn
1.20
\
o
o 1.15
+>
-
i
o
o
0.05
43 .C 5
0.00 . 1C
x>
'
55 0.05 1.00
cn
2Q /
eo-
/
V T = 0.90 3.95
0.15 3.85

0.25
0.2 0.3 0.4 0.6 0.8 1.0 2.0 3.0
Figure 5.7 Generalized compressibility factors correction term .
 Properties of Real Gases 121

EXAMPLE 5.6 Using the Lydersen method, determine the molar volume of n-butane at 510 K
and 26.6 bar. The critical pressure and temperature of /7 -butane are 38 bar and 425.2 K respectively,
and the critical compressibility factor is 0.274.
Solution The reduced properties of /7 -butane are:
pr = 26.6 = 0.70
38
510
Tr = 425.2 = 1.20
From Figures 5.4 and 5.5
Z = 0.865
D = 0.15
Using Eq. (5.19),
Z' = 0.865 + 0.15(0.274 - 0.27) = 0.8656
The molar volume is
_ RTZ _ (8.314)(510)(0.8656)
P 26.6 x l O5
3
= 1.3798 X 10 m 3/mol

EXAMPLE 5.7 Using the Pitzer correlation, determine the molar volume of /7-butane at 510 K
and 26.6 bar. The critical pressure and temperature of n-butane are 38 bar and 425.2 K,
respectively and the acentric factor is 0.193.
Solution The reduced properties of n-butane are:

p, = 26.6 = 0.70
38
510
Tr = 425.2 = 1.20
From Figures 5.6 and 5.7
Z(°) = 0.855
ZO > = 0.042
Using Eq. (5.22)
Z = 0.855 + 0.193(0.042) = 0.8631
The molar volume is
_ RTZ _ (8.314)(510X0.8631)
P 26.6 xlO5
= 1.3798 x lO 3 m 3/mol "
122 Stoichiometry and Process Calculations

5.5 MIXTURE OF REAL GASES

We have already seen several methods for the evaluation of the P-V-T relationship of pure
gases. For mixtures of ideal gases, the properties can be determined by adding together the
properties of the individual components. This simple technique fails in the case of mixtures of
real gases. However, it is possible to estimate the P-V-T properties of real gaseous mixtures from
the properties of pure constituents. Three such methods are discussed in the following sections.

5.5.1 Equations of State

An equation of state may be used to evaluate the properties of the mixture provided the
constants appearing in the equations are obtained by combining the constants of the pure
components by an appropriate method . We will discuss only the van der Waals equation of state
in this section. For example, the constants a and b in the van der Waals equation are evaluated
as
2
a = {yyia )12 ) (5.23)

b = 2 y b, , (5.24)
where at and bt are the van der Waals constants for the component / in the mixture and yt is
its mole fraction in the mixture. The constants a and b , calculated as above, may be treated as
the van der Waals constants for the mixture, which may be used in Eq. (5.4) for evaluation of
P-V-T properties of the mixture. Alternatively, the pseudo -critical temperature and pressure
( Tc' and PJ ) discussed later in this chapter may be used for the evaluation of the van der Waals
constants of the mixture as given below.
,
27 R 2 ( TC ' ) 2
a=
64 Pcf
Rjy
b=
8Pc’
The constants are substituted into the van der Waals equation and the pressure, volume or
temperature of the gas mixture is determined .

5.5.2 Mean Compressibility Factor

A mean compressibility factor Zm may be defined such that the P -V-T relation for the mixture
is written as
PV = ZJCT (5.25)
Zm is a function of the pressure, temperature and composition of the mixture. It may be evalu-
ated as
= (5.26)
Since the compressibility factor of component /, Zi is a function of the reduced pressure,
the question may naturally arise : what pressure should be used for determining ZP If volumes
are additive at constant temperature and pressure (i.e., Amagat’ s law is applicable), it is
 Properties of Real Gases 123

recommended that Zi be evaluated at the temperature and the total pressure of the mixture .
When Dalton’s law is applicable, Zz is evaluated at the temperature and the partial pressure of
the component / in the mixture. Thus
p
Prj ~ p (Amagat ’s law) (5.27)
rc,i
p
-
, ;; II (Dalton’s law) (5.28)

5.5.3 Pseudo-critical Properties

We define an effective critical parameter for a gas mixture as the mole fraction weighted
average of the critical properties of the constituent gases. Since it is different from the true
critical property of the mixture, it is called pseudo-critical property. Thus the pseudo-critical
temperature ( T f ) of the mixture is
Tc' = 2 ytTcj (5.29)

The pseudo-critical pressure = is

^
The pseudo-reduced temperature (71 ) and pressure
Pc = yAi
(Ptf )
-
(5 3 )
°
/ are now evaluated :
T
T'/ =—
rp
1
t
(5.31)
c

p/ = —Pc '
(5.32)

In the Kay ’s method for the evaluation of P -V-T behaviour of mixtures of real gases, these
pseudo-reduced parameters are used to find the compressibility factor of the gas mixture with
the help of a generalized compressibility chart.

EXAMPLE 5.8 A gas mixture contains 40.0% nitrogen and 60.0% ethane at 6000 kPa and
325 K. The van der Waals constants: nitrogen ( a = 0.1365 N m 4/mol 2 and b = 3.86 x 10-5
m 3/mol), ethane ( a = 0.557 N m 4/mol2 and b = 6.51 x 10-5 m 3/mol). The critical constants:
nitrogen (Pc = 3394 kPa, Tc = 126.1 K), ethane ( Pc = 4880 kPa , Tc = 305.4 K) . Calculate the
molar volume of the mixture using the following:
(a) The ideal gas equation
(b) The van der Waals equation
(c ) The mean compressibility factor based on (i) Amagat’s law and (ii) Dalton’s law.
(d) The Kay ’s method
Solution (a) One mole of an ideal gas will occupy volume
RT 8.314 x 325 4
V = = 4.503 xlO m 3/mol
"

P 6000 x l O3
124 Stoichiometry and Process Calculations

(b) The van der Waals constants for the mixture are evaluated using Eqs. (5.23) and
(5.24). The mole fractions of nitrogen and ethane are y = 0.4 and Ethane = 0.6.

a = ( Tyia )12 ) = [0.4(0.1365)1/2 + 0.6(0.557)1/2]2 = 0.3547 N m 4/mol 2

b = ~L yibi = 0.4(3.86 x 10 “ 5) + 0.6(6.51 x 10 5) = 5.45 x 10 5 m 3/mol

Substituting these values in the van der Waals equation, we get
0.3547 \
6000 x 103 + 2
(V - 5.45 x 10-5 ) = 8.314 x 325
k

V V
v /

This may be rearranged as

_
V3 5 0484 x 10-4 y2 + 5 9117 x 10 8
-
v_ 3 2217 x 10-12 = 0
On solving this equation, we get
V = 3.680 x 10-4 m 3/mol
(c ) (i) Assume that the mixture follows Amagat ’s law. Then the compressibility factors of
the components are evaluated as
P
P r ,i =
Rc ,i
For nitrogen,
6000 o 325
pri
r7 = 3394 = 1.768
1 ; Tri
T
r, z = = 2.5773
’ 126.1
For ethane,
6000 t 325
Prr’ i = 4880 = 1.230; T^r’, = 305.4 = 1.0642
7 7

Using the compressibility charts, we get ZN ^ = 1.0 and Zethane = 0.42.

Combining these,

Zm = 0.40 x 1.00 + 0.60 x 0.42 = 0.652

Now,
V=
Z „RT 0.652 x 8.314 x 325 ...
3
_
= 2.94 x 10 4 m 3/mol
_
P 6000 x 10 '

(ii) Alternatively, if Dalton’s law is used, i.e.

Pi y, p
P r ,i =
PC ,J
1 PC ,1
1

For nitrogen,
x 6000
Pr ,i = —0.4r3394
— — = 0.707;A "7 A "7
^ =
Tri 126.1
o 325
= 2.5773
 Properties of Real Gases 125

For ethane,
0.6 X 6000
1
'v
r’
' v
= — i o642
4880
OOA A
305.4
Using the compressibility charts, we get ZN = 1.02
and Zethane = 0.76.
Combining these,
Zm = 0.40 x 1.0 + 0.60 x 0.76 = 0.856
ZmR T 0.856 x 8.314 x 325
Therefore, V= = 3.855 xl 0 4 m 3/mol
“

P 6000 x 103 *

(d) The pseudo-critical properties are:

Tc' = I, y Tci 1
= 0.4 x 126.1 + 0.6 x 305.4 = 233.68 K

=I = 0.4 x 3394 + 0.6 x 4880 = 4285.6 kPa

The pseudo-reduced properties are calculated as :
T 325
Tr' = = 1.391
Tf
c 233.68
P 6000
Pr' = = 1.4
Pc' 4285.6
For these reduced parameters, Z = 0.83 and the molar volume is

V=
ZmRT 0.83 x 8.314 x 325
= 3.738 xl 0
_ 44 3
m 7mol
_ “

P 6000 x 103

EXAMPLE 5.9 The molar volume of a gas mixture analyzing 40% nitrogen and 60% ethane
at 325 K is 4.5 x 10 4 m 3/mol. Determine the pressure of the gas by
~

(a) The ideal gas equation

( b) The van der Waals equation
The van der Waals constants: nitrogen ( a = 0.1365 N m 4/mol2 and b = 3.86 x 10 5 m 3/mol),
ethane ( a = 0.557 N m 4/mol 2 and b = 6.51 x 10-5 m 3/mol).
Solution
RT
(a) P= ~ ~

V
8.314 x 325
4 =
6.005 x 106 N/ m 2 (= 6005 kPa )
4.5 x 10
“

( b) The van der Waals constants for the mixture are evaluated using Eqs. (5.23) and
(5.24). The mole fractions of nitrogen and ethane are j;N = 0.4 and Ethane = 0.6.
126 Stoichiometry and Process Calculations

2
a = (yyia) '2} = [0.4(0.1365)1/2 + 0.6(0.557)1/2]2 = 0.3547 N m 4/mol 2

b = 'L y i b i = 0.4(3.86 x 105) + 0.6(6.51 x 10 5) = 5.45 x 10 5 m 3/mol

Substituting these values in the van der Waals equation, we get,

_ RT
p~ a 8.314 x 325 0.3547
~
V -b V2 4.5 xl 0 4 - 5.45 xl 0
“ “ 5
( 4.5 x 10 4 ) 2

= 5.08 x 106 N/m 2 (= 5080 kPa)

EXERCISES
Equations of state
5.1 A pressure gauge connected to a cylinder containing 175 kg propane indicates 50 bar
absolute pressure. Using van der Waals equation, determine the temperature of the gas
in the cylinder. The capacity of the cylinder is 1 m 3. The van der Waals constants are
a = 0.9252 N m 4/mol 2 and b = 9.05 x 10-5 m 3/mol.
5.2 One mole of a gas obeying van der Waals equation is contained in a cylinder of
volume 0.05 m 3 at 100 kPa. If the van der Waals constants are a = 0.135 N m 4/mol 2
and & = 3.22 x 10 5 m 3/mol, calculate the temperature of the gas.
5.3 One kmol C02 occupies a volume of 0.381 m 3 at 313 K . Compare the pressures given
by the
(a) Ideal gas equation
(b) van der Waals equation
Take the van der Waals constants to be a = 0.365 N m 4/mol2 and b = 4.28 x 10 5 m 3/mol.
5.4 Use the Redlich-Kwong equation to calculate the pressure of 0.5 kg gaseous ammonia
contained in a vessel of 0.03 m 3 at a constant temperature of 338 K. The critical
temperature and pressure are 405.5 K and 112.8 bar respectively.
5.5 Calculate the pressure exerted by one mole gaseous ammonia contained in a vessel of
volume 0.03 m 3 at a temperature of 340 K using the Redlich-Kwong equation of state .
The critical constants of ammonia are 405.5 K and 112.8 bar. Compare the result with
the value obtained using the ideal gas equation.
5.6 Ethylene at 500 bar and 375 K is contained in a cylinder of volume 0.03 m 3. The
critical properties of ethylene are 282.4 K and 50.4 bar. How many kilograms of
ethylene are there in the cylinder? Use the van der Waals equation.
5.7 A fire extinguisher of capacity 0.04 m 3 contains C02 at 101.3 kPa and 300 K . It is
to be charged with C02 to a pressure of 20 bar at the constant temperature of 300
K. Determine the kilograms of gas to be admitted assuming the van der Waals equation.
The critical constants of C02 are 304.2 K and 73.8 bar.
 Properties of Real Gases 127

5.8 Calculate the molar volume and the compressibility factor of methanol vapour at 450 K
and 10 bar using
(a) The truncated virial equation, given the following virial coefficients:
B = -2.19 x 10-4 m 3/mol and C = -1.73 x 10-8 m 6/mol2
( b) The Redlich-Kwong equation, given the critical constants of methanol as 512.6
K and 81.0 bar
5.9 Calculate the volume of vessel that should be provided to store 1 kmol of methane at
325 K and 600 bar using the ideal gas equation and the van der Waals equation. The
critical constants of methane are 190.6 K and 46.0 bar.
5.10 Calculate the molar volume of a gas at 9 MPa and 373 K using the van der Waals
equation given that the constants a and b of the gas are respectively, 0.231 N m 4/mol2
and 4.49 x 10-5 m 3/mol.
5.11 Calculate the volume occupied by one mole of oxygen at 300 K and 100 bar using
(a) The ideal gas law
(b) The van der Waals equation.
Take a = 0.1378 N m 4/mol2, and b = 3.18 x 10-5 m 3/mol
5.12 Calculate the molar volume of ammonia at 373 K and 10 bar using (a) the van der
Waals equation and (b) the Redlich-Kwong equation given that the critical temperature
is 405.5 K and the critical pressure is 112.8 bar.
5.13 Determine the van der Waals constants and the molar volume of ethane at the critical
point given that the critical temperature and pressure are respectively 305.2 K and
49.4 bar.
5.14 Using the Redlich-Kwong equation calculate the molal volumes of saturated liquid and
saturated vapour of methyl chloride at 333 K . The saturation pressure of methyl chloride
at 333 is 13.76 bar. The critical temperature and pressure are respectively 416.3 K and
66.8 bar.
5.15 Using the virial equation calculate the molar volume and compressibility factor of
isopropanol vapour at 473 K and 10 bar. The virial coefficients are:
B = -3.88 x 10-4 m 3/mol and C = -2.6 x 10-8 m 6/mol 2.
5.16 Determine the molar volume of gaseous methane at 300 K and 600 bar by the following
methods:
(a) Using the ideal gas equation
(b) Using the van der Waals equation given that a = 0.2285 N m 4/mol 2; b = 4.27 x
10 5 m 3/mol
-

(c) Using the Redlich-Kwong equation given that Tc = 191.1 K and Pc = 46.4 bar.

Generalized compressibility charts

5.17 Using the Nelson-Obert chart calculate the pressure developed by 4.0 kg oxygen
contained in a vessel of volume 0.03 m 3 at 250 K . The critical constants of oxygen
are 154.6 K and 50.5 bar.
128 Stoichiometry and Process Calculations

5.18 A 6.0 m 3 tank contains 25 kmol of a gas at 275 bar and 882 K. Determine the critical
temperature of the gas using a generalized method given that the critical pressure is
50 bar.
5.19 Using the Nelson-Obert chart, estimate the volume occupied by 1 kg water vapour at
17 bar and 500 K; given the critical pressure and temperature of water as 221.2 bar and
647.3 K respectively. Compare the result with the volume calculated using the ideal gas
equation.
5.20 Estimate the molar volume of water at 973.2 K and 200 bar using
(a) The Lydersen method
(b) The Pitzer method
The critical pressure and temperature of water are 221.2 bar and 647.3 K respectively,
and the critical compressibility factor and the acentric factor are, 0.234 and 0.3448
respectively.
5.21 Calculate the molar volume and the compressibility factor of isopropyl alcohol at
475 K and 10 bar using
(a ) The van der Waals equation
(b) The Lydersen method
(c) The Pitzer correlation
The critical pressure and temperature of isopropyl alcohol are 47.64 bar and
508.3 K . The critical compressibility factor and the acentric factor are 0.248 and
0.6689 respectively.
5.22 Calculate the molar volume of isobutene at 428 K and 86.2 bar using
(a) The van der Waals equation
(b) The Lydersen method
(c) The Pitzer correlation
The critical pressure and temperature of isobutene are 36.48 bar and 408.1 K. The
critical compressibility factor and the acentric factor are 0.2627 and 0.282 respec -
tively .

Mixture of real gases

5.23 A gas mixture containing 20% ethanol and 80% carbon dioxide has a molar volume
equal to 2.0 x 10-4 m 3/mol at 500 K. The critical parameters are: ethanol ( Pc = 6383 kPa,
Tc = 516.3 K) and carbon dioxide (Pc = 7382 kPa, Tc = 304.1 K). What is the pressure
of the gas? Use pseudo-critical method .
5.24 The molar volume of a gas mixture is experimentally found to be 1.4 x 10 4 m 3/mol
“

at 121.6 x 105 N /m 2 and 298 K . The analysis of the mixture showed that it contained
57% ethylene, 40% argon and 3% helium . By how much does the molar volume
calculated using the pseudo-critical properties deviate from the experimental result? The
critical properties are: ethylene (Pc = 5032 kPa, Tc = 282.4 K), argon (Pc = 4898 kPa,
Tc = 150.9 K) and helium (Pc = 228 kPa, Tc = 5.2 K).
 Properties of Real Gases 129

5.25 20 kg of a gas mixture analyzing 10% carbon dioxide, 40% methane and 50% ethylene
is to be contained in a cylinder at a maximum pressure of 165 bar at 355 K. What
should be the volume of the cylinder? Use Kay ’s method. The critical properties are:
carbon dioxide ( Pc = 7382 kPa, Tc = 132.9 K), methane ( Pc = 4604 kPa, Tc = 190.6 K)
and ethylene ( Pc = 5032 kPa, Tc = 282.4 K).
5.26 A gas mixture analyzed 20% methane , 30% ethylene and 50% nitrogen. The molar
volume of the mixture at 100 bar is found to be 3 x 10 4 m 3/mol. The critical parameters
~

are: methane ( Pc = 4604 kPa, Tc = 190.6 K), ethylene ( Pc = 5032 kPa , Tc = 282.4 K)
and nitrogen ( Pc = 3394 kPa, Tc = 126.1 K) . Using the pseudo-critical method, determine
the temperature of the gas.
5.27 A gas mixture analyzes 20% methane , 30% ethylene and the rest nitrogen. Determine
the molar volume of the gas at 100 bar and 375 K using
(a) The ideal gas equation
(b) The van der Waals equation. The constants a and b are : methane ( <a = 0.225 N m 4/
mol2, b = 3.159 x 10-5 m 3/mol), ethylene ( a = 0.448 N m 4/mol 2, b = 5.72 x 10-5
m 3/mol) and nitrogen ( a = 0.1347 N m 4/mol2, b = 3.86 x 10-5 m 3/mol).
(c) The mean compressibility factor, given the critical constants as : methane ( Pc =
4604 kPa, Tc = 190.6 K ), ethylene ( Pc = 5032 kPa , Tc = 282.4 K) and nitrogen
( Pc = 3394 kPa, Tc = 126.1 K)
(d) The pseudo-critical properties.
5.28 A gas mixture consists of 70% nitrogen, 20% oxygen, 9% ammonia and 1% water.
Determine the density of the gas at 800 kPa and 925 K
(a) Using the van der Waals equation with average values of the constants. The van
der Walls constants are: nitrogen ( a = 0.1347 N m 4/mol 2, b = 3.86 x 10 5 m 3/mol),
-

oxygen ( a = 0.1360 N m 4/mol 2, b = 3.19 x 10-5 m 3/mol), ammonia ( <a = 0.419 N

m 4/mol 2, b = 3.73 x 10-5 m 3/mol) and water vapour ( <a = 0.548 N m 4/mol 2,
b = 3.06 x 10-5 m 3/mol).
(b) Using the van der Waals equation with the constants evaluated using the pseudo-
critical properties. The following are critical properties: nitrogen ( Pc = 3394 kPa,
Tc = 126.1 K), oxygen ( Pc = 5043 kPa, Tc = 154.6 K), ammonia ( Pc = 1128 kPa,
Tc = 405.7 K) and water ( Pc = 22090 kPa , Tc = 647.3 K).
 6 Vapour Pressure

All solids and liquids exert definite vapour pressures which are characteristic of the substances.
Vapour pressure is considered to be one of the important thermodynamic properties of the
substance. For pure substance, it is defined as the pressure exerted by its vapours in thermo-
dynamic equilibrium with its condensed phase (solid or liquid) in a closed system at a given
temperature . Vapour pressure indicates the tendency of the particles to escape into vapour phase
from the liquid or solid phase. A liquid with a high vapour pressure is referred to as highly
volatile. For solutions, vapour pressure determines the volatility of the components in a solution,
which in turn decides the relative volatility of the system . The relative volatility of a solution
is a measure of the easiness of separating liquid mixtures into their components by distillation.
Distillation is the most widely used technique in chemical engineering for separation and
purification of solutions. Besides, vapour pressure data is useful for the estimation of many
physical properties required in the design of chemical equipment. Thus, a good knowledge
about the methods for the estimation of vapour pressure in the absence of experimental data
as well as the methods to predict the effect of temperature on vapour pressure, etc. is very
essential for chemical engineers.

6.1 VAPOUR PRESSURE AND BOILING POINT

6.1 .1 Vapour Pressure
Vapour pressure of a substance depends only on temperature. For solids, the vapour pressure
may be immeasurably low under normal circumstances, whereas liquids exert reasonably high
vapour pressures. Consider a pure liquid taken in a closed container at a given temperature . As
the potential energy due to molecular interaction far exceeds the kinetic energy of translation,
the molecules are not free to escape into the vapour phase and the substance exists as liquid.
When the temperature is increased, the molecules attain translational kinetic energy that is
sufficient to overcome the intermolecular attractive forces and the molecules escape into the
vapour phase. This process is known as vaporization . The pressure exerted by the vapour
130
 I Tapour Pressure 131

increases with the formation of more and more vapour. This also means that with the formation
of more and more vapour there will be a corresponding increase in the number of molecules
colliding with the surface of liquid. Some of these molecules get attracted by the molecules in
the liquid and returns to the liquid phase. This process is just the reverse of vaporization and
is known as condensation . Eventually, a dynamic equilibrium is established at which the number
of molecules of vapour that condense to form the liquid equals the number of molecules of
liquid that vaporize at constant temperature. At this state, as the rate of vaporization is equal
to the rate of condensation, the pressure attained by the vapour remains unchanged. This
pressure is the vapour pressure of the substance at the given temperature.
The magnitude of the vapour pressure is not affected by the quantity of liquid and vapour
as long as a free liquid surface is present in the system . It is a characteristic physical property
of the substance, which is determined by the potential energy of molecular interaction that is
to be overcome for vaporization to occur. This molecular interaction depends on the size and
nature of the molecules. Among chemically similar materials, the size of the molecules and the
attractive force between molecules increase with increase in the molecular weight. Consequently,
substances with higher molecular weights have lower vapour pressures at any specified
temperature .

6.1 .2 Boiling Point

Consider a liquid being heated in an open vessel . As temperature increases the vapour pressure
also increases, and at a particular temperature, it matches the external pressure . Vaporization
now takes place throughout the bulk of the liquid and the vapour so produced can displace the
surroundings. We treat the vaporization under this condition as boiling of the liquid and the
temperature at which this occurs as the boiling point of the liquid at the given external
pressure . The boiling point of a liquid when the external pressure is 101.3 kPa (atmospheric
pressure) is designated as the normal boiling point (NBP) of the liquid . For water, the normal
boiling point is 373.2 K, as at this temperature, the vapour pressure of water is 101.3 kPa .

6.2 PHASE BEHAVIOUR OF PURE SUBSTANCES

Gases are substances that are normally in the gaseous state at room temperature and atmospheric
pressure . If the temperature of a gas is below its critical temperature, it is called vapour. The
vapour can be condensed to a liquid by compression at constant temperature or by cooling at
constant pressure . A gas whose temperature is above the critical temperature cannot be condensed
by increasing the pressure at constant temperature.
When a vapour is compressed, the condensation starts when the pressure becomes equal to
the saturation pressure or the vapour pressure. The vapour at the point of condensation is called
a saturated vapour and the liquid condensate is called a saturated liquid. The saturation pressure
at a given temperature is a characteristic property of the substance and will not change till the
entire vapour is condensed. For water, the saturation pressure at 373.2 K is 1.013 bar. Alternatively,
the vapour pressure of water is 1.013 bar at 373.2 K . If the pressure of the vapour is below its
vapour pressure, it is called a superheated vapour. Alternatively, the temperature of a superheated
vapour is above the saturation temperature at the specified pressure . For example, the water
vapour at, say, 0.75 bar and 373.2 K is a superheated vapour, because the vapour pressure at
132 Stoichiometry and Process Calculations

373.2 K is 1.013 bar or because the saturation temperature at 0.75 bar is 365 K. When water
vapour at 0.75 bar and 373.2 K is compressed at constant temperature, condensation begins
when the pressure reaches 1.013 bar. The liquid and vapour phases coexist in equilibrium at
this condition. The amount of liquid formed increases at the expense of the vapour and
eventually the entire vapour is condensed.
For a pure fluid there is a unique set of saturation temperature and saturation pressure
values at which the two phases exist in equilibrium . At constant temperature, further increase
in pressure is possible only when the vapour is completely condensed. The substance is now
—
a subcooled liquid a liquid whose temperature is below the saturation temperature at a given
pressure or one whose pressure is above the vapour pressure at the specified temperature .
The ideas presented above can be illustrated clearly with the help of a P T diagram, as -
shown in Figure 6.1.

Critical
Fusion point
line c
<D
-
l
£
i

Vi h
<U
-
l l
Vaporization
3 line
zr.
O
Ui m n
— o T

a
P

-
1
3
o
oo

Sublimation Triple O
line ^ point >

Temperature
Figure 6.1 Pressure temperature diagram of a pure substance.
-

The compression of a superheated vapour initially at point a is represented by a vertical

line like the dotted line a-b -c in the figure. At point b, the liquid and vapour are in equilibrium .
The pressure and temperature at this point represent the saturation conditions. On complete
condensation, the material enters the subcooled liquid region represented by the line b-c. The
vaporization of a liquid is possible by the reverse process, i.e. by reducing the pressure over
the liquid at constant temperature. This is represented by the line c b a. --
Figure 6.1 includes the solid region also. A horizontal line such as the line m-n-o-p in the
figure represents the phase changes occurring by heating at constant pressure . Consider unit
mass of solid at pressure and temperature corresponding to point m in the figure. When it is
heated at constant pressure, the temperature increases and at point n the solid starts to melt.
The temperature corresponding to point n is the fusion temperature . The fusion line represents
the state of the system at which the solid is in equilibrium with the liquid. If transfer of heat
is continued the temperature remains constant till the entire solid is liquefied. The fusion
 I Tapour Pressure 133

temperature is a function only of the pressure. On further heating, the substance enters the
liquid region, and when it attains the temperature corresponding to point o lying on the
vaporization curve, the liquid begins to vaporize . This temperature is the saturation temperature
at the specified pressure and it remains constant till the vaporization is completed. The
saturation temperature is also known as the boiling point of the liquid at the given pressure .
Any point on the vapour liquid-equilibrium curve indicates the saturation temperature and the
pressure at which a vapour and liquid coexist in equilibrium . As seen from Figure 6.1, the
-
vapour liquid equilibrium curve extends only up to the critical point. When all liquid has been
vaporized, temperature increases along the line o-p in the vapour region. Heating beyond the
critical temperature Tc takes the substance into the gas region.
The fusion curve and the vaporization curve meet at the triple point where the three phases
coexist in equilibrium . For water at the triple point, T = 273.21 K and P = 6.1 x 10-3 bar. If
the pressure of the system is below the triple point pressure, the heating of the solid results in
sublimation, i.e ., the transformation of solid directly into vapour. The sublimation curve in
Figure 6.1 represents the state of the system in which the vapour is in equilibrium with solid.
It may be noted that the fusion curve extends up to infinity whereas the vaporization curve
terminates at the critical point.
Quality of vapour and use of steam tables: A pure fluid in vapour-liquid equilibrium exists
as a mixture of saturated liquid and saturated vapour, the amounts of which depend on the
extent of vaporization of the liquid . Quality of vapour measures the fraction of the mixture that
is vapour. For water and water vapour in equilibrium, the weight fraction of the mixture that
is dry steam is called the quality or dryness fraction of steam .
Steam tables provide a tabular representation of the thermodynamic properties of water in
the saturated liquid state or in the saturated or superheated vapour state. A detailed discussion
on the features of steam tables is provided in Chapter 12. Steam tables can be used to read
the vapour pressure of water at any given temperature or the saturation temperature of water
at a given pressure .
Refer to steam tables (thermodynamic properties of saturated steam) given in Appendix A3.
Consider the data given in the first four columns of the table. They are the saturation pressure,
saturation temperature and specific volumes of saturated liquid and saturated vapour, respectively,
of water.

Pressure (kPa) Temperature (K) Specific volume (xlO3 m 3/kg)

Saturated liquid Saturated vapour
40.00 349.02 1.027 3993
50.00 354.48 1.030 3240

At 40 kPa pressure, the saturation temperature of water is 349.02 K and the saturated liquid
at this condition has a specific volume of 1.027 x 10-3 m 3/kg and saturated vapour has a
specific volume of 3.993 m 3/kg. Alternatively, the steam table can be used to determine the
vapour pressure of pure water at a given temperature. For example, at 354.48 K, the vapour
pressure of water is 50 kPa. The steam tables which give temperature in the first column and
134 Stoichiometry and Process Calculations

other properties in the subsequent columns facilitate determination of vapour pressure as a

function of temperature easily.
Suppose that at 40 kPa, a mixture of saturated liquid and saturated vapour exist in equi-
librium . The specific volume of the mixture depends on the quality y or the fraction of the
mixture that is dry steam .
v = (1 - y )VL + yVG = VL + y(VG - VL ) (6.1)

where VL is the specific volume of saturated liquid, VG is the specific volume of saturated
vapour and .y is the quality of the steam . For a two-phase mixture of water at 50 kPa consisting
of 40% dry saturated steam and 60% saturated liquid, y = 0.4 and the specific volume is
3 ~ 3 3
V = VL + y(VG - VL ) = 1.030 x 10 “

+ 0.4(3.240 - 1.030 x 10 ) = 1.297 m /kg

EXAMPLE 6.1 The specific volume of wet steam at 500 kPa is 0.2813 m 3/kg. Using the data
from steam tables, determine the quality of steam .
Solution The following data are obtained from steam tables:
The specific volume of saturated liquid at 500 kPa = 1.093 x 10-3 m 3/kg and the specific
volume of saturated vapour = 0.3747 m 3/kg. Let y be the quality of steam . Then y is the
fraction that is vapour and 1 - y is the fraction of liquid .
(1 - y )( 1.093 x 10 3) + X0.3747) = 0.2813
"

Solving for y, we get y = 0.75. Therefore, the steam is 75% vapour and 25% liquid.

6.3 VAPOUR PRESSURE AND TEMPERATURE

The vapour pressure of a liquid increases with increase in temperature. The variation is as
shown in Figure 6.1. The following paragraphs deal with some of the different correlations that
have been proposed to represent the dependence of vapour pressure on temperature .

6.3.1 The Clapeyron Equation

The Clapeyron equation predicts the dependence of vapour pressure on temperature. It is given
by
dPs ~
X
(6.2)
dT TAV
where Ps is the vapour pressure of the liquid at temperature T , X is the latent heat of vaporization
and AV is the volume change accompanying vaporization.

6.3.2 The Clausius-Clapeyron Equation

Equation (6.2) can be modified to yield the Clausius-Clapeyron equation applicable for vapour-
liquid equilibrium by using the following simplifications:
1. The latent heat of vaporization is constant and independent of temperature .
2. The molar volume of liquid is negligible compared to that of vapour.
3. The vapour behaves as an ideal gas.
 I Tapour Pressure 135

If the temperature is not too near the critical point, the volume of the liquid is small in
comparison with the volume of vapour. The volume change accompanying vaporization
AV = VG - Vl , is therefore, approximately equal to VG , the molar volume of vapour. Equation (6.2)
now becomes
dPs _ X
~ (6.3)
dT TVG
The vapour pressure in regions well below the critical point is relatively so small that the vapour
can be assumed to behave as an ideal gas. The molar volume VG can now be replaced by
RT / PS so that Eq. (6.3) becomes
dPS _ ps A
dT RT 2

d In Ps X
(6.4)
dT RT 2
This result is known as the Clausius-Clapeyron equation . Assuming that the heat of vaporization
remains constant in the temperature range of Tx to T2 , Eq. (6.4) can be integrated to give the
following equation.

P2s X ( }_ _
In (6.5)
Rs
l R { TX r2 y

Pi and P\ are the saturation pressures at temperatures T2 and Tx respectively.

The assumption of constant latent heat of vaporization involved in the derivation of Clausius-
Clapeyron can be expected to be true only for moderate temperature ranges. Besides, at high
vapour pressures the vapour deviates considerably from ideal behaviour. Therefore, the Clausius-
Clapeyron equation is only an approximation and experimental data should be relied upon if
they are available. However, for rough estimates, the equation is found to be quite satisfactory
in many cases.

EXAMPLE 6.2 Calculate the vapour pressure of water at 363 K if the vapour pressure at
373 K is 101.3 kPa. The mean heat of vaporization in this temperature range is 2275 kJ /kg.

Solution Refer to Eq. (6.5). Tx = 363 K; T2 = 373 K; P 2S = 101.3 kPa

X = 2275 x 18 kJ/kmol; R = 8.314 kJ/kmol K; Pxs = ?
Substituting the values in Eq. (6.5), we get

101.3 2275 x 18 f 1
In ~ - 0.3638
PT 8.314 v 363 373 )

Pxs = 70.41 kPa

136 Stoichiometry and Process Calculations

EXAMPLE 63 The vapour pressure of acetone at 273 K is 8.52 kPa and that at 353 K is
194.9 kPa. Dry air initially at 101.3 kPa and 300 K is allowed to get saturated with the vapours
of acetone at constant temperature and volume . Determine
(a) The final pressure of the mixture
(b) The mole percent of acetone in the final mixture
Assume that the Clausius-Clapeyron equation is applicable to acetone .
Solution Using the Clausius-Clapeyron equation, i.e. Eq. (6.5), we get
8.52 _X( 1 1_ N

* 194.9 1^ 353 273 y

Therefore, XJR = 3770.52, and it is assumed constant in the given interval.
The vapour pressure at 300 K is evaluated as

In
Ps A r 1 1 \
194.9 R v 353 300 /
Substituting X /R = 3770.52 in the above equation, we get Ps = 29.53 kPa at 300 K .
(a) When air is saturated with the acetone vapours at 300 K, the partial pressure exerted
by acetone will be equal to its vapour pressure at 300 K . The partial pressure of air is
101.3 kPa at constant volume . Therefore, total pressure = 101.3 + 29.53 = 130.83 kPa.
moles of acetone , ^ partial pressure
(b) Mole percent = x 100 = x 100
total moles total pressure
29.53
x 100 = 22.6%
130.83

6.3. 3 The Antoine Equation

The Clausius-Clapeyron equation, i.e. Eq. (6.4) can be put in the following form
dPs
^=
X ( dT x d, r n
R IT )
ps 1 (6.6)
R
Integrating this equation, we get

In P s = A -- (6.7)
T
where A and B are constants. The Antoine equation is an empirical correlation for vapour
pressure and resembles Eq. (6.7). It is written as

In P s = A (6.8)
T -C
where A, J5, and C are known as Antoine constants. Equation (6.8) reduces to Eq. (6.7) when
C = 0. The Antoine constants for a few systems are listed in the Table 6.1 with Ps in kPa and
T in K. An exhaustive list is available in Reid, R.C, J.M. Prausnitz and B. E . Pauling, The
Properties of Gases and Liquids, 4th ed ., McGraw -Hill (1988) .
 I Tapour Pressure 137

Table 6.1 The Antoine constants

Name A B C Range of temperature (K )

Water 16.26205 3799.887 46.854 284^141
Acetone 14.39155 2795.817 43.198 241-350
Ammonia 14.9331 2940.46 56.34 179 261
-

Benzene 13.8858 2788.51 52.36 280 377

-

Chloroform 13.9582 2696.79 46.16 26-370

Ethyl alcohol 16.5092 3578.91 50.50 270-369
w-Heptane 13.8587 2911.32 56.51 270^100
w-Hexane 13.8216 2697.55 48.78 245-370
Methyl alcohol 16.5725 3626.55 34.29 257-364
Toluene 13.9987 3096.52 53.67 280^110
w -Pentane 13.8183 2477.07 39.94 220-330
Acrylonitrile 13.9103 2782.21 51.15 255-385
Nitromethane 14.2043 2972.64 64.15
Ethyl benzene 14.0045 3279.47 59.95
Chlorobenzene 13.9926 3295.12 55.60 335^105
Acetonitrile 14.2724 2945.47 49.15
Ethylene glycol 18.23507 6022.18 28.25 364^194
Glycerol 15.22417 4487.04 140.2 440-600
1,4-Dioxane 14.1177 2966.88 62.15 275^110
Methyl isopropyl ketone 12.16287 1993.12 103.2 271^106
Benzoic acid 15.14837 4190.70 125.2 405-560

It is to be remembered that the use of the Antoine equation outside the recommended range
of temperature leads to incorrect results. The Antoine equation provides an excellent correlating
equation for vapour pressures lying in the range of 1 to 200 kPa (Reid et al.).
More complex multi-parameter empirical correlations are available in literature for accurate
representation of vapour pressure of pure substances. The Riedel equation is one such model, i.e.

lnPs = A -- + ClnT + DT 6
T
where A , B , C and D are constants.
Lee and Kesler (AlChEJ ., 21, 510, 1975) have proposed the following equation for predicting
the vapour pressure of pure hydrocarbons knowing the critical properties and the acentric factor.
The equation gives the vapour pressure at the reduced temperature Tr as
In Prs = (In Pr)(°) + to (In Pr )< L
where P.s = —PP
L
c
and I’
T
= —T
c
and co is the acentric factor.

With P and Pc in kPa, the following equations may be used to evaluate (In Pr)(0) and
(In Pr )Q\
(0 ) 6 096 48
(In Pr ) = 5.927 14 - - 1.288 62 In Tr + 0.169 347T 6r
Tr

QnPr )a ) = 15.2518
1
^:^
07
^
13.4721 In Tr + 0.435 771f
Tr
138 Stoichiometry and Process Calculations

This equation predicts the vapour pressure of pure hydrocarbons within 3 to 4 percent if
0.30 < Tr < 1.0.

EXAMPLE 6.4 The Antoine constants for /7-heptane are A = 13.8587, B = 2911.32, and
C = 56.56. Ps is in kPa and T is in K. Calculate
-
(a) The vapour pressure of /7 heptane at 325 K
(b) The normal boiling point of /7-heptane
Solution (a) The Antoine equation is

In Ps = A - —
T -C

For /7 -heptane at 325 K, the vapour pressure is

2911.32
In Ps = 13.8587 - = 3.0134
325 - 56.56
Therefore, Ps = 20.36 kPa.
(b) The normal boiling point is the temperature at which the vapour pressure is 101.3 kPa.
Substitute Ps = 101.3 kPa in the Antoine equation.
2911.32
In 101.3 = 13.8587 -
T - 56.56
Solving this equation, T = 371.62 K.

6.4 VAPOUR PRESSURE PLOTS

Vapour pressure, as we have seen, is a strong function of temperature. Generally, a large number
of experimental data would be necessary to establish a functional relationship between vapour
pressure and temperature graphically. Frequently in chemical engineering calculations, it becomes
necessary to interpolate or extrapolate vapour pressure data from a very few experimental
observations, these being easily carried out if a straight line results when the vapour pressure
is plotted against temperature . The Clapeyron equation, i.e. Eq. (6.2) provides a relationship
which indicates that a plot of the logarithm of the vapour pressure against the reciprocal of
temperature is a straight line. It is observed that this relationship predicts the dependence of
vapour pressure on temperature accurately when the pressure is low. But, there is a considerable
deviation from the linear behaviour at higher pressures. The simplifications that were used in
arriving at this relationship are no longer valid if the pressure is high. At high pressures, the
molar volume of the liquid is comparable with that of the vapour and cannot be neglected. Also,
the vapour deviates from ideal behaviour and the latent heat of vaporization is not constant. The
reference substance plots for vapour pressures are useful in such cases, as these provide the
vapour pressure as linear functions of temperature even at higher pressures. Two such plots
are in common use: The equal-pressure reference-substance plots and the equal-temperature
reference -substance plots.
 I Tapour Pressure 139

6.4.1 Equal -Temperature Reference- Substance Plots

In equal-temperature reference-substance plots, the logarithm of the vapour pressure of a
substance is plotted against the logarithm of the vapour pressure of a reference substance, both
at the same temperature . Since the vapour pressure versus temperature data for water are
readily available, water is usually chosen as the reference substance .
The Clapeyron equation (Eq. 6.6) may be written as

d \nPs (- (6.9)
R J' J

where Ps is the vapour pressure of the substance . The vapour pressure of the reference
substance ( PR ) at the same temperature may be written as

d In PRS AR
.
d T (6.10)
R
Dividing Eq. (6.9) by Eq. (6.10), we get
d In Ps _ ( XIR )d (\IT )
— (6.11)
d In PR ( XR / R )d (\ / T )
Equation (6.11) leads to

In P - = —AA
c s'
In PD + constant (6.12)
*
If the ratio X / XR is constant, this equation predicts a linear behaviour when the logarithm of
vapour pressure of a substance is plotted against the logarithm of the vapour pressure of the
reference substance. Though the latent heat of vaporisation may vary with temperature, it is a
reasonably good approximation to assume that A and XR both vary to the same extent that their
ratio remains constant. Thus, Eq. (6.12) provides a better means for predicting the vapour
pressure variation with temperature than Eq. (6.1)
The equal-temperature reference -substance plots are known as the Cox chart because these
are prepared based on the method suggested originally by E . R. Cox ( Ind. Eng. Chem. , 15, 592,
1923). Figure 6.2 gives the Cox chart in which the vapour pressure of different substances are
given in mm Hg. and temperature is given in °C. In these plots, the logarithm of the vapour
pressure of the substance is plotted as the ordinate against the logarithm of the vapour pressure
of the reference substance at the same temperature as the abscissa. For convenience, the
abscissa scale is converted to read temperature instead of vapour pressure. This non-linear
temperature axis is created as follows. Refer Figure 6.3. The ordinate reads the vapour
pressure on the logarithmic scale . A straight line with positive slope is drawn, which represents
the vapour pressure of the reference substance, say water. Take the vapour pressure of water
at a desired temperature on the .y-axis, and move horizontally to the straight line representing
the vapour pressure. For example, the vapour pressure of water at 75°C is 289.2 mm Hg
(38.55 kPa). From 289.2 on the .y-axis, move horizontally to point C on the straight line AB .
From point C move vertically downwards to point D on the x-axis. Point D is marked to read
75°C (348 K). The temperature 50°C (323 K) can be marked by taking the vapour pressure
92.6 mm Hg (12.34 kPa) on the vertical axis, moving horizontally to the line AB and then
140 Stoichiometry and Process Calculations

100,000 / /
,
CoH
2 6
CO 2 NH 3

10000 X
C3 H8 J^ so 2 C ,4“H 10
/

^^ 10
/
22 Cadmium
/
,
/
12 0
Methyl /
Ethyl
ether X alcohol £5 x / ^i 12 26
1000 /
/X X / / / u
600 X H

400
/ / O
«2
CC
CC1 i
s.
/ Toluene CI 6H34 C
O
CS 2 /
200 3
3
100 / /W6 / K
X ' / 00
C6 H ] 4
/ c 25^52
<r
60 ~ C8H 18
40 /
/ Sodium

20
^ 20* *42

10
X
XEthyl /
Zinc

6 alcohol
4 Mercury
C3(/*62
Antimony
2
i
0
/
10 20 30
/
75
/
100
/
150 200 250 300 400
L /
500 600 700 1000
Temperature, °C
Figure 6.2 The Cox chart.

vertically to the x-axis to locate 50°C (323 K). Similarly, temperatures 10°C, 25°C, 100°C,
150°C, etc ., can be marked off by taking the vapour pressures of water at the respective
temperatures. Figure 6.3 illustrates the construction of the Cox chart .
The vapour pressures of other substances plotted on this special coordinate scales will yield
straight lines over a considerable range of temperature . These lines can be drawn from the
vapour pressure of a substance at just two temperatures. Another feature of the Cox chart is that
the lines of vapour pressures of the members of a homologous series of compounds or members
of a group of closely related compounds converge at a point, called the infinite point which is
characteristic of that group. This feature makes it possible to establish the complete vapour
pressure-temperature relationship of a member of the group with only one experimental value
and the infinite point.
It has been shown that the temperature scale on the Cox chart with water as the reference
substance is nearly equivalent to the function ( T+ C)-1 where C is approximately equal to
-43 K. Thus the Cox chart resembles the Antoine vapour pressure equation:

In Ps = A - (6.13)
T - 43
 I Tapour Pressure 141

10,000

3571.2

1000
760.0

^ 289.2
-
C

CD 92.6 =
g
co
a
PH
23.8 -

9.2 : 10

D
10 25 DO 75 100 150
Temperature, °C
Figure 6.3 Construction of Cox chart .

EXAMPLE 6.5 Construct the Cox chart for the vapour pressure of acetone given that the
vapour pressures are 8.52 kPa and 194.9 kPa at 273 K and 353 K respectively. The vapour
pressure of water is obtained from steam tables as given below:

T (K) 273 293 313 323 333 353 373

Ps ( kPa) 0.61 2.33 7.37 12.34 19.90 47.35 101.3

Compare the vapour pressure at 323 K given by the Cox chart with the experimental value of
73.94 kPa.
Solution Pressures are marked on the logarithmic scale on the vertical axis. A straight line
AB is drawn with a convenient slope as shown in Figure 6.4. The temperature scale is established
by the procedure explained earlier. For example, consider the second data point. At 293 K, the
vapour pressure is 2.33 kPa. From 2.33 kPa on the vertical axis, move horizontally to line AB
and make point C. From point C, move vertically downwards and mark T = 293 K, on the
horizontal axis. Thus all temperatures can be marked . Points D and E are located such that they
give the vapour pressures of acetone at 273 K and 353 K respectively. Line DE is drawn which
can be used for interpolating and extrapolating the vapour pressure data of acetone at any
temperature. Read the vapour pressure of acetone at 323 K from the graph. Vapour pressure
of acetone at 323 K = 74.5 kPa.
142 Stoichiometry and Process Calculations

194.9 200

B
101.3 Zr 100
/
74.50 7
7
/
47.35
z7
19.90
12.34
D
/ 10
« 8.52 /
Sa 737 /
<LT. /
u
3
C/2
7 4-
C/2
<D
UH
PH
2.33 +

7 1.0
7
0.61
7
7

i
0.1
273 293 313 323 333 353 373
Temperature, K
Figure 6.4 Construction of the Cox chart for Example 6.5 .

Alternatively, the vapour pressure of acetone at 323 K can be determined analytically since
the equal-temperature reference -substance plot can be assumed linear. That is, the vapour
pressure of water is plotted against the vapour pressure of acetone at the same temperature, the
resulting curve should be a straight line. We have the following vapour pressure data:
At 273 K, the vapour pressure of water = 0.61 kPa. The vapour pressure of acetone
= 8.52 kPa. At 353 K, the vapour pressure of water = 47.35 kPa. The vapour pressure of
acetone = 194.9 kPa. The vapour pressure of water at 323 K is 12.34 kPa.
The vapour pressure of acetone at 323 K (Ps) is now obtained by linear interpolation,
knowing that the vapour pressure of water at this temperature is 12.34 kPa .
log 194.9 - log 8.52 log Ps - log 8.52
log 47.35 - log 0.61 log 12.34 - log 0.61
2 2898 - 0 9304
, , log Ps - 0 9304
,
~

1.6753 + 0.2147 1.0913 + 0.2147

log Ps = 1.8698. Therefore, the vapour pressure of acetone at 323 K, Ps = 74.09 kPa.
 I Tapour Pressure 143

The vapour pressure given by the equal-temperature reference-substance method is greater

than the experimental value of 73.94 kPa by 0.15 kPa. Therefore,

percent
F deviation = x 100 = 0.20%
73.94

6.4.2 Equal -Pressure Reference - Substance Plots

In equal-pressure reference-substance plots, the temperature at which a substance has a given
vapour pressure is plotted against the temperature at which the reference substance has the same
vapour pressure. These are analogous to the Cox chart and the underlying equations can be
derived in the same way as Eq. (6.11) was derived.
It is observed that if boiling point of a substance is plotted against the boiling point of a
reference substance at the same pressure, a straight line results. This is found to be true for
moderate ranges of pressures, though there may be variation over wide ranges of pressures. The
Duhring lines are examples of equal-pressure reference-substance plots.
In Figure 6.5 the Duhring lines of various concentrations of sodium hydroxide are plotted
with water as the reference substance . The temperature of water is taken as ordinate against the
cs co
© © ©

X X X
200
V / * = 0.50
* = 0.55
x = o. i * = 0.60
* = 0.65
x = mass fraction of NaOH * = 0.70
150

u
o y /
£ 25
03
£ * = 0.0
o y y
B 00
o
y

CIJJ
S 75 y
o

50
y
V
y y
25
y
25 50 75 100 125 150 175 200 225 250
Boiling point of solution, °C
Figure 6.5 Duhring lines for sodium hydroxide-water.
144 Stoichiometry and Process Calculations

temperature of solution having the same vapour pressure as the abscissa . These charts can be
used to find the boiling point of a solution of known composition at a given pressure or the
vapour pressure of the solution at a given temperature . For example, let the boiling point of a
30% solution of sodium hydroxide in water at a pressure of say, 80 kPa is to be measured.
At 80 kPa, the boiling point of water is 93.3°C (366.5 K). From 93.3°C on the vertical axis
move horizontally to the Diihring line of 30% NaOH and then vertically to the horizontal axis
to get the boiling point of 30% solution at 80 kPa as 106.8°C (380 K).

EXAMPLE 6,6 The vapour pressure over a 25% solution of sulphuric acid in water is 6.08
kPa at 313 K and 39.33 kPa at 353 K. Assuming that the Diihring line is linear over this range,
predict the vapour pressure over the solution at 333 K. The vapour pressure of water is given
by the Antoine equation

3799.887
In Ps = 16.26205 -
T - 46.854
where pressure is in kPa and temperature in K. If the experimental value of the vapour pressure
of a 25% solution of sulphuric acid in water at 333 K is 16.53 kPa, what is the percent
deviation of the vapour pressure predicted by the equal-pressure reference -substance method
from the actual value?
Solution The boiling point of water at 6.08 kPa is calculated using the Antoine equation,
i. e .
3799.887
In 6.08 = 16.26205
T - 46.854
Solving this, we get T = 309.69 K.
Similarly, at 39.33 kPa,
3799.887
In 39.33 = 16.26205 -
T - 46.854
Solving this, we get T = 348.67 K.
A graph is drawn (Figure 6.6) with boiling point of water as the ordinate and the boiling
point of solution as the abscissa. Point A is marked to represent the boiling points of water and
the solution at a pressure of 6.08 kPa and point B is marked to represent the boiling points at
39.33 kPa. The straight line AB is the Diihring line . To find the vapour pressure of the solution
at 333 K, take 333 K on the horizontal axis and read the boiling point of water at the same
pressure from the Diihring line. This is found to be 329 K. The vapour pressure of water at
329 K is obtained from the Antoine equation.
3799.887
InP5 = 16.26205 -
329 - 46.854
or Ps = 16.35 kPa
The vapour pressure of the solution at 333 K and the vapour pressure of water at 329 K are
equal. Therefore, the vapour pressure of the solution at 333 K is equal to 16.35 kPa.
 I Tapour Pressure 145

350
348.7 5

340

uf
& 330
% 329
'
—
o
4 >
c
o
OH
00
c 320
*
o
CQ

309.7 310
7f4
300
300 313 320 333 340 353 360
Boiling point of solution, K
Figure 6.6 Equal pressure reference plot for sulphuric acid (Example 6.6).

Alternatively, assuming the Duhring line to be a straight line, the boiling point of water ( TR )
can be calculated as
348.67 - 309.69 _
"
TR - 309.69
353 - 313 333 - 313
which gives TR = 329.18 K . Water at 329.18 K and 25% sulphuric acid at 333 K have the same
vapour pressure . The vapour pressure of water at 329.18 K is determined using the Antoine
equation.
3799.887
In Ps = 16.26205 -
329.18 - 46.854
Therefore, Ps = 16.49 kPa. Thus, the vapour pressure of the solution at 333 K = 16.49 kPa.
This is less than the experimental value of 16.53 kPa by 0.04 kPa. Therefore, the percent
deviation is as follows:

% deviation = -
16.53^ixioo = 0.24%
146 Stoichiometry and Process Calculations

EXERCISES
Vapour pressure and boiling point
6.1 The vapour pressure of ethyl ether at 273 K is 25 kPa and its latent heat of vaporization
is 4.185 x 102 kJ/kg. Using the Clausius-Clapeyron equation, estimate the vapour
pressure at 293 K and 308 K.
6.2 The vapour pressure of ethyl ether at 273 K is 25 kPa and at 293 K is 63.5 kPa.
Estimate the latent heat of vaporization of ether in kJ/kg in this temperature range.
6.3 Using the Clausius-Clapeyron equation [Eq. (6.5)], calculate the vapour pressure of
water as a function of temperature and compare the result with the following values
taken from steam tables.

T (K ) 273 293 313 323 333 353 373

Ps (kPa) 0.61 2.33 7.37 12.34 19.90 47.35 101.3

The latent heat of vaporization of water at the triple point (0.611 kPa, 273.16 K)
is 45.05 kJ/mol and that at the normal boiling point (101.325 kPa, 373.15 K) is
40.66 kJ /mol. These may be assumed constant for the lower temperature range and the
higher temperature range respectively.
6.4 Nitrogen from a cylinder is bubbled through acetone at 1.1 bar and 323 K at the rate
of 2 x 10-4 m 3/min. The nitrogen saturated with acetone vapour leaves at 1.013 bar,
308 K at the rate of 3.83 x 10 4 m 3/min. What is the vapour pressure of acetone at
“

308 K ?
6.5 Mercury has a density of 13.69 x 103 kg/m 3 in the liquid state and 14.193 x 103
kg/m 3 in the solid state both measured at the melting point of 234.33 K at 1 bar. If
the heat of fusion of mercury is 9.7876 kJ/kg, what is the melting point of mercury
at lObar?
6.6 The vapour pressure of chloroform is given by the Antoine equation
2696.79
In Ps = 13.9582 -
T - 46.16
where pressure is in kPa and temperature in K . Determine (a) the boiling point of
chloroform at 50 kPa and (b) the vapour pressure at 300 K .
6.7 The Antoine constants of acrylonitrile are A = 13.9103, B = 2782.21, and C = 51.15,
when the vapour pressure is in kPa and temperature in K. Calculate the vapour pressure
at 300 K .
6.8 How many kilograms of acetone must have vaporized before an atmospheric chamber
of volume 10 cubic metres gets saturated with the vapours of acetone at 313 K? The
Antoine constants (pressure in kPa and temperature in K) for acetone are A = 14.5463,
B = 2940.46 and C = 49.15 .
 I Tapour Pressure 147

6.9 The vapour pressure of water (kPa) is represented by the equation

h g p S = - A+ B - e ~ 2o(
^ )2

Tr
where A = 3.142 and b = 0.163 and temperature is in K. If the vapour pressure of
water at 303.15 K is 4.241 kPa and the critical temperature of water is 647.3 K, what
is the vapour pressure of water at 350 K? Get the vapour pressure of water from steam
tables and calculate the percent deviation.
6.10 Air at 300 K and 1.0 bar containing 0.02 moles water per mole dry air is compressed
and stored at 100 bar and 300 K for use in an experimental wind tunnel. How much
water will condense in the high-pressure storage vessel per 100 cubic metres of air
compressed? The vapour pressure of water at 300 K = 3.564 kPa.
6.11 A stream of gas at 302 K and 100 kPa, 50% saturated with water vapour is passed
through a drying tower where 90% of the water vapour is removed . For 100 cubic
metres of gas admitted through the tower, how many kilograms of water is removed?
The vapour pressure of water at 302 K is 4.0 kPa.
Reference- substance plots
6.12 Prepare the Cox chart for /7-heptane if the vapour pressures are 12.28 kPa at 313 K
and 105.60 kPa at 373 K. Estimate the vapour pressure of /7-heptane at 333 K using
the chart. If the experimental value is 27.91 kPa, what is the percent deviation in the
estimate? The following data for vapour pressure of water is taken from steam tables:

T (K ) 273 293 313 323 333 353 373

Ps ( kPa) 0.61 2.33 7.37 12.34 19.90 47.35 101.3

6.13 Construct the Cox chart for predicting the vapour pressure of ethanol and using the
chart estimate the normal boiling point of ethanol and the vapour pressure at 323 K.
By how much % these values depart from the actual values? The vapour pressure of
ethanol at 293 K and 363 K are respectively, 5.76 kPa and 157.03 kPa. The vapour
pressure of water is as follows:

T ( K) 273 293 313 323 333 353 373

Ps (kPa) 0.61 2.33 7.37 12.34 19.90 47.35 101.3

The experimental value of the normal boiling point is 351.7 and the vapour pressure
at 323 K is 29.2 kPa.
6.14 The following data refer to the vapour pressure of sulphur dioxide:

T (K) 279.5 328.7

Ps (kPa) 202.7 1013
148 Stoichiometry and Process Calculations

(a) Fit the data into an equation of the form lnPs = A where Ps is in kPa
T - 43
and T in K.
(b) What is the vapour pressure of sulphur dioxide at 373 K?
6.15 The boiling points of methanol, ethanol and /7-propanol at 8 kPa are 285.25 K, 299.15 K
and 316.65 K respectively. Construct the Cox chart for methanol and ethanol given that
their normal boiling points are 337.85 K and 351.7 K respectively. Using this chart
predict the normal boiling point of /7-propanol. How does your result compare with the
experimental value of 370.95 K ? The vapour pressure of water is given below :

T (K) 273 293 313 323 333 353 373

Ps (kPa) 0.61 2.33 7.37 12.34 19.90 47.35 101.3

6.16 The following table gives the vapour pressures of benzene and water. Plot the reference
temperature vapour pressure curve with the logarithm of vapour pressure of benzene
on the y-axis and the logarithm of vapour pressure of water on the x-axis.

T (K) 288.6 299.3 315.4 333.8 353.3 377.0 415.7 452

PB (kPa) 8.0 13.3 26.7 53.3 101.3 202.7 506.6 1013.0
4 (kPa) 1.8 3.4 8.3 26.1 49.0 116.3 382.5 980.0

(a) Determine the vapour pressure of benzene at 373 K .

(b) Determine the latent heat of vaporization of benzene at 298 K given that the latent
heat of vaporization of water at 298 K is 2443 kJ/kg. Compare your result with
the experimental value of 434 kJ/kg.
6.17 Construct the Duhring line for ethylene glycol if it is given that its normal boiling point
is 470.45 K and the boiling point at a pressure of 8 kPa is 402.65 K . The vapour
3799:887
pressure of water is given below : lnPs = 16.26205 .
T - 46.854
(a) By how much does the vapour pressure of ethylene glycol at 432 K deviate from
the experimental value of 26.66 kPa?
(b) What is the boiling point of ethylene glycol at 2.67 kPa?
6.18 Construct the Duhring line for ethanol if it is known that the vapour pressure of ethanol
at 299.1 K is 8 kPa and that at 351.55 K is 101.3 kPa. The vapour pressure of water
is given by the Antoine equation
3799.887
In Ps = 16.26205 -
T - 46.854
where pressure is in kPa and temperature is in K. Compare the vapour pressure of
ethanol at 321.6 K given by the Duhring line with the experimental value 26.66 kPa.
 7 Solutions and
Phase Behaviour

Chemical engineering unit operations are concerned with transport, storage, concentration and
separation of solutions containing two or more components. The components constituting the
solution may exist as a miscible liquid solution or as two immiscible or partially miscible liquid
phases. The components in the solution may be volatile or certain of the constituents may be
non-volatile. The vapour pressure over the solutions is a very important consideration in the
design and operation of process equipment. In this chapter, we are concerned with the evaluation
of vapour pressure over solutions, calculation of the composition of the vapour in equilibrium
with the given liquid, the evaluation of the bubble -point and dew-point temperatures of binary
and multi-component mixtures.

7.1 IDEAL SOLUTIONS AND RAOULT’ S LAW

7.1.1 Ideal Solutions
The vapour pressure of a constituent of a solution at any temperature will be different from
the vapour pressure it exerts in the pure state . Consider a pure liquid A in equilibrium with its
vapour. The number of molecules of A per unit area of the liquid surface is more than the
number of molecules when A is in solution with another liquid, say, B . This is the reason why
the vapour pressure over a solution is less than that of the pure liquid . Also, the forces that
hold the molecules together in the liquid and thus prevent their escape into the vapour phase
are not the same as the forces that are present in the pure liquid state . If the molecular forces
of interaction between the like molecules ( A-A or B-B interaction) were of the same order of
magnitude as those between unlike molecules (the A-B interaction), the forces that a molecule
of A experiences in the solution with B will be the same as it experiences in the pure state .
If this is the case, the difference between the vapour pressure of a constituent in the solution
and that in the pure state will be entirely due to the decrease in the number of molecules per
unit area of the liquid surface, which in turn depends on the concentration of the particular
component in the solution. Therefore, it is natural to expect the vapour pressure exerted by the
149
150 Stoichiometry and Process Calculations

constituents in the solution formed by chemically similar substances with approximately equal
intermolecular forces to be directly proportional to the concentration in the solution. Such
solutions are known as ideal solutions. A solution conforming to the ideal behaviour has the
following general characteristics, all interrelated .
1 . The components are chemically similar. The average intermolecular forces of attraction
and repulsion in the pure state and in the solution are of approximately the same order
of magnitude.
2 . There is no volume change on mixing or the volume of the solution varies linearly with
composition.
3. There is neither absorption nor evolution of heat when an ideal solution is formed by
mixing the constituents; that is, there is no enthalpy change and no temperature change
on mixing.
4. The components in an ideal solution obey Raoult ’s law.

7.1.2 Raoult’s Law

Raoult’s law states that the vapour pressure of a component in a solution (or the equilibrium
partial pressure of the component) is directly proportional to its concentration. That is,
Pi = * AS ( 7.1)
where pt is the partial pressure of component / and xz is its mole fraction in the liquid . Pf is
the vapour pressure of pure i at the same temperature as that of the solution.
Raoult’s law is obeyed by ideal solutions over the entire range of compositions. However,
it should be understood that there exists no ideal solution in the strict sense of the word; but
actual mixtures approach ideality as a limiting behaviour. Ideality requires that the molecules of
the constituents are similar in size, structure and chemical nature ; only optical isomers of
organic compounds meet these requirements. Thus a mixture of ortho- , meta-, and para -xylene
conforms very closely to the ideal solution behaviour. Practically, adjacent or nearly adjacent
members of the homologous series of organic compounds can be expected to form ideal
solutions. Thus, in engineering calculations, mixtures of benzene and toluene , ^-octane and n-
hexane, ethyl alcohol and propyl alcohol, acetone and acetonitrile, paraffin hydrocarbons in
paraffin oils, etc. can be treated as ideal solutions. Raoult’s law applies as fair approximation
to mixtures of hydrocarbons that show a reasonable similarity in molecular structure such as
the ones encountered in petroleum industry. In most other cases Raoult’s law applies only over
a limited concentration range.

7.1 .3 Raoult’s Law and Vapour-Liquid Equilibrium Calculation

Consider a liquid mixture in equilibrium with its vapour. The vapour composition will be
different from that of the liquid with which it is in equilibrium . The determination of the
compositions of the vapour and liquid in equilibrium at specified conditions of temperature and
pressure is important in many chemical engineering calculations, particularly in computations
involved in separation operations. Also important is the establishment of conditions of temperature
and pressure at which the vapour and liquid of known composition exist in equilibrium . These
calculations are relatively simple for solutions obeying Raoult’s law.
 Solutions and Phase Behaviour 151

Consider a binary mixture of components A and B . Assume that Raoult’s law is applicable
to the solution over the entire composition range. When the solution is in equilibrium with its
vapour, we can write for the equilibrium partial pressure of the constituents, the following:

PA = XAPAS ( 7.2)

PB ~
XBPB ( 7.3)
where pA and pB are the partial pressures of components A and B respectively, and xA and xB
are their respective mole fractions in the liquid . We know that for a binary solution,
xA + xB = 1 or xB = (1 - xA ) ( 7.4)
By Dalton’s law, the total pressure of the vapour ( P ) is equal to the sum of the partial pressures
of the constituents. Therefore,
p = P A + PB
That is,
P = xAPAs + xBPBs = xAPAs PBs
+ (1 - xA ) ( 7.5)
Using Eq. (7.5), the total pressure over a solution of known composition can be calculated. The
mole fraction of a component in a gas phase, by Dalton’s law, is the ratio of partial pressure
to the total pressure. Let yA and yB be the mole fractions of components A and B respectively,
in the vapour phase. By Dalton’s law,

yA = PPA
_ _ ( 7.6)

Equation (7.6) can be rewritten as given below using Equations (7.2) and ( 7.5) .

yA = XAPA ( 7.7)
XAPA + XBPB
Similarly, for component B,

= ~~
XBPB ( 7.8)
Zs S
XAPA + XBPB
It may be noted that yA + yB = 1.
7.1.4 P-x-y Diagram
Equations ( 7.2) and ( 7.3) indicate that when the partial pressures over the solution at constant
temperature are plotted against the mole fraction xAt we would get two straight lines shown as
dotted lines in Figure 7.1.
We can write Eq. ( 7.5) as given below which indicates that the total pressure versus xA
also will be a straight line.
P = xAPAs + (1 - xA )PBs = CPi ~ P$)XA + Pi ( 7.9)
Equation ( 7.9) means that the total pressure over an ideal solution also varies linearly with
152 Stoichiometry and Process Calculations

liquid composition. Figure 7.1 also shows the total pressure versus yA at constant temperature .
--
The P x y diagram of Figure 7.1 is one method of representing the vapour-liquid equilibrium
data at constant temperature.
150
Constant temperature

P vs y
a
C3

3
P VS X
C/2
C/5

PA VS V
V'--
PB vs X
0
u Mole fraction , x ory

--
Figure 7.1 The P x y diagram of ideal solutions .

7.1 .5 --
Boiling- point Diagram (T x y Diagram )
The P -x-y diagram gives the vapour-liquid equilibrium relation at constant temperature . Another
method of expressing equilibrium is the T-x-y diagram , also known as the boiling point dia-
gram . This refers to constant pressure conditions and is important in distillation calculations.
Consider Eq. (7.5). The vapour pressures of the pure components depend on the temperature
and therefore the equilibrium temperature at constant pressure is determined by trial and error
so that at equilibrium Eq. (7.5) is satisfied for a given liquid concentration xA . Equilibrium
vapour composition 3/ 4 is then calculated using Eq. (7.6) . This is repeated for different xA values
ranging from 0 to 1. When xA = 0, the equilibrium temperature is the boiling point of pure B,
and when xA = 1.0, the equilibrium temperature is the boiling point of pure A . The plot of T
versus xA and T versus yA are known as the bubble -point curve and the dew -point curve of the
mixture at the given pressure P . These two curves together constitute the boiling point diagram
(Figure 7.2).
The calculations for establishing the boiling point diagram can be simplified if we can
eliminate the trial-and-error route for calculation of equilibrium temperature. This is achieved
by assuming a temperature and using the vapour pressure values at this temperature in Eq. (7.5)
to calculate the liquid composition , and Eq. (7.6) to calculate the vapour composition. For this
purpose, Eq. ( 7.5) and Eq. (7.6) may be rearranged as
P ~ PB
XA = pS _ pS ( 7.10)
rA rB
 Solutions and Phase Behaviour 153

T Pressure constant

r vs xA
Vapour

—
*
3
C3

H
Q
s - p

Liquid
PvsyA

Mole fraction, xA oi[ yA 1

Figure 7.2 The boiling point diagram .

S
yA = XAPA ( 7.11)
p
It may be noted that the temperature assumed should lie between the boiling points of pure
components at the given total pressure.

7.1 .6 Equilibrium Diagram ( y-x Diagram )

A horizontal line such as the line PQ in Figure 7.2 connects the composition of liquid and
vapour in equilibrium at a specified temperature. Such a line connecting the composition of the
equilibrium phases is called a tie line . Several such tie lines can be drawn, each giving a set
of x and y values representing the composition of the liquid and vapour phases in equilibrium .
On a plot with vapour composition ( y ) as the ordinate against the liquid composition x as
the abscissa, these equilibrium compositions are represented as points such as point M in
Figure 7.3.
A smooth curve drawn through such points gives the equilibrium distribution diagram or
simply, the equilibrium curve . The equilibrium diagram also refers to a specified constant total
pressure. The farther the equilibrium curve from the diagonal, the richer the vapour in component
A. Separation of the solution into its components by distillation will be difficult if the equilibrium
curve is very close to the diagonal.

7.1 .7 Flash Vaporization

In flash vaporization, also known as equilibrium distillation, a liquid mixture is partially vaporized
producing liquid and vapour products that are in equilibrium . The determination of the degree
or extent of vaporization for producing a distillate (and a residue) of specified composition and
154 Stoichiometry and Process Calculations

the establishment of the conditions of temperature and pressure for the process are typical flash
vaporization problems. Also important is the estimation of the composition of the products for
a given degree of vaporization.
1

Equilibrium curve
y 5/ W
u -
C
Cu
CG
>
c
G M
O
VP
o
«3
45° reference line
(diagonal), y - x
1)
c
E
*

0 x , mole fraction in liquid 1

Figure 7.3 The equilibrium diagram.

Consider the flash vaporization process which is schematically represented in Figure 7.4.
The liquid is heated by passing through a heat exchanger and the pressure is then reduced by
passing the mixture through a valve . The sudden reduction in pressure results in partial
vaporization of the liquid. The product liquid and vapour streams can be considered to be in
equilibrium with each other owing to the intimate contact which prevails during the flashing
operations. The products are then introduced into a vapour-liquid separating vessel and separated
as distillate and residue.

- Distillate,
Heat exchanger ^
Feed , xF
4
-
/M)- -tXh
Valve
>
Product
separator

- Residue , xw

Figure 7.4 Flash distillation process .

If / is the fraction of the feed that is vaporized in a flash vaporization process, and if xw
and yD are the mole fraction of component A in the liquid and vapour products respectively,
 Solutions and Phase Behaviour 155

then moles of A in the feed = moles of A in the vapour product + moles of A in the liquid
product
xF = JyD + ( l - J )xw
where x F is the mole fraction of A in the feed liquid . This equation may be rearranged as
Xw
Xp ~
f = ( 7.12)
XD XW
Equation ( 7.12) gives the fraction of the feed that is vaporized. Here x w andy are equilibrium
compositions, which are interrelated through Raoult’s law if the solution is ideal. ^
EXAMPLE 7.1 At 360 K the vapour pressures of ^ -heptane and toluene are respectively 71.2
kPa and 48.9 kPa. Determine the composition of the liquid and vapour in equilibrium at 360 K
and 65 kPa, if it is given that ^-heptane and toluene form ideal solutions.
Solution Refer to Eq. (7.9)
P/ = 71.2; Pjf = 48.9, P = 65.0
65 = 48.9 + (71.2 - 48.9)x
where x is the mole fraction of heptane in the liquid. On solving this, x = 0.722.
Using Eq. (7.6),
0.722 x 71.2
y= = 0.791
65
The liquid and the vapour at the given conditions contain respectively 72.2% (mol) and
79.1% (mol) heptane.

EXAMPLE 7.2 The vapour pressures of two pure liquids A and B are respectively 100 kPa
and 60 kPa at 320 K. The concentration of A in the vapour in equilibrium with a solution of
A and B is found to be 50% (mol). Determine the following:
(a) The composition of the liquid
(b) The total pressure of the vapour
Solution Partial pressures of the components are obtained by using Eqs. (7.2) and (7.3),
i.e.
PA = xAPj = 100x 4
PB = XBPB = 60XB
Equation ( 7.5) gives the total pressure:
P = xAP$ + (1 - xA )P § = IOOX 4 + (1 - X 4)60 = 60 + 40x 4 (A)
(a) By Dalton’s law
156 Stoichiometry and Process Calculations

Substitution of the values gives

100x
0.5 = ^
60 + 40 x
^
Solving the above equation, we get xA = 0.375 . The liquid contains 37.5% (mole) A .
(b) Using Eq. (A), the total pressure is
60 + 40 x 0.375 = 75 kPa

EXAMPLE 7.3 A liquid mixture containing 25% A , 30% B and the rest C is in equilibrium
with the vapour which contains 50% B. All percentages are on a mole basis. The equilibrium
pressure and temperature are 200 kPa and 350 K. At 350 K the vapour pressure of C is 50 kPa.
What is the percentage of A in the vapour?
Solution xA = 0.25, xB = 0.30, xc = (1.0 - 0.25 - 0.30) = 0.45
= 50 kPa. Using Raoult’s law, the partial pressure of C in the vapour is
Pc = xCPc = 0 - 45 x 50 = 22.5 kPa

22.5
yc = Pc
p = 0.1125
200
It is given that yB 0.50. Therefore, yA = 1 - 0.1125 - 0.50 = 0.3875 . The vapour contains
38.75% A .

EXAMPLE 7.4 A liquid mixture containing 65 mol % benzene and 35 mol % toluene is
subjected to flash vaporization at 363 K and 101.3 kPa . The vapour pressure of benzene at this
temperature is 136.09 kPa and the vapour pressure of toluene is 54.21 kPa . Flash vaporization
is essentially an equilibrium stage operation. Calculate the mole percent of the feed that is
vaporized.
Solution The concentration of liquid and vapour phases that exist in equilibrium at 363 K
and 101.3 kPa are calculated using Eqs. (7.10) and (7.11) :
P - PBS 101.3 - 54.21
XA = pS _ pS ~
136.09 - 54.21
= 0.575
rA rB
X Ps
0.575 x 136.09
= xArA
P 101.3
= 0.773
These are the compositions of the liquid and vapour products that result on flash vaporization.
Therefore, xw = 0.575 and yD = 0.773. Substituting these in Eq. (7.12), we can calculate the
fraction of the feed that is vaporized.
xF - xw 0.65 - 0.575 Q
,?g
J
yD — xw 0.773 - 0.575
That is, 37.9% of the feed is vaporized during flash vaporization.
 Solutions and Phase Behaviour 157

EXAMPLE 7.5 Mixtures of ft -heptane ( 4 ) and ft -octane (B) are expected to behave ideally.
/

The total pressure over the system is 101.3 kPa . Using the vapour pressure data given below,
(a) Construct the boiling point diagram and, (b) construct the equilibrium diagram .

T ( K) 371.4 378 383 388 393 398.6

P/ (kPa ) 101.3 125.3 140.0 160.0 179.9 205.3

PB* ( kPa) 44.4 55.6 64.5 74.8 86.6 101.3

Solution
Sample calculation. Consider the second set of data :
T = 378 K ; P/ = 125.3 kPa; P/ = 55.6 kPa .
Using Eq. (7.9),
101.3 = 55.6 + xA (125.3 - 55.6)
Therefore, xA = 0.656. Using Eq. (7.6), we see
yA = 0.656 x 125.3/101.3 = 0.811

These calculations are repeated for other temperatures. The results are tabulated below :

T (K ) 371.4 378 383 388 393 398.6

XA 1.000 0.656 0.487 0.312 0.157 0

yA 1.000 0.811 0.674 0.492 0.279 0

(a) A plot of T versus x and y gives the boiling point diagram [ Figure 7.5 (a)].

400

390

<LT
WH

|380
Q
S
0)
- T-y curve
H
370 T-x curve

360 -|
0 0.2 0.4 0.6 0.8 1
Mole fraction , xor y
Figure 7.5(a) Boiling point diagram for Example 7.5 .
158 Stoichiometry and Process Calculations

(b) A plot of y against x gives the equilibrium diagram [Figure 7.5 (b)] .

H 0.8
3
I
.a o6 ,

G
O
• H
f
-

'
—
,Mi«3iI
<D
0.4 /

o
S 0.2

0
0 0.20.4 0.6 0.8 1
x, mole fraction in liquid
Figure 7.5(b) Equilibrium curve for Example 7.5 .

EXAMPLE 7.6 A mixture of /7-hexane and /7 -heptane containing 25% /7 -hexane is vaporized
at a pressure of 100 kPa. Determine the following:
(a) The bubble point temperature
(b) The composition of the vapour
The vapour pressures are given by the Antoine equation

In Ps = A -C
T
where P is in kPa and T in K . The Antoine constants are given as follows :
A B c
// -heptane 13.8587 2911.32 56.51
/7 -hexane 13.8216 2697.55 48.78

Solution Let us evaluate the boiling points of the pure liquids at 100 kPa total pressure .
These are obtained as the equilibrium temperatures calculated using the Ps = 100 kPa. The
boiling point of /7-heptane = 371.13 K and the boiling point of /7-hexane = 341.47 K .
(a) The bubble-point temperature is calculated by trial and error. A temperature lying
between the pure component boiling points may be assumed as the initial guess value.
Assume, 360 K. Evaluate the vapour pressures of the pure liquids at this temperature
using the Antoine equations.
Let ^-hexane be component A and /7-heptane be component B . Then xA = 0.25.
T = 360 K
269755
?
In P = 13.8216
360 - 48.78
=> Pi = 173.11 kPa
 Solutions and Phase Behaviour 159

2911.32
In Pg = 13.8587 -
360 - 56.51
=> PBS = 71.23 kPa

P = xAP/ + (1 xA )P§ = 0.25 X 173.11 + 0.75 X 71.23 = 96.7 kPa

-

Since the total pressure is less than 100 kPa, equilibrium temperature is not equal to
360 K.
Assume another value for I, say, 365 K.
T = 365 K
2697 55
Inf /
A = 13.8216 - => f / = 198.54 kPa
365 - 48.78
2911 32
Inf / = 13.8587 => f / = 83.21 kPa
365 - 56.51
P = xAPA + ( l - x A )f / = 0.25 x 198.54 + 0.75 x 83.21 = 112.04 kPa
As the pressure is greater than 100 kPa, the temperature lies between 360 K and 365
K. By a few more trials we can see that at
T = 361.125 K
2697.55
Inf / = 13.8216 - f / = 178.60 kPa
361.125 - 48.78
2911.32
Inf / = 13.8587 - => f / = 73.80 kPa
361.125 - 56.51
P = XAPA + 0 - x A )f / = 0.25 x 178.60 + 0.75 x 73.80 = 100 kPa
Therefore, the bubble point temperature = 361.125 K
(b) The partial pressure of ^-Hexane in the vapour at the bubble point is

PA = XAPA = 0 25 x 178.60 = 44 65 kPa

Since y A P = p A = 44.65 kPa, the mole fraction of hexane in the vapour is
44 - 65
= PA = 0.4465
f 100
The vapour contains 44.65% hexane and 55.35% heptane.
EXAMPLE 7.7 The vapour pressures of acetone ( A ) and acetonitrile ( B ) can be evaluated by
the following Antoine equation.
2795.817
Inf / = 14.39155 - T
- 43.198

2945.47
/
In f = 14.2724 - -
T - 49.15
160 Stoichiometry and Process Calculations

where T is in K and P is in kPa. Assume that acetone and acetonitrile form ideal solutions. For
a vapour phase consisting of 40% acetone and 60% acetonitrile, calculate the following:
(a) The dew point temperature and concentration of the first drop of liquid at 65 kPa
(b) The dew point pressure and concentration of the first drop of liquid formed at 327 K
Solution
(a) Equation (7.10) gives
P - PB>s
xA = pS _ pS
rA rB
Consider Eq. (7.11)

P
yA = XA ^ A

When Eq. (7.10) is substituted in Eq. (7.11) this, we get

PAs P - PiBs
XA = P
X
pS _ pS
rA rB
Here yA = 0.4 and P = 65. Therefore,
C 65 - P/
= 0.4
65 /» - /»
/ /
Assume a temperature and calculate the vapour pressures using the Antoine equation.
Substitute the vapour pressure values in the above equation. See that the LHS is equal
to 0.4. This is repeated till the LHS of the above equation becomes equal to 0.4.
At T = 333.55 K, PA = 117.03 kPa and P* = 50.18 kPa
PAs P - PiB5
P
X
p$ = 0.3991
rA rB
As this is very close to the required value of 0.4, T = 334.15 K. Using Eq. (7.11),
yAP 0.4 x 65
XA = PAs 117.03
= 0.222
(b) At 327 K, we have PA = 93.71 kPa and Pjjj = 39.31 kPa . Here y = 0.4
Equation (7.7) relates y to x, i.e.
XAP s
A1 A

XAP1 + XBPB
This can be rearranged to the following form.

. yAPBs
^ = pA -
X
y A( PSA - PSB )
 Solutions and Phase Behaviour 161

Substituting the given values, we get xA = 0.2185. From Eq. (7.11), dew-point pressure
is
Ps
xxArA 0.2185 x 93.71
= 51.2 kPa
yA 04

7.2 NON-IDEAL SOLUTIONS

7.2.1 Deviation from Ideal Behaviour
Components in an ideal solution obey Raoult’s law over the full concentration range. For
solutions to be ideal, the components must be chemically similar and the intermolecular forces
must be of the same order of magnitude whether they are in the pure state or in the solution.
Only a very few systems approach ideal behaviour in the true sense of the term, although many
can be treated as ideal solutions for engineering calculations. The non-ideal behaviour of liquid
mixtures arises due to the dissimilarity among molecules. The dissimilarities may be due to the
difference in the molecular structure or due to the difference in the molecular weight. For such
solutions, the plot of partial pressure against liquid composition will not be a straight line as is
the case with ideal solutions. The partial pressure curves will be above or below the straight
line representing ideal solution behaviour. If the partial pressure is greater than that given by
Raoult’s law, the solution is said to exhibit a positive deviation from ideality, and if it is less
than the partial pressure given by Raoult’s law, the solution is said to exhibit a negative
deviation from ideality. The total pressure versus liquid composition also will be above or below
the Raoult’s law line depending upon whether the solution exhibits a positive or negative
deviation from ideality. The general nature of the vapour pressure curves showing positive and
negative deviations are shown in Figure 7.6.

Positive deviation Negative deviation

P vs . x /

P x s. x / / /

/ y
/ P v s. y /

° A vs - *
—
<D
•

C/3
C/3
<

'
s
/ / /F vs y
//'
s
.

fy/ / PH

/PA VS X

/'
s pB VS X

*> y x, y

Figure 7.6 P-x-y curves for non-ideal solutions .

162 Stoichiometry and Process Calculations

These diagrams refer to constant temperature conditions. The uppermost curves give the
total vapour pressure as a function of liquid composition (P-x curve). The corresponding
curves as a function of the vapour composition ( P-y curve) lie below the P -x curves as the
vapour is rich in the more volatile component. An important characteristic of real solutions is
evident from these curves. As the mole fraction of the components approach unity, the partial
pressure becomes asymptotic with the straight line that is applicable to ideal solutions. That is,
all real solutions exhibit ideal behaviour as the mole fraction of the components tends to unity
or mathematically,
PA = XAPA as xA > 1 ( 7.13)
In dilute solutions, since the solvent is present in larger proportions, we can say that the solvent
in a dilute solution obeys Raoult’s law.

7.2.2 Henry’s Law

Henry ’s law describes another form of ideal behaviour shown by all real solutions. Henry ’s law
states that the partial pressure of a component over a liquid solution is directly proportional to
the concentration of the component in the liquid . Mathematically,
Pi = ( 7.14)
the proportionality constant Ht is known as the Henry ’s law constant. Like vapour pressure,
the constant depends on temperature. When it is numerically equal to the vapour pressure of
the component, Henry ’s law reduces to Raoult’s law. Figure 7.7 gives the partial pressure over
a real solution.

Henry’s law,
ag PA HAXA
aOH
PAVSX
1
PH

Raoult’s law
PA = PASXA
0 JC, liquid composition 1
Figure 7.7 Partial pressure over real solution .

It shows that Henry ’s law is obeyed by a component in a real solution when its mole
fraction approaches zero. Essentially all liquids will obey Henry ’s law in the region close to mole
fraction zero, but many will deviate from the law above 0.01-0.02 mole fraction. And almost
all liquids deviate above 0.1 mole fraction. But in some exceptional cases, Henry ’s law is found
 Solutions and Phase Behaviour 163

to be obeyed quite well up to xi = 0.5. In a dilute solution as the solute is present in very small
proportions it obeys Henry ’s law. Combining it with our earlier observation, we can generalize
that in dilute solution , the solute obeys Henry ’s law and the solvent obeys Raoult ’s law.

7.2.3 Henry’s Law and Gas Solubility

The solubility of a gas in a liquid can be predicted using the Henry ’s law constant of the gas.
Since the solubility of the gas in a liquid is usually very low, the mole fraction of a gas in a
saturated liquid solution is very small. The solute gas obeys Henry ’s law and therefore its partial
pressure will be directly proportional to its mole fraction, the proportionality constant being the
Henry ’s law constant. It means that the mole fraction or the solubility of the gas in the liquid
is proportional to the partial pressure of the gas over the liquid as given by
Pi
*, = 7T ( 7.15)

EXAMPLE 7.8 An aqueous solution of acetaldehyde contains 2% acetaldehyde by weight.

The partial pressure of acetaldehyde over the solution is found to be 41.4 kPa at 367 K. What
will be the partial pressure over a 0.1 molal solution at the same temperature ?
Solution The mole fraction of acetaldehyde (MW = 44.032) in the 1% aqueous solution
2 / 44.032 3
= 8.28 xl (T
(2 / 44.032) + (98 / 18.016)
The Henry 's law constant for acetaldehyde H 4 is given by Eq. ( 7.14)
41.4 = 8.28 x 10 3
“

HA
41.4
or HA 3 = 5.00 x 103 kPa
8.28 xl 0
“

The mole fraction of acetaldehyde in 0.1 molal solution is

0.1 3
= 1.8 x 10
1000 / 18.016 + 0.1
Partial pressure over 0.1 molal solution is computed by Eq. (7.14) :
3 3
PA = HAXA = 5.00 x 10 x (1.8 x 10 ) = 9 kPa
" “

7.3 VAPOUR-LIQUID EQUILIBRIUM CALCULATONS

7.3.1 Vaporization Equilibrium Constants
For high-pressure vapour-liquid equilibrium calculations, it is convenient to express the phase
equilibrium relations in terms of vaporization equilibrium constants or K factors. It is defined
as the ratio of mole fraction in the vapour phase y to that in the liquid x or K = ( y/ x ). The
vaporization equilibrium constant is a complex function of temperature , pressure, and the
164 Stoichiometry and Process Calculations

vapour phase and liquid phase compositions. If Raoult’s law is applicable to the liquid solution
and Dalton’s law is obeyed by the vapour phase, the vaporization constant becomes
y Pi IP P (7.16)
p
xP, / C
Thus, K factors of ideal solutions depend only on temperature and pressure. Equation ( 7.16)
can be applied to components below their critical temperatures and low pressures even for non-
ideal solutions. However, at high pressures and high temperatures, Eq. (7.16) will give incorrect
results. Many correlations are available for estimating K values. DePriester [ Chem. Eng. Progr.,
Symposium Ser., 7, 49 (1953)] nomographs provide such correlations for many hydrocarbons.
Calculations of the temperature and pressure at the bubble point and dew point of a multicom -
ponent mixture as well as flash vaporization calculations are easily done using the vaporization
equilibrium constants as detailed below.

7.3.2 Bubble- Point Temperature and Pressure

The temperatures at which a given mixture can exist as liquid and vapour phases in equilibrium
at a specified pressure lie between the bubble point and dew point of the mixture. At the bubble
point, the mixture begins to vaporize and the liquid phase has the same composition as the
original mixture. The vapour in equilibrium with this liquid will have composition
yt = Kixi
Since the sum of the mole fractions is unity, we have
yLyl = 'LKixi = 1 ( 7.17)
If the vaporization constants can be expressed as a function of temperature , Eq. (7.17) can be
solved for the equilibrium temperature which in this case is the bubble point of the mixture .
If K values are obtained from charts or nomographs, a temperature is assumed and the K values
at this temperature are substituted into Eq. (7.17) . The bubble point is determined by trial such
that Eq. (7.17) is satisfied. For ideal solutions, the bubble point is determined by solving the
following equation:

=P ( 7.18)
which is a generalization of Eq. (7.5) for multicomponent solutions. To find the bubble-point
pressure, a similar procedure as above is adopted, but by assuming various values of pressure
until 2 Klxl = 1.

7.3.3 Dew-Point Temperature and Pressure

The temperature at which the first drop of condensate is formed when a vapour is cooled at
constant pressure is the dew point of the vapour. The vapour in equilibrium with the liquid at
the dew point has the same composition as the original mixture. In order to find the dew-point
temperature, a temperature is assumed arbitrarily and the Kx is determined for this temperature .
Then,
 Solutions and Phase Behaviour 165

xi ZL
Ki
At the dew point,
Ex, = 2 —Ki = 1.00 (7.19)

If the sum on the left-hand side of the equation is not equal to unity, repeat the calculation by
assuming another temperature till this equation is satisfied . The trial-and -error solution is not
needed if the vaporization constants are expressed as an explicit function of temperature. For
ideal solutions, Eq. ( 7.19) can be put in the following form:

E x, = P E -
^=
pf
L 1.00
( 7.20)

Given the vapour pressure as a function of temperature through an equation such as the Antoine
equation, Eq. (7.20) can be directly solved for the dew-point temperature .

7.3.4 Flash Vaporization Calculations

The general flash vaporization problem can be stated thus: Given a mixture of known overall
composition zz at a temperature T and a pressure P , what is the fraction that is vapour ( V ) and
what are the compositions of the liquid and vapour phases in equilibrium ?

P , T , z , known

Vapour, V
-* mol / h,
Composition
Feed , F
mol / h,
Composition *l>=3 >
z.
Liquid , L
-> mol / h,
Composition xt

Figure 7.8 Flash vaporization calculation.

The overall material balance for the system is

F = V + L
where F is the total number of moles of the initial mixture. The component i balance for the
system is
Fz , = Vyt + Lx, (7.21)
166 Stoichiometry and Process Calculations

Since y, = Kpch it can be eliminated from Eq. (7.20) to get the following:
/ \
F Zj F zi
xi = ( 7.22)
Ky + L V \K j + L /V /
Since 2JC , = 1, we have
z V
2 ' (723)
K, + LIV F
The above equation can be used for the calculation of T, P or fractional vaporization in an
iterative procedure. Alternatively x{ can be eliminated from Eq . (7.21) which leads to
r \
Fzt F Zi
yt = (7.24)
V +L/ Kf V V 1 + LIQrKii ) J
'
As Zy, = 1
Zi V
2 ( 7.25)
1 + LKyKj ) F
Equation (7.25) also can be utilized in an iterative procedure to estimate T , P or the fraction
of the initial mixture that is vaporized.

7.3.5 Solution of VLE Problems

Vapour-liquid equilibrium calculations for multicomponent solutions require a trial-and-error
solution and the calculations are very lengthy and involved when we take the vapour and liquid
phase non-idealities into account. For ideal solutions, however, the algorithms for the VLE
problems are simpler and is described in the following paragraphs.
Bubble- point pressure (Problem): Given the liquid compositions {*,} and temperature T ,
calculate the bubble-point pressure and the vapour-phase compositions {yt } .
1 . Input the temperature and the liquid compositions.
2 . Get the vapour pressures of the pure components { P f } at T. Use any of the vapour
pressure-temperature relations, such as the Antoine equation for this purpose .
3. Using Raoult’s law calculate pv
s
Pi = x f ,
4. Calculate the total pressure as the sum of the partial pressures.
P = 'Lpi = 2 xtPf
5 . The vapour-phase compositions are calculated using Dalton’ s law :

s
_ Pi _ xip,
yv
‘ P 2 x Pf ,
 Solutions and Phase Behaviour 167

Bubble- point temperature (Problem): Given the liquid compositions {x7} and pressure P ,
calculate the bubble-point temperature and the vapour-phase compositions {y7}.
1 . Input the pressure and liquid compositions.

^
2 . Evaluate the boiling points of the pure species {7 } at the given pressure .
3. Start with an initial guess value for the bubble point temperature. The mole fraction
weighted average of the boiling points of the pure components may be chosen as the
initial guess value.

T = I xp
„
4. Get the vapour pressure at temperature T and calculate XjK which for an ideal solution
s
R
is x, -L- . Since yt = xtKb
P
ps p
—
Z x -Jp = 1.0 or
Z x, /f
= 1.0 (7.26)

5 . If the above equality is satisfied, go to step 7. Otherwise change the temperature

assumed for the bubble point. To ensure faster convergence to the desired value, first
evaluate Pks using the relation

P
Z xtaik
= Prks
which is obtained by multiplying both sides of Eq . (7.26) with Pks the vapour pressure
9

Pf
of the least volatile component and by letting alk = —— , the relative volatility of
Pk
component / with reference to component k.
6. Using the Pkscalculated in step 5, evaluate the saturation temperature using the Antoine
-
equation or any other vapour pressure temperature relation. Let this be the new guess
-
value for bubble point temperature and go to step 4.
7. Calculate the vapour phase compositions using
Ps
y , = Kixi

Dew- point pressure (Problem ): Given the vapour compositions {y7} and temperature T,
calculate the dew -point pressure and the liquid-phase compositions {x7 }.
1 . Input the temperature and the vapour compositions.
2 . Get the vapour pressures of the pure components at T. Use any of the vapour
pressure-temperature relations, such as the Antoine equation for this purpose.
168 Stoichiometry and Process Calculations

3. Calculate the total pressure using Eq. (7.20) :

1
P=
Z
^Pi
4. The liquid-phase compositions are calculated using the following relation :
yt _ ytp

Dew - point temperature ( Problem): Given the vapour -phase compositions {y,} and pressure
P , calculate the dew-point temperature and the liquid-phase compositions {*,-}.
1. Input the pressure and liquid compositions.
2 . Evaluate the boiling points of the pure species { Tf } at the given pressure .
-
3. Start with an initial guess value for the dew point temperature. The mole fraction
weighted average of the boiling points of the pure components is chosen as the initial
guess value.
T = E y,7 f

4 . Get the vapour pressure at temperature T and calculate —Pf .

—Piy j
.
5 . If P Z = 1 go to step 7. Otherwise change the temperature assumed for the dew

point. To ensure faster convergence to the desired value, first evaluate Pk using the
relation

P Z — = p/
which is obtained by multiplying both sides of Eq. (7.20) with Pks, the vapour pressure
of the least volatile component and by letting alk =
p* —rkPf—
, the relative volatility of

component / with reference to component k .

6. Using the Pks calculated in step 5, evaluate the saturation temperature using the Antoine
equation or any other vapour pressure-temperature relations. Let this be the new guess
value for dew-point temperature and go to step 4.
7. Calculate the liquid phase compositions using

’•i
T
= —/ = T,
K, —Pf
P
a
 Solutions and Phase Behaviour 169

Flash vaporization ( Problem 1): Determine the fraction of the feed vaporized ( V/F ) from
a mixture of composition {zz}, given temperature T and pressure P of flash vaporization.
1. Input the composition of the feed and the temperature and pressure.
2 . Get the vapour pressures of the pure liquids at the given temperature.
3. Check whether vapour and liquid phases exist in equilibrium under the given condition.
This is done by evaluating the bubble-point and the dew -point pressures at the given
temperature. The bubble-point pressure is

n = 2 x,Pts
1
and the dew-point pressure is Pd = . If the given pressure lies between Pb and
z
2 '
Pf
Pd flash vaporization is possible and proceed with step 4. Otherwise stop.
4. Assume fractional vaporization V and calculate
s

I
z7 _
P ^
f Ps - 1 i
\

1+ V
v P /

The above expression results on rearranging the left-hand-side of Eq. (7.24). If the
assumed fractional vaporization is the correct value, the expression evaluates to unity.
Otherwise change V and repeat the step 4 calculation.
5 . The vapour phase and liquid phase compositions are evaluated using the following
relations:
Pf_
z7 '

p
yl = / \
P[
\+ v - 1.0
p
V
p

Problem 2: Determine the temperature and composition of the liquid and vapour products
on flash vaporization of a mixture of composition {zz }, given the fraction of the feed vaporized
( V/F ) and the pressure of vaporization.
1 . Input the composition of the feed, the pressure and the fraction of the feed vaporized.
2 . Evaluate the boiling points of pure liquids { 77s} at the given total pressure P . Start with
an initial guess value T for the equilibrium temperature, where
T ='ZziTis
170 Stoichiometry and Process Calculations

3. Get the vapour pressures of the pure liquids at the given temperature and calculate
s
z* 5p_
E \
f Ps
i
1+V -1
v P /

4. If the assumed temperature is the equilibrium temperature, the above expression evaluates
to unity. Otherwise change temperature and repeat the step 4 calculation.
5 . The vapour phase and liquid phase compositions are evaluated using the following
relations:
Pf_
z1
P
Tz = /
ps \

l +V
, - 1.0
p
V

p
x =y
' ' Ts
EXAMPLE 7.9 A solution contains 60.0% ^-pentane, 25.0% w -hexane and 15.0% ^-heptane.
The Antoine constants for the constituents are given below :

Name A B c
w- pentane 13.8183 2477.07 39.94
/7-hexane 13.8216 2697.55 48.78
// -heptane 13.8587 2911.32 56.51

Assuming that Raoult’s law is applicable, determine the following:

-
(a) Bubble point temperature at 400 kPa
(b) The composition of the vapour formed at the bubble point in part (a)
-
(c ) Bubble point pressure at 300 K
Solution
x1 Ps
(a) As Raoult’s law is applicable, K , = y j x j = P f / P and yx =

^
Z >', = Z
^=Z
^ =1
Assume a temperature, evaluate the vapour pressure at this temperature and calculate
XT . If the temperature assumed is the bubble point of the mixture,
/ = 1 - If this
equality is not satisfied, another temperature is assumed and the calculations are repeated
till the above equality will be satisfied .
 Solutions and Phase Behaviour 171

Let us assume that T = 369 K. The vapour pressures are evaluated using the
Antoine equation.

PAS = 539.47 kPa, I§ = 220.86 kPa , = 93.90 kPa

Vapour-phase compositions are calculated and evaluated .

Z y, = Z xAs
p

(0.6 x 539.47 + 0.25 x 220.86 + 0.15 x 93.90)

400
= 0.9825
Since Z * 1 0, let us assume that T = 370 K.
if = 551.9 kPa, if = 226.73 kPa, Pcs = 96.73 kPa
x,P,s
Z yt = Z p
(0.6 x 551.91 + 0.25 x 226.73 + 0.15 x 96.73)
= 1.0058
400
It is clear that the bubble-point temperature lies between 369 and 370 K . By a few more
trials, we can find that at 369.75 K, = 1.0. At 369.75 K,
P/ = 548.78 kPa, if = 225.25 kPa, Pcs = 96.01 kPa
Z y,- = Z .
x Pf
p
(0.6 x 548.78 + 0.25 x 225.25 + 0.15 x 96.01)
400
= 1.0000
Therefore, the bubble-point temperature of the mixture is 369.75 K .
-
(b) The vapour formed at the bubble point in part (a) has the composition

XA?A (0.6 x 548.78)

X4 = P 400
= 0.8232
(0.25 x 225.25)
yB = XBP^B 400
= 0.1408

Tc =
XC
P
C
^ (0.15 x 96.01)
400
= 0.0360
The vapour formed at the bubble point contains 82.32% ^ -pentane, 14.08% ^-hexane
and 3.60% ^-heptane.
(c ) The bubble-point pressure is directly found out. At the given temperature, calculate the
vapour pressures of the components and evaluate the partial pressure using Raoult’s
law. The sum of the partial pressures is equal to the bubble -point pressure .
172 Stoichiometry and Process Calculations

At 300 K, the vapour pressures are:

Pj = 73.21 kPa, Pi = 21.84 kPa , P$ = 6.70 kPa
Substituting the values, we get
Pi =
pA = 43.93 kPa, pB = 5.46 kPa , pc = 1.005 kPa
p = YJpi = 43.93 + 5.46 + 1.005 = 50.4 kPa
Therefore, the bubble point pressure is 50.4 kPa .

EXAMPLE 7.10 A vapour contains 60.0% /7-pentane , 25.0% /2 -hexane and 15.0 % /7-heptane.
The Antoine constants for the constituents are given below :

Name A B c
/7- pentane 13.8183 2477.07 39.94
/7-hexane 13.8216 2697.55 48.78
/7 -heptane 13.8587 2911.32 56.51

Assuming that Raoult’s law is applicable, determine the following:

(a) Dew-point temperature at 400 kPa
(b) Dew-point pressure at 300 K
Solution
(a) Dew-point temperature is the temperature at which the first drop of condensate is
formed when the vapour is cooled at constant pressure. At the dew point the vapour
will have the composition of the original mixture and the liquid will have the compo-
sition in equilibrium with the original mixture. The temperature is to be obtained by trial.
The initial guess value for the dew point may be taken to be the mole fraction weighted
average of the pure component boiling points at the specified pressure . The pure
component boiling points are evaluated using the Antoine equation with P = 400 kPa .
These are as follows:
TA = 356.42 K, TB = 393.29
K, Tc = 426.57 K
The mole fraction weighted average value is
T = (0.6 x 356.42 + 0.25 x 393.29 + 0.15 x 426.57) = 376.16 K
Take this to be the initial guess value for the dew point. At this temperature, the vapour
pressures are:
Pi = 633.27 kPa, P§ = 265.55 kPa, Pg = 115.68 kPa
Since
p_
xi = yl
c
 Solutions and Phase Behaviour 173

/ N
0.6 0.25 0.15
>
2 ,- = 400 v 633.27 265.55 115.68, = 1.274
Since the sum of the mole fractions is not equal to unity, the temperature is not the
correct dew point. Assume another temperature and repeat the calculations. With a few
trials the dew -point temperature can be found to be 385.94 K .
At 385.94 K, the vapour pressures are
P/ = 779.8 kPa, P § = 33724 kPa, Pi = 151.60 kPa
N
0.6 0.25 0, 15
= 400 779.88 336.24 151.60,
= 1.000
v
Therefore, the dew -point temperature is 385.94 K.
-
(b) The dew point pressure is calculated using the equation
1
P=
y,
Z
where yl and Pf are the mole fraction and vapour pressure of component /.
At 300 K, the vapour pressures are:
P/ = 73.21 kPa, Pi = 21.84 kPa, Pi = 6.70 kPa
Therefore, the dew -point pressure is
1
P= = 23.79 kPa
' 0.6 0.25 0 15 '
, 0.0420
, 73.21 21.84 6.70 ,

EXAMPLE 7.11 A mixture contains 45 mol % methanol ( A ), 30 mol % ethanol ( B) and the
rest ^-propanol (Q. Liquid solution may be assumed to be ideal and the perfect gas law is valid
for the vapour phase. Calculate the following at a total pressure of 101.3 kPa :
-
(a) The bubble point and the vapour composition
-
(b) The dew point and the liquid composition.
The vapour pressures of the pure liquids are given as follows:

Temperature 333 343 353 363

(K)

Pj, kPa 81.97 133.29 186.61 266.58

P§, kPa 49.32 73.31 106.63 166.61
PS , kPa 39.32 62.65 93.30 133.29
174 Stoichiometry and Process Calculations

Solution The vapour pressures of the components are plotted against temperature so that
the interpolation of vapour pressure can be done easily.
(a) If the vapour phase can be treated as an ideal gas and liquid phase , an ideal solution,
-
the K values can be written as K = yjxi = Pf / P . Equation (7.17) can be written as
}

x Ps
Z y i = ZKixi = T - j- = i .
Now temperatures are assumed till the above equality is satisfied . It is seen that at
344 K,

Z ( x,Pf / P ) = 0.98
and at 345 K,

y xPs i
I
= 1.015
P^
Therefore, the bubble-point lies between 344 and 345 K. By interpolation, the bubble-
point is obtained as 344.6 K. At this temperature the vapour pressures are obtained
from the P vs T plots. P$ = 137.3 kPa , PBS = 76.20 kPa and P <§ = 65.40 kPa.
Component p ,s Kj = P ,s/ P yi = KfCi

Methanol 0.45 137.30 1.355 0.610

Ethanol 0.30 76.20 0.752 0.226
Propanol 0.25 65.40 0.646 0.162
TK x, . 0.998

The equilibrium vapour contains 61% methanol, 22.6% ethanol and 16.2% propanol ,

(b) Equation (7.20) for the present case becomes

1.00
K, P,
The dew -point temperature is to be determined by trial such that the above relation is
satisfied. By trial it can be seen that at 347.5 K P% = 153.28 kPa , p£ = 85.25 kPa and
P* = 73.31 kPa.
Component % Pis II s
7 x, = y / K ,
Methanol 0.45 153.28 1.5131 0.2974
Ethanol 0.30 85.25 0.8416 0.3565
Propanol 0.25 73.31 0.7237 0.3454
0.9993

The values in the last column are the liquid composition at the dew point . Thus the
liquid contains 29.7% methanol, 35.7% ethanol and 34.5% propanol.
 Solutions and Phase Behaviour 175

EXAMPLE 7.12 A hydrocarbon mixture contains 25 mol % propane, 40 mol % n-butane and
35 mol % // -pentane at 1447.14 kPa. Assume ideal solution behaviour and calculate the following:
-
(a) The bubble point temperature and composition of the vapour
-
(b) The dew point temperature and the composition of the liquid
(c ) The temperature and the composition of the liquid and vapour in equilibrium when
45 mol % of the initial mixture is vaporized. (The values of K , can be obtained from
Figure 13.6 of Chemical Engineer 's Handbook, 5th ed .)
Solution
(a) Assume temperature say, 355.4 K and the K , values are found out from the nomograph
(Figure 13.6b in Chemical Engineer ’s Handbook ) . The products of Kx and x, are
calculated and their sum Yjxi i f un<i out - The results for two temperatures 355.4
K and 366.5 K are shown below.
^ °
T = 355.4 K T = 366.5 K
Component K, K ,x , K,
Propane 0.25 2.000 0.500 2.30 0.575
/7- butane 0.40 0.780 0.312 0.90 0.360
/7- pentane 0.35 0.330 0.116 0.40 0.140
TK , x, 0.928 HKix, 1.075

The bubble-point temperature lies between 355.4 K and 366.5 K. By interpolation the
temperature is found out to be 361 K. The calculations are carried out at this tempera-
ture and the results are as follows :
Component x7 K , KjXi
Propane 0.25 2.12 0.530
/7- butane 0.40 0.85 0.340
/7-pentane 0.35 0.37 0.130
TKiXi 1.000

Since is approximately 1.00, the bubble -point temperature is 361 K . The values
in the last column are the mole fraction of various components in the vapour. At the
bubble-point the vapour contains 53% propane, 34% butane and 13% pentane .
(b) At the dew -point temperature Y yi!Ki = 1. At 377.6 K this value is 1.1598, and at
'

^
388.8 K it is 0.9677.
T = 377.6 K T = 388.8 K
Component % K, yt / K, Ki y, / K ,
Propane 0.25 2.6 0.0962 2.9 0.0862
/7- butane 0.40 1.1 0.3636 1.3 0.3077
/7- pentane 0.35 0.5 0.7000 0.61 0.5738
Z n / K , 1.1598 T y t / Ki 0 9611
176 Stoichiometry and Process Calculations

By interpolation the dew-point temperature is found to be 387 K. The calculations for

this temperature is given below.
Component y, K, y, /K ,

Propane 0.25 2.85 0.0877

//- butane 0.40 1.25 0.3200
//- pentane 0.35 0.59 0.5932
1.0009

The last column in the above table is the liquid compositions. The equilibrium liquid at
the dew -point contains 8.77% propane, 32.0% butane and 59.32% pentane.
(c ) In the following calculations temperature is assumed so as to satisfy Eq. ( 7.25) . For
a basis of 100 mol of the initial mixture , F = 100 mol, V = 45 mol and L = 55 mol .
Equation ( 7.25) becomes

z 1 + ( Lzi/VKt ) = 0.45
T = 366.5 K T = 377.6 K
Component K, ,
z,/[ l + ( L/ VK )\ K, z/[ l + ( L/ VK ,) ]
Propane 0.25 2.30 0.1632 2.6 0.1701
//- butane 0.40 0.90 0.1697 1.1 0.1895
n- pentane 0.35 0.40 0.0863 0.5 0.1016
/[1 + ( L/ l TKt )] 0.4192 £ z, /[l + a / IX, )] 0.4612

From the calculations given above , we see that the equilibrium temperature is between
366.5 K and 377.6 K. By interpolation, T = 374.6 K.
T = 374.6 K
Component Z\ K, Z /[ 1 + ( L/VKj ) ]
Propane 0.25 2.50 0.1679
/7- butane 0.40 1.08 0.1876
/2- pentane 0.35 0.48 0.0987

i>, /[1 + CL/1X, )] 0.4542

Comparing Eqs. (7.23) and (7.24) we can see that

Z,. ,
/[1 + ( L / VK ) ]
2>
1
, / [i + (£/ , )]
^
 Solutions and Phase Behaviour 177

These are calculated using the values in the last column. Corresponding x7 values are
found out using the material balance [Eq. (7.21)].
Fz, = Vy, + Lx,
The results of the calculation are given as follows:
Component T/ X,

Propane 0.3697 0.1521

w- butane 0.4130 0.3894
w- pentane 0.2173 0.4586

7.4 VAPOUR PRESSURE OF IMMISCIBLE SYSTEMS

When a mixture of two immiscible liquids is in equilibrium with its vapour, each component
in the solution contributes its full vapour pressure towards its partial pressure in the vapour
phase. In a mixture of two immiscible liquids, the liquid surface will be made up of two pure
liquid surfaces and vaporization occurs as if it is occurring from a pure liquid. The vapour
pressure exerted is independent of the amount of the surface , but depends only on the nature
and temperature of the liquid. Therefore, both components are free to exert their full vapour
pressure as though they alone are present in the liquid phase.
We know that a pure liquid boils when its vapour pressure becomes equal to the surrounding
pressure. Since both components contribute their full vapour pressures, the total pressure
exerted by the vapour over a mixture of two immiscible liquids becomes equal to the surrounding
pressure at a lower temperature than the boiling points of either of its constituents. Therefore,
the boiling point of a mixture of immiscible liquids will be lower than the boiling points of its
components. This property is made use of in steam distillation of high -boiling and heat-
sensitive materials to free off non-volatile impurities. Assume that the impure material is mixed
with water with which it is immiscible and heated . When the liquid attains the temperature at
which the sum of the vapour pressures is equal to the existing pressure, the liquid boils. This
temperature is definitely less than the boiling point of water irrespective of the material. Thus,
any high-boiling material which is immiscible with water can be distilled below 373 K at
atmospheric pressure.
The temperature at which an immiscible liquid mixture boils is known as the three-phase
temperature as two liquid phases and one vapour phase coexist in equilibrium at this condition.
Consider two immiscible liquids A and B in equilibrium with its vapour. At the three -phase
temperature, we have
P= PSA
+ Pj; ( 7 - 26)
By the Gibbs phase rule, the system is univariant (the number of components, C = 2, the number
of phases, n = 3 and therefore the number of degrees of freedom , F = C - n + 2 = 1), which
means that by fixing any one phase rule variable, the system is uniquely determined . Thus at
a given total pressure P, the three-phase temperature as well as the vapour composition are
uniquely determined and cannot be altered at will. The equilibrium temperature can be determined
by plotting the vapour pressures Pf , p/ and Pf + P/ against temperature as the abscissa. To
178 Stoichiometry and Process Calculations

find the three-phase temperature at a given total pressure P, move horizontally from P on the
n o o
vertical axis to the PA + PB curve and read the temperature on the x-axis. Alternatively, PA
versus temperature and ( P - PB ) versus temperature can be drawn as shown in Figure 7.9
(Hausbrandt Chart).

P constant

s
PA VS T
(P PB„ ) v s T
-5
=
l
72
72
<L>
H

i- H
PH

Temperature
Figure 7.9 Determination of three- phase temperature .

The temperature corresponding to the point of intersection of these curves in Figure 7.9
gives the three-phase equilibrium temperature (7*) . This is because at the point of intersection,
pS _ rp _ pS
rA ~
rB
or p= pi + pi
The mole ratio of A to B in the vapour is equal to the ratio of the respective vapour
pressures at the three-phase temperature. Let nA and nB be the number of moles of A and B
in the vapour. Then
_
nA
nB ^Pi
A_ (7.27)

PAS
X4 = pS __ PS
+J rB
( 7.28)
rA
The phase diagram for an immiscible system is shown in Figure 7.10. When a mixture of
two immiscible liquids having an overall composition represented by point M is heated, at
temperature T* the sum of the vapour pressures equals the surrounding pressure and the
9

vapour of composition represented by point E is formed. On further addition of heat, the

temperature remains constant at T* and more vapour of the same composition as given by point
E is formed. This continues till one of the components disappears from the liquid, and the
system becomes a two-phase mixture either LA- Vor LB- Vdepending upon the initial composition.
 Solutions and Phase Behaviour 179

B Vapour- r
0
%
3 A
ts L n- f
aOH A E / LA
E2 T

_
L4 ~LB
M

x , y (mole fraction of ^4 )

Figure 7.10 Temperature composition diagram of immiscible system .

EXAMPLE 7.13 A high boiling organic liquid is purified from non-volatile impurities by
allowing it to mix with steam directly at a total pressure of 93.30 kPa . The vapour pressure
data are as follows:
Temperature (K ) 353 373
Vapour Pressure of water (kPa) 47.98 101.3
Vapour pressure of liquid (kPa) 2.67 5.33

Assume that water and the organic liquid are immiscible and the impurities do not affect
the vaporization characteristics. The vapour pressures vary linearly with temperature . Calculate
the following under three-phase equilibrium :
(a) The equilibrium temperature
(b) The composition of the resulting vapour
Solution
(a) At 353 K, the sum of the vapour pressures is 50.65 kPa, and at 373 K it is 106.63 kPa.
Assuming that the vapour pressures vary linearly, the temperature at which the sum of
vapour pressures is 93.3 kPa is obtained by interpolation.
373 - 353
T * = 353 + (93.3 - 50.65) = 368.2 K
106.63 - 50.65
(b) At 368.2 K the vapour pressure of water is 88.50 kPa and that of the liquid is 4.80
kPa. Since at three-phase equilibrium , the partial pressure is equal to the vapour
pressure, the ratio of mole fractions of the components will be same as the ratio of
vapour pressures. Let y be the mole fraction of water in the vapour. Then
88.5
y= = 0.9486
93.30
The vapour contains 94.86 mol % water vapour.
180 Stoichiometry and Process Calculations

EXAMPLE 7.14 Assuming that benzene is immiscible with water, prepare a temperature-
composition diagram for benzene ( l )-water (2) system at 101.3 kPa using the following vapour
pressure data:

T (K ) 323 333 343 348 353 363 373

P f (kPa) 12.40 19.86 31.06 37.99 47.32 70.11 101.3
P f (kPa) 35.85 51.85 72.91 85.31 100.50 135.42 179.14

The boiling point of pure benzene at 101.3 kPa is 353.1 K .

Solution The three-phase temperature is first found out. At T*, P = Pf + P 2 P 1 +
is calculated for each given temperature , and this is plotted against temperature . T * is the
temperature at which P is equal to 101.3 kPa . This is found out to be 342 K . The horizontal
line CD in Figure 7.11 is drawn at this temperature . The vapour pressures at this temperature
are Pf = 71.18 kPa and P $ = 30.12 kPa . The mole fraction of benzene in the vapour
represented by point E in Fig. 7.11 is 71.18/101.3 = 0.70.
-
The dew point curve BE is plotted by choosing a temperature lying between 373 K (boiling
-
point of water) and 342 K (the three phase temperature) . For example , take T = 353 K . The
partial pressure of water at the dew point is equal to the vapour pressure . For the dew point -
temperature of 353 K the partial pressure of water is
47.32 = (1 - y )P
where y is the mole fraction of benzene in the vapour y = 0.5329. ,

B To = 373 K
370 -

360 -
i>
f -
H

B- 350 -
SH TA = 353.1 K
a C E D
H 7 * = 342 K
340 -

330 -

320
0.2 0.4 0.6 0.7 0.8
v, y ( mole fraction of benzene )
Figure 7.11 Temperature-composition diagram for Example 7.12 .

This calculation is repeated for various temperature and the entire curve BE is drawn. For
getting the curve AE the procedure is the same. Here temperatures are assumed between 342 K
 Solutions and Phase Behaviour 181

and 353.1 K , the latter being the boiling point of pure benzene . On the curve A E, the
partial pressure of benzene in the vapour phase equals its vapour pressure . For example ,
for a dew -point temperature of 348 K,
85.31 = P x y or y = 0.8422
The following table gives the results of a few such calculations:

T (K ) 342 348 353 353.1 363 373

y (curve AE ) 0.70 0.84 0.99 1.00
y (curve BE ) 0.70 0.53 0.31 0

7.5 VAPOUR PRESSURE OF SOLUTIONS OF NON- VOLATILE SOLUTES

The presence of non-volatile solutes in the solution lowers the vapour pressure of the volatile
components and raises the boiling point of the solvent. The difference between the boiling point
of the solution and the boiling point of the pure solvent is known as the boiling point elevation .
Unless the solute and the solvent are chemically similar, the equilibrium vapour pressure cannot
be determined as product of mole fraction and the vapour pressure of the pure solvent . When
Raoult’s law is used, the vapour pressure of the solvent is independent of the nature of the
solute. This is not true for ionizing solutes. For ionizing solutes the effective mole fraction in
-
the liquid will be greater than that of the non ionizing type. It is found that an aqueous 0.1 M
solution of sodium chloride is about twice as effective as a 0.1 M solution of sucrose in raising
the boiling point. Assumption of ideal solution behaviour will therefore lead to erroneous results
when estimating the vapour pressure over a solution containing non -volatile solutes. The vapour
pressure and the boiling point of such solutions are usually estimated using reference substance
plots. The Diihring lines described earlier in Chapter 6 provide a convenient method for
predicting the vapour pressure and the boiling point elevation. If the vapour pressures of the
solution are known at two temperatures, the temperatures at which the pure solvent also has
the same vapour pressures can be determined from standard tables of experimental values or
through correlations. When the temperature of pure solvent is plotted against the temperature
of the solution having the same vapour pressure as the pure solvent, a straight line results.
Several such lines can be drawn with the concentration of the solute as the parameter.
Though it cannot be generalized, for sodium hydroxide-water solutions these lines are found
to be approximately parallel, indicating that the difference between the boiling point of the
solution and the boiling point of pure water, or the boiling point elevation, is independent of
temperature or pressure.

7.5.1 Relative Vapour Pressure

Frequently the vapour pressure over a solution containing non-volatile solutes is expressed as
p = kPs
where p is the effective vapour pressure of the solution, Ps is the vapour pressure of pure
solvent and k is the relative vapour pressure of the solution which depends on concentration,
182 Stoichiometry and Process Calculations

temperature or pressure. For ideal solutions, the factor k is equal to the mole fraction of the
-
solvent and is independent of temperature or pressure . For non ideal solutions k will be different
from mole fraction. Assuming that the factor k is independent of temperature or pressure, the
value of k can be determined from a single measurement of the vapour pressure or the boiling
point of the solution.

EXAMPLE 7.15 The normal boiling point of a 5-molal solution of sodium chloride in water
is found to be 379.2 K. What will be the boiling point of the solution at 70 kPa? The vapour
pressure of water is given by

3799.887
In Pw = 16.26205 =
T - 46.854
where P is in kPa and T is in K . Assume that the relative vapour pressure is independent of
temperature.
Solution The relative vapour pressure of a 5 -molal solution can be computed as

rw
where p is the vapour pressure of the solution at 379.2 K and P w is the vapour pressure of
water at 379.2 K. The latter value is determined using the Antoine equation :
3799 887 p* = 125.03 kPa
In Pw* = 16.26205 = - .
=>
379.2 - 46.854
Substituting this in Eq. ( 7.30), we can compute the relative vapour pressure .
101.3
125.03
= 0.8102
When the solution boils at 70 kPa, the vapour pressure of the solution, p = 70 kPa . Since the
relative vapour pressure is assumed constant, the vapour pressure at the solution boiling
point is from Eq. (7.30)
_P 70
FPws ~ j 0.8102
= 86.4 kPa
The temperature at which the vapour pressure of water is 86.4 kPa is calculated using the
Antoine equation.
3799.887
In 86.4 = 16.26205 => T = 368.8 K
T - 46.854
Therefore, the boiling point of the solution at 70 kPa = 368.8 K.
 Solutions and Phase Behaviour 183

EXERCISES
Ideal solutions and RaouWs law
7.1 ^-Heptane and toluene form an ideal solution. At 373 K their vapour pressures are
106 kPa and 74 kPa respectively. Determine the composition of the liquid and the
vapour in equilibrium at 373 K and 101.3 kPa .
7.2 The vapour pressures of benzene and toluene are given by the Antoine equation

In Ps = A --? —
T -C
where P is in kPa and T in K . The Antoine constants are

A B c
Benzene 13.8858 2788.51 52.36
Toluene 13.9987 3096.52 53.67

Determine the partial pressures and the weight composition of the vapour in equilibrium
with a liquid mixture consisting of equal weights of the two components at 300 K.
7.3 At 300 K, the vapour pressures of two pure liquids A and B are respectively 80 kPa
and 50 kPa. The concentration of A in the vapour in equilibrium with a solution of A
and B is found to be 35% (mol). Determine
(a ) The composition of the liquid
( b) The total pressure of the vapour
7.4 Air is cooled to 80 K at 101.3 kPa. Calculate the composition of the liquid and the
vapour phases at this condition assuming that the mixture behaves ideally. The
vapour pressure of nitrogen at 80 K = 135.74 kPa and the vapour pressure of
oxygen at 80 K = 30.04 kPa .
7.5 A mixture of A and B conforms closely to Raoult’s law. The pure component vapour
ri O

pressures and PB in kPa at temperature T in K are given by

2945
In Pi = 14.27 - T - 4 9
2973
lnPBs = 14.20 - r - 6 4
If the bubble point of a certain mixture of A and B is 349 K at a total pressure of
80 kPa, find the composition of the first vapour that forms.
7.6 The vapour pressures of substances A and B can be evaluated by the Antoine
equations
2940.46
In Pi = 14.5463 - T - 35.93
184 Stoichiometry and Process Calculations

In Pi = 14.2724 - T2945.47
- 49.15
where T is in K and P is in kPa. Assuming that the solutions formed by these are ideal,
calculate the compositions of the vapour and the liquid in equilibrium at 327 K and
65 kPa.
7.7 A mixture of /7-hexane and /7-heptane containing 10% // -hexane is vaporized at a
pressure of 100 kPa. Determine the following:
(a ) The bubble point temperature
( b) The composition of the vapour
The vapour pressures are given by the Antoine equation

In P s = A -
^—
T -C
where P is in kPa and T in K. The Antoine constants are
Name A B C
w-heptane 13.8587 2911.32 56.51
/7-hexane 13.8216 2697.55 48.78

7.8 The vapour pressures of benzene and toluene are given below.

T (K ) 353.1 358 363 368 373 378 383 383.6

?
P (kPa) 101.3 116.9 135.4 155.7 179.1 204.2 233.0 240.0
P§ (kPa) 39.6 46.0 54.0 63.3 74.2 86.0 99.0 101.3

Calculate the equilibrium data for the system at 101.3 kPa .

7.9 At 303 K the vapour pressures of benzene ( A ) and toluene ( B) are 15.75 kPa and
4.89 kPa respectively. Determine the partial pressures and the weight composition of
the vapour in equilibrium with a liquid mixture consisting of equal weights of the two
components.
7.10 The vapour pressures of benzene { A ) and chlorobenzene (B) are given below :

T (K ) 352.8 363.2 373.2 383.2 393.2 405.3

PI (kPa) 101.3 135.1 178.7 232.5 298.0 395.3

P i (kPa) 18.2 27.7 39.06 53.7 72.3 101.3

Assume that benzene and chlorobenzene form ideal solution .

(a ) Prepare the P -x-y diagram for the system at 373.2 K.
( b) Using the P -x-y diagram of part (a), determine the bubble point pressure and
dew -point pressure of an equimolar mixture of benzene and chlorobenzene at
373.2 K.
 Solutions and Phase Behaviour 185

7.11 An equimolar mixture of benzene and toluene is contained in a cylinder at 65 kPa.

Determine the temperature range in which the mixture exists as two phases. The
vapour pressure of benzene and toluene are given by the Antoine equation with the
following constants. Pressure is in kPa and temperature in K.

Name A B C
Benzene 13.8858 2788.51 52.36
Toluene 13.9987 30%.52 53.67

7.12 A 40% (mol) solution of methanol in water boils at 348.5 K . The vapour analyzed
72.9% methanol . How does this compare with the vapour composition given by
Raoult’s law? The vapour pressures (kPa) are given by the Antoine equation with
following constants:

Name A B c
Water 16.26205 3799.887 46.854
Methyl alcohol 16.5725 3626.55 34.29

7.13 An equimolar solution of benzene and toluene is totally evaporated at a constant

temperature of 363 K. At this temperature, the vapour pressures of benzene and toluene
are 135.4 kPa and 54 kPa respectively. What are the pressures at the beginning and
at the end of the vaporization process?
7.14 A liquid mixture containing 15% A , 25% B and the rest C is in equilibrium with the
vapour which contains 40% B . All the percentages are on a mole basis. The equilibrium
pressure and temperature are 200 kPa and 350 K . At 350 K the vapour pressure of C
is 20 kPa. What is the percentage of A in the vapour ?
7.15 A liquid mixture contains 10% A , 15% B and the rest C, all compositions being in mole
percent. At equilibrium the pressure was 230 kPa and temperature was 340 K, and the
vapour was found to contain 34% B . The vapour pressure of C at the equilibrium
temperature is 3.5 kPa. Assuming ideal behaviour for the gas and the liquid, calculate
the vapour composition.
7.16 Three liquids A (MW = 40), B (MW = 60) and C (MW = 80) form an ideal solution.
At 370 K, the vapour pressures are found to be 50 kPa , 25 kPa and 12.5 kPa
respectively for A , B and C. A vapour analyzing 40% A , 40% B and 20% C on a
volume basis is in equilibrium with the liquid at 370 K . Determine the following:
(a ) The equilibrium pressure
( b) The composition of the liquid in weight percent
7.17 Liquids A and B form ideal solutions while liquid C is immiscible with both A and B .
A mixture of A , B and C is found to boil at 240 K under a pressure of 100 kPa. What
is the composition of the liquid on a C-free basis? The vapour pressures at 240 K are
15 kPa, 3 kPa and 95 kPa respectively for A, B and C.
186 Stoichiometry and Process Calculations

7.18 Three liquids A , B and C form an ideal solution . The dew point of a vapour
mixture consisting of A , B and C at pressure of 15 kPa is found to be 323 K .
The vapour pressures of pure liquids A , B and C are correlated by the Antoine
equations. With vapour pressure in kPa and temperature in K , the Antoine constants
are as follows:
Liquid A B c
A 13.9 2800 52.4
B 14.0 3100 53.7
c 16.3 3800 46.9

Determine the following :

(a ) The composition of the vapour assuming that the vapour contains equimolar
quantities of A and B.
( b) The composition of the first drop of liquid formed at 323 K and 15 kPa
7.19 The vapour pressures of substances A and B can be evaluated by the Antoine equations

In Pi = 14.5463 - T2940.46
- 35.93
2945.47
In PB = 14.2724 -
T - 49.15
where T is in K and P is in kPa . Assuming that the solutions formed by these are ideal,
calculate the following:
(a ) The bubble-point temperature of a liquid containing 40% (mole) A at 65 kPa and
the composition of the vapour in equilibrium with this liquid.
( b) The bubble-point pressure for a liquid containing 40% (mole) A and the com -
position of vapour in equilibrium at 327 K .
7.20 The vapour pressures of substances A and B can be evaluated by the Antoine equations
2940.46
In PA = 14.5463 -
T - 35.93
2945.47
In PB = 14.2724 -
T - 49.15
where T is in K and P is in kPa. Assuming that the solutions formed by these are ideal,
calculate the fraction of the system that is liquid and the composition of the liquid and
the vapour in equilibrium at 327 K and 65 kPa when the overall composition of the
system is 70 mole percent A .
7.21 A solution of methanol in water containing 0.158 mole fraction methanol boils at
357.3 K and 101.3 kPa and produces a vapour containing 0.553 mole fraction methanol.
 Solutions and Phase Behaviour 187

Is Raoult’s law valid? If not determine the percent deviation from it for each component.
The vapour pressure of methanol may be estimated using the Antoine equation
3626.55
In Ps = 16.5725 -
T - 34.29
7.22 Two substances A and B are known to form ideal liquid solutions. A vapour mixture
containing 50 mol % A and 50 mol % B is at 311 K and 101.3 kPa. This mixture is
compressed isothermally until condensation occurs. At what pressure does condensation
occur and what is the composition of the liquid that forms? The vapour pressures of
A and B are 142 kPa and 122 kPa respectively.
7.23 A liquefied fuel gas consists of 60% // -butane , 35% propane and 5% ethane. All
compositions are on mole basis. The vapour pressures at 303 K are: ethane = 4.72 x
103 kPa, propane = 1.09 x 103 kPa and /7 -butane = 3.45 x 102 kPa. Calculate the
following:
(a ) The vapour pressure of the liquid at 303 K
( b) The composition of the vapour at 303 K
( c ) Repeat parts (a) and (b) if all ethane is removed from the liquid
7.24 Hexane ( A ) and heptane (B) form an ideal solution. The vapour pressures of pure
hexane and heptane are:

T (K ) 342 343 348 353 358 363 368 372.4

Pi (kPa) 101.3 104 122 141.3 163.3 187.3 210.2 235.3

Pi (kPa) 39.3 40.3 46.4 56.8 66.4 78.4 90 101.3

(a ) Plot the boiling point diagram for the system at 101.3 kPa .
( b) Plot the equilibrium diagram at 101.3 kPa.
7.25 The binary system, acetone (,4 )-acetonitrile (B) may be treated as an ideal solution.
Using the vapour pressure data given below prepare the following:
(a ) A plot of P versus x and P versus y at 323 K
( b) Boiling point diagram

T (K ) 311.45 315 319 323 327 331 335.33

Pi (kPa) 53.32 61.09 70.91 81.97 94.36 108.2 124.95

Pi (kPa) 21.25 24.61 28.90 33.79 39.35 45.62 53.32

ie vapour pressures of benzene { A ) and chlorobenzene (B) are given below

T (K ) 352.8 363.2 373.2 383.2 393.2 405.3

Pi (kPa) 101.3 135.1 178.7 232.5 298.0 395.3

Pi (kPa) 18.2 27.7 39.06 53.7 72.3 101.3
188 Stoichiometry and Process Calculations

Assume that benzene and chlorobenzene form an ideal solution.

(a ) What are the normal boiling points of benzene and chlorobenzene ?
( b) Prepare the T-x-y diagram for the system at 101.3 kPa .
( c ) Using the T-x-y diagram of part (b) determine the bubble point and dew-point of
an equimolar mixture of benzene and chlorobenzene at 101.3 kPa.
7.27 Assuming Raoult’s law to be valid for the system benzene (4) -ethyl benzene (.B) and
the vapour pressures are given by the Antoine equations:
2788.51
In Pj = 13.8858 -
T - 52.41
3279.47
In Pi = 14.0045 -
T - 60.00
where P is in kPa and T is in K.
(a) Construct the P-x-y diagram at 370 K .
( b) Construct the T-x-y diagram at 100 kPa .
7.28 A liquid mixture containing 65 mol % benzene and 35 mol % toluene is subjected to
flash vaporization at 363 K and 101.3 kPa. The vapour pressure of benzene at this
temperature is 136.09 kPa and the vapour pressure of toluene is 54.21 kPa . Flash
vaporization is essentially an equilibrium stage operation. Calculate the following:
(a) The exit vapour composition
( b) The exit liquid composition
( c ) The mole percent of the feed that is vaporized
7.29 A solution containing 25% benzene (MW = 78.048), 35% toluene (MW = 92.064) and
40% xylene ( MW = 106.08) is in equilibrium with its vapour at 373 K. All percentages
are on a weight basis. Determine the following:
(a) The total pressure
( b) The composition of the vapour
( c ) The average molecular weight of the liquid and vapour
The vapour pressures at 373 K are: benzene = 178.7 kPa, toluene = 74.7 kPa and
xylene = 28 kPa.
7.30 For the system ^-pentane (4 )-ft -heptane (.B) the vapour pressures are given by the
Antoine equation

T -C

where P is in kPa and T is in K . The constants are as follows:

System A B c
w- pentane 13.8183 2477.07 40.00
w-heptane 13.8587 2911.32 56.56
 Solutions and Phase Behaviour 189

Assuming that the solution formed is ideal, calculate the following:

(a ) The composition of the liquid and the vapour in equilibrium at 130 kPa and 335 K
( b) The composition of the vapour in equilibrium with a liquid containing 30% (mol)
pentane and the equilibrium temperature at P = 100 kPa
( c ) The total pressure and the vapour composition in equilibrium with a liquid of
composition x = 0.40 at T = 335 K
7.31 The vapour pressures of ethanol and water are given by the Antoine equation. The
Antoine constants are:
Name A B c
Water 16.26205 3799.887 46.854
Ethyl alcohol 16.5092 3578.91 50.50

Compare the equilibrium data calculated using Raoult’s law with the experimental
values given below:

T (K ) 373.2 368.7 359.9 357.3 355.5 353.9 352.9 351.94 351.61 351.35 351.61
X 0 0.019 0.097 0.166 0.261 0.397 0.52 0.676 0.747 0.894 1
y 0 0.17 0.438 0.509 0.558 0.612 0.66 0.739 0.782 0.894 1

An ethanol-water solution containing 25% by mole ethanol at 313 K is being heated

in a closed container at a constant pressure of 101.3 kPa . Calculate the following using
the experimental values:
(a ) The temperature at which vaporization begins
( b) The composition of the first bubble of vapour formed
( c ) The composition of the residual liquid when 25 mole % is vaporized
Non-ideal solutions
7.32 An aqueous solution of acetaldehyde contains 1% acetaldehyde by weight. The partial
pressure of acetaldehyde over the solution is found to be 20.6 kPa at 367 K . What will
be the partial pressure over a 0.1 molal solution at the same temperature ?
7.33 The Henry ’s law constant for oxygen in water at 298 K is 4.4 x 104 bar. Estimate the
solubility of oxygen in water at 298 K for a partial pressure of oxygen of 0.25 bar.
7.34 How many cubic metres of oxygen at 100 kPa can be dissolved in 10 kg water at 293 K
if the Henry’s law constant for oxygen in water at 293 K is 4.4 x 109 N/m 2 .
7.35 At 293 K, the solubility of oxygen in water is found to be 1 g in 100 g water for a
partial pressure of 0.25 bar for oxygen. Estimate the Henry ’s law constant of oxygen
in water at 293 K.
7.36 The partial pressure of acetone (4) and chloroform (B) were measured at 298 K and
are reported below:
190 Stoichiometry and Process Calculations

xB 0 0.2 0.4 0.6 0.8 1.0

PA (bar) 0.457 0.355 0.243 0.134 0.049 0

Pit (bar) 0 0.046 0.108 0.187 0.288 0.386

Determine the Henry ’s law constants.

7.37 Calculate the concentration of nitrogen in water exposed to air at 298 K and 1 bar if
the Henry ’s law constant for nitrogen in water is 8.68 x 104 bar at this temperature .
Express the result in moles of nitrogen per kg water ( Hint : Air is 79 percent nitrogen
by volume).
7.38 The partial pressure of methyl chloride in a mixture varies with its mole fraction at
298 K as detailed below :

X 0.0005 0.0009 0.0019 0.0024

p (bar) 0.27 0.48 0.99 1.24

Estimate the Henry ’s law constant of methyl chloride .

Vapour-liquid equilibrium calculations
7.39 A solution contains 50.0% // -pentane, 30.0% // -hexane and 20.0% // -heptane . The
Antoine constants for the constituents are given below:

Name A B c
n -pentane 13.8183 2477.07 39.94
// -hexane 13.8216 2697.55 48.78
// -heptane 13.8587 2911.32 56.51

Assuming that Raoult’s law is applicable, determine the following:

(a ) The dew -point pressure of the mixture at 295 K
( b) The dew -point temperature at 400 kPa
(c ) The bubble-point temperature at 400 kPa
(d ) The bubble-point pressure at 295 K
7.40 A solution of hydrocarbons contains // -propane 5.0%, /7-butane 30.0%, // -pentane
40.0% and // -hexane 25.0%. Compute the bubble -point and the dew -point at 350 kPa.
The -values can be taken from the DePriester nomographs.
^
7.41 A mixture of hydrocarbon vapours containing 21.8% ethane , 66.5% propane , 10.73%
isobutane and 0.97% //-butane is cooled at constant temperature of 311 K . Using the
following K values determine the dew-point pressure and the liquid composition.
 Solutions and Phase Behaviour 191

Component P = 1310 kPa P = 1380 kPa P = 1450 kPa

Ethane 3.22 3.07 2.92
Propane 1.005 0.973 0.92
Isobutane 0.45 0.43 0.41
/7- butane 0.315 0.305 0.295

7.42 A solution has the following composition in mol %: ethane 0.25%, propane 25.00%,
isobutane 18.5%, ^ -butane 56.0%, isopentane 0.25%. For a pressure of 10 bars,
calculate the following:
(a ) The bubble-point
( b) The dew-point
( c ) The composition of the liquid and vapour when 40% of the mixture is vaporized
7.43 1000 moles of a mixture of the following composition is contained in a vessel at
2200 kPa and 355 K.

Component Mole percent K value

Methane 16.0 8.8
Ethane 23.0 1.82
Propane 36.0 0.71
Isobutane 11.0 0.35
77- butane 14.0 0.27

How many moles of liquid and vapour will be there at these conditions? Also calculate
the liquid and vapour compositions.
7.44 A stream of gas in a natural gasoline plant has the following composition by volume :
ethane 10%, propane 14%, isobutane 19%, /7-butane 54% and isopentane 3%.
(a ) Calculate the pressure necessary to condense this gas completely at 311 K .
( b) For a condenser operating at the pressure in part (a), calculate the temperature at
which condensation starts and the temperature at which 50 mol % of the vapour
gets condensed. Also calculate the composition of the first liquid to condense and
the composition of the liquid and vapour phases at 50% condensation.
7.45 Determine the composition of the vapour in equilibrium with the liquid and the pressure
of the system at 313 K for a liquid mixture of 5 mol % methane, 10 mol % ethane,
30 mol % propane, 25 mol % iso-butane , and 30 mol % /7-butane . Determine the
pressure and the composition of the liquid in equilibrium with a vapour mixture of the
above composition.
7.46 Calculate the pressure at which condensation starts and the pressure at which
condensation is complete when a vapour mixture of the following composition is
subjected to condensation at a temperature of 300 K: 20 mol % ethylene, 20 mol % ethane,
40 mol % propane and 20 mol % /7 -butane.
192 Stoichiometry and Process Calculations

7.47 A vapour mixture containing 15% ethane, 20% propane , 60% isobutane and the rest
^-butane is subjected to partial condensation so that 75% of the vapour is condensed.
If the condenser temperature is 300 K, determine the pressure.
7.48 An equimolar mixture of propane (1) and ^ -butane (2) is partially condensed so that
50 mol % of the mixture is in the liquid state at 311 K . Using the DePriester nomograph,
determine the following:
(a) The pressure
( b) The vapour and liquid compositions
( c ) The pressure at which condensation begins at the constant temperature of 311 K
7.49 The following table gives the vapour pressures of alcohols in kPa at different temperature
(K ).

T (K ) Vapour pressure (kPa )

Methanol Ethanol n-Propanol n-Butanol
323 55.3 29.3 11.9 4.5
333 83.9 46.9 19.9 7.9
338 102.2 58.4 25.3 10.4
343 123.9 72.3 32.1 13.3
348 149.2 88.7 40.3 17.5
353 178.5 108.3 50.1 22.0
358 212.4 131.2 62.0 27.5
363 251.2 158.0 76.1 30.1
373 346.4 227.4 112.4 51.7

For an alcohol mixture of composition 30% methanol, 20% ethanol, 15% /^ -propanol
and 35% ^-butanol, calculate the following for a total pressure of 101.3 kPa :
(a ) The bubble-point temperature and vapour composition
( b) The dew-point temperature and liquid composition
Vapour pressure of immiscible systems
7.50 Ethyl ether and water are charged into a still in the weight ratio 3:1 and allowed to boil.
Ether and water are immiscible . The temperature of the contents is maintained at 303 K
at which the vapour pressures of the pure liquids are 4.2 kPa for water and 80 kPa
for ether. Calculate the following:
(a ) The pressure inside the still
( b) The composition of the residual liquid when half the original mixture is vaporized
7.51 A vapour mixture contains 85% (mol) benzene and 15% (mol) water at 101 kPa and
373 K. Assume that liquid benzene and water are immiscible. The vapour pressures are
given by Antoine equations, the constants of which are:
A B c
Benzene 13.8858 2788.51 52.36
Water 16.26205 3799.887 46.854
 Solutions and Phase Behaviour 193

(a ) On cooling this vapour at constant pressure, at what temperature does condensation

begin and what is the composition of the condensate ?
( b) If cooling is continued, at what temperature do both liquids condense together?
7.52 A liquid of molecular weight 150 is insoluble in water and is to be purified by steam
distillation at a total pressure of 101.3 kPa. The vapour pressure of the liquid at the
temperature of distillation is 3.5 kPa . How many kilograms of steam is required
theoretically to distil one kilogram of the liquid?
7.53 A high-boiling organic liquid (MW = 185) is being steam -distilled. The vapour temperature
is measured to be 374.2 K .
(a ) What is the pressure in the still?
( b) If the vapour analyzed 87% water by weight, what is the vaporization efficiency ?
(The vaporization efficiency may be defined as the ratio of the minimum steam
required for steam distillation to the actual steam consumption.)
The vapour pressure of water at 374.2 K is 105 kPa and that of the organic liquid is
2.3 kPa.
7.54 It is proposed to purify benzene from small amounts of non-volatile impurities by
subjecting it to distillation with saturated steam at 99.3 kPa . Calculate the temperature
at which distillation will proceed and the weight of steam accompanying 1 kg benzene .
The vapour pressure data is given below :

T (K ) 323 333 343 348 353 363 373

P2S (kPa) 12.40 19.86 31.06 37.99 47.32 70.11 101.3

Pf (kPa) 35.85 51.85 72.91 85.31 100.50 135.42 179.14

7.55 Benzene (1) is to be purified from non-volatile impurities by subjecting it to steam

distillation at a pressure of 100 kPa . It may be assumed that benzene is immiscible with
water (2). The following vapour pressure data are available :

T (K ) 323 333 343 348 353 363 373

Pf (kPa) 35.85 51.85 72.91 85.31 100.50 135.42 179.14

P2S (kPa) 12.40 19.86 31.06 37.99 47.32 70.11 101.3

Determine the following:

(a ) The temperature of distillation
( b) The mole fraction of benzene in the vapour
( c ) The mass of steam required to distil 1 kg benzene
7.56 Ethyl aniline is purified from dissolved non-volatile impurities by steam distillation at
101.3 kPa pressure. The vapour pressure of aniline and water are as follows:
194 Stoichiometry and Process Calculations

T (K ) 353.8 369.2 372.3 386.4

Aniline (kPa) 1.33 2.67 3.04 5.33
Water (kPa ) 48.5 87.7 98.3 163.3

Calculate the following:

(a ) The boiling points of the mixture
( b) The composition of distillate
7.57 A mixture containing chlorobenzene and water is being distilled . The liquids may be
assumed immiscible. The distillation is carried out under such conditions that two liquid
layers are present in the still. The vapour pressure data as follows :
3295.12
Chlorobenzene: In P s = 13.9926 -
T - 55.60
3799.887
Water: ln P s = 16.26205 -
T - 46.854
Determine the temperature of distillation and the composition of the vapour if
(a ) The pressure is 4 kPa.
( b) The pressure is 40 kPa.
7.58 It is desired to separate CHC13 from a non-volatile insoluble impurity by steam distillation
at a total pressure of 175 kPa. Saturated steam at 200 kPa is introduced directly into
the liquid. Calculate:
(a ) The boiling point of the mixture
( b) The composition of the distillate
( c ) The composition of the distillate if 20% more steam than the theoretical amount
distils over
The vapour pressure data are as follows :

T (K ) 299.1 315.9 334.5 357.05 393.2

Chloroform (kPa) 26.7 53.3 101.3 202.7 506.6
Water (kPa ) 3.3 8.5 21.1 55.3 198.2

7.59 A gas mixture contained 2 x 105 kg of hexane and 5 x 103 kg of water vapour at 373 K
and 200 kPa. The mixture is cooled at constant pressure till water begins to condense .
Assume that hexane and water are immiscible in the liquid phase.
(a ) What is the initial partial pressure of hexane in the gas?
( b) What is the temperature at which condensation begins?
The vapour pressure of /7-hexane is given by the Antoine equation with the following
constants when pressure is in kPa and temperature in K:
A = 13.8216 B = 2697.55 and C = 48.78
 Solutions and Phase Behaviour 195

7.60 A vapour mixture contains 85 mol% CS2 and 15 mol% H20 at 101.3 kPa and 373 K.
The liquids CS2 and H20 are immiscible. Vapour pressure data for the pure fluids are
given as follows:

T (K ) 283.2 293.2 303.2 313.2 323.2 333.2

CS2 (kPa) 26.34 39.69 57.95 82.35 114.26 155.15
Water (kPa ) 1.227 2.337 4.241 7.375 12.34 19.92

The vapour is cooled at 101.3 kPa till condensation begins. Determine the following:
(a ) The temperature at which condensation begins
( b) The composition of the first condensate
(c ) The temperature at which both liquids condense together
7.61 Dime thy laniline is distilled with steam at 90 kPa to free it from non-volatile impurities.
Assuming it to be completely immiscible with water, determine the following:
(a ) The distillation temperature
( b) The composition of the vapour produced
vapour pressure data are as follows :

T (K ) 343.2 374.8 399

Ps (aniline), kPa 1.333 5.332 13.329
Ps (water), kPa 31.19 106.91 285.86

The plot of InPs versus \ IT may be assumed linear.

7.62 A stream contains 30 mol % toluene, 40 mol % ethyl benzene and 30 mol % water.
Assuming that mixtures of ethylbenzene and toluene obey Raoult’ s law and they are
completely immiscible in water, calculate the following for a total pressure of
101.3 kPa :
(a ) The bubble-point temperature and the composition of the vapour
( b) The dew -point temperature and the composition of the liquid .
The vapour pressure data are given below:

T (K ) 352.6 361.0 366.5 383.2 388.8

Ps (water), kPa 46.29 64.33 79.42
Ps (toluene), kPa 38.49 50.65 60.78 99.27 116.50
Ps (ethyl benzene), kPa 16.41 22.79 27.35 47.61 56.73

7.63 /7 -heptane ( 1) and water (2) are essentially immiscible as liquids. A vapour mixture
containing 65 mol % water at 373 K and 101.3 kPa is cooled slowly at constant
pressure until condensation is complete . Construct a plot for the process showing
temperature versus equilibrium mole fraction of heptane in the residual vapour. For
/7 -heptane,
196 Stoichiometry and Process Calculations

2918.738
In if = 13.87770 - T - 56.404
The vapour pressure of water is
3799.887
In Ps = 16.26205 -
T - 46.854
where P is in kPa and T in K.
7.64 Toluene (1) and water (2) are essentially immiscible in the liquid state . Determine the
dew-point temperature and the composition of the first drops of liquid formed when
the vapour mixtures of these species containing
(a ) 23 mol % toluene
( b) 77 mol % toluene at 101.3 kPa .
At 101.3 kPa, what are the bubble-point temperature and the composition of the last
drop of vapour in each case? The vapour pressure of toluene is
3103.010
In if = 14.00976 - T - 53.413
The vapour pressure of water is
3799.887
In Ps - 16.26205 -
T - 46.854
where P is in kPa and T is in K.
7.65 Components 1 and 2 are insoluble in the liquid phase. Estimate the dew -point temperature
and the compositions of the first drops of liquid formed when vapour mixtures of
components 1 and 2 containing
(a ) 75 mol % component 1 and
( b) 25 mol % component 1
are cooled at a constant pressure of 101.33 kPa. The vapour pressures of the pure
components in kPa are given against temperature in K in the following table.

T 358 363 368 373 378 383 388 393 398.6

Px 23.53 33.56 39.58 46.59 54.62 63.97 74.32 86.34 101.33

Pi 57.82 70.13 84.53 101.33 120.79 143.28 169.02 198.51 239.54

Vapour pressure of solutions of non-volatile solutes

1.66 An aqueous solution containing 20% by weight dissolved non-volatile solute (MW = 120)
is sent to a flash distillation chamber maintained at 5 kPa and 330 K. The effective
vapour pressure of the solution ( p) is given as

P = xw w^
 Solutions and Phase Behaviour 197

where xw and
^
P are the mole fraction of water in the solution and the vapour pressure
of pure water respectively. The vapour pressure of water at 330 K is 17.147 kPa. Per
100 kg of the solution, determine the following:
(a ) The amount of pure water obtained as vapour
( b) The concentration of the solute in the liquid leaving the chamber
7.67 A liquid mixture consisting of 15% A, 70% B and 15% C is flashed at 250 K and
10 kPa. All compositions are on a mole basis. The vapour pressure of component C
is negligible in comparison with those of A and B . The vaporization equilibrium constants
of A and B may be taken as 5.25 and 0.65 respectively. Determine the following:
(a ) The moles of liquid and vapour at equilibrium
( b) The mole fractions in the liquid and vapour
7.68 The normal boiling point of a 5 -molal solution of sodium chloride in water is found
to be 379.2 K . The vapour pressure of water at this temperature is 124.8 kPa.
Assuming that the relative vapour pressure is independent of temperature, determine
the vapour pressure of the solution at 300 K if the vapour pressure of water at
300 K is 3.5 kPa.
7.69 The normal boiling point of a 5-molal solution of sodium chloride in water is found to
be 379.2 K. What will be the boiling point of the solution at 80 kPa? The vapour
pressure of water is given by

In Pi = 16.26205 - T3799.887
- 46.854
where P is in kPa and T is in K . Assume that the relative vapour pressure is independent
of temperature .
7.70 The normal boiling point of a 10 molal solution of sodium nitrate in water is 382 K.
Determine the following:
(a ) The boiling point elevation of the solution
( b) The boiling point elevation at 50 kPa
Assume that the vapour pressure of water is given by the Antoine equation
3799.887
In Pw = 16.26205 -
T - 46.854
where P is in kPa and T is in K, and the relative vapour pressure is independent of
temperature.
 8 Humidity and
Humidity Chart

Air conditioning, water cooling, humidification, drying operations, etc . are processes in which
one has to deal with vapours that will be present in association with a non-condensable gas or
a mixture of non-condensable gases. In good number of such situations, the vapour is water
vapour and non-condensable gas is air. Air conditioning is the process of maintaining the water
content in the air at some desired level. Maintaining the humidity and temperature of air at some
specified levels is important not only for houses and buildings, but also for certain plant areas
in process industries. This is achieved by either condensation of water vapour from air or by
evaporation of liquid water into an unsaturated air stream. Cooling of process water is achieved
in cooling towers by evaporation of water into air stream . Air conditioning and water cooling
operations fall under the general category of operations designated in chemical engineering
parlance as humidification-dehumidification operations. Another important unit operation which
also makes use of an air stream or a stream of hot flue gases picking up moisture by
evaporation is the drying operation. In drying, a wet material will be exposed to a relatively dry
hot air or flue gas. The material gets dried by giving off its moisture to the unsaturated gas
stream with which it is contacted. The air -water vapour system is not the only system of
importance involving mixtures of condensable vapours and non-condensable gases. Frequently,
vapours of organic compounds such as benzene, carbon tetrachloride , acetone, etc. present in
air or process gases are to be recovered as part of a solvent recovery operation or are to be
removed from the gas stream as part of a purification step. A clear understanding of the
concepts of humidity and saturation, degree of saturation and the conditions under which the
gas stream remains saturated are therefore very essential to a chemical engineer.

8.1 SATURATION
Consider a liquid A (say, water) in contact with a non-condensable gas B (say, air) in a closed
container at constant temperature and pressure . Initially the air is dry so that the partial pressure
of water vapour in the air is zero. When the dry air comes in contact with liquid water, it picks
198
 Humidity and Humidity Chart 199

up moisture from the liquid and as a result the partial pressure of water in the gas increases.
Finally when equilibrium between the liquid and the gas is established, the partial pressure of
water vapour in the gas stream remains at a constant value. Even if we provide an infinitely
long period for contact between the liquid and the gas, the equilibrium partial pressure exerted
by the vapours of the liquid in the gas will not change so long as the temperature is not altered.
This is the state at which the gas is saturated with the vapours of the liquid . The partial
pressure exerted by the vapour under saturation is equal to the vapour pressure of the liquid
at the given temperature. Since the total pressure P is constant, we have under saturation, the
partial pressure of vapour, pA = PAS, where PAS is the vapour pressure of component A, and the
partial pressure of the gas, pB = P - PAS . If the gas is unsaturated, the partial pressure of the
vapour is less than the vapour pressure of the liquid at the temperature of the gas.

EXAMPLE 8.1 The vapour pressure of acetone at 280 K is 13.25 kPa. For a mixture of
nitrogen gas saturated with the vapours of acetone at 280 K and 105 kPa, calculate the following:
(a) The mole percent of acetone in the mixture
(b) The percent composition by weight
(c) The amount of vapour in kilograms per m 3 of the mixture.
Solution Since the nitrogen gas is saturated with acetone vapours, the partial pressure of
acetone in the gas at 280 K, pA = the vapour pressure of acetone at 280 K, PAS = 13.25 kPa.
(a) The mole fraction of acetone is

_ = A_ = 13.25 =
partial pressure PA
total pressure
= P
^P 105
The mole percent = mole fraction x 100 = 12.62%
(b) The molecular weight of acetone = 58.048 and the molecular weight of nitrogen = 28.0.
One mole of the gas mixture contains 0.1262 mole of acetone and 0.8738 mole of
nitrogen.
Or one mole of the gas mixture contains 0.1262 x 58.048 = 7.3257 g of acetone and
0.8738 x 28 = 24.4664 g of nitrogen. Therefore , the composition in weight percent is:
7.3257
acetone = x 100 = 23.04%
(7.3257 + 24.4664)
24.4664
nitrogen x 100 = 76.96%
(7.3257 + 24.4664)
(c) Volume of one kmol gas at 280 K and 105 kPa is

T_ = 22.4 x 101.3 x 280

Vo x ^
p
x
To 105 273.15
= 22.17 m 3
The mass of vapour present in one kmol of gas is 7.3257 kg.
7.3257 3
Concentration of the vapour =
22.17
= 0.3304 kg/m
200 Stoichiometry and Process Calculations

EXAMPLE 8.2 It is desired to prepare a 10% benzene vapour-air mixture by saturating dry
air with benzene from a container of the liquid at 101.3 kPa. What temperature should be used
to achieve the desired composition? The vapour pressure of benzene is given by the Antoine
equation

2788.51
In Ps = 13.8858 -
T - 52.36
Solution The partial pressure of benzene in a 10% benzene vapour-air mixture at 101.3 kPa
is 101.3 x 0.1 = 10.13 kPa. For saturated air, the partial pressure is equal to the vapour
pressure. Using the Antoine equation, the temperature of benzene at which the vapour pressure
is 10.13 kPa is determined.
2788.51
In 10.13 = 13.8858 - T = 293.4 K
T - 52.36

EXAMPLE 8.3 Dry air is blown through acetone at 285 K and a constant pressure of 101.3
kPa. If it is desired that 5 kg of acetone be evaporated what is the minimum amount of dry air
required in kilograms? The vapour pressure of acetone at 285 K is 16.82 kPa .
Solution The minimum quantity of air that is required to contain 5 kg of acetone corresponds
to the condition when air is saturated with 5 kg of acetone vapours. Under the saturated
condition, the ratio of moles of acetone to moles of dry air is
pj 16.82
p - pj
= 0.1991
101.3 -16.82
The ratio of mass of acetone to mass of dry air is
58.048
0.1991 x = 0.3985
29
where 58.048 is the molecular weight of acetone and 29 is the molecular weight of dry air. One
kilogram of dry air under saturated state contains 0.3985 kg of acetone vapour. The amount of
dry air required to evaporate 5 kg of acetone is
5
12.55 kg
0.3985

8.2 HUMIDITY, PERCENT HUMIDITY AND DEW POINT

8.2.1 Humidity
The term humidity is used to indicate the concentration of the vapour in a gas-vapour mixture.
For the air -water vapour system , humidity is defined as the amount of water vapour present
per unit quantity of dry air and can be expressed on a mole basis or a mass basis. The molal
humidity is defined as the number of moles of water vapour present per one mole of dry air.
 Humidity and Humidity Chart 201

Let there be nA moles of water vapour and nB moles of dry air in a given sample of air-water
vapour mixture. Then,
moles of water vapour nA
molal humidity, Y = ; :
moles ol dry air
= —
nB
—
(8.1)

Assuming that the air-water vapour mixture behaves as an ideal gas, the following equations
can be used to determine the number of moles of the constituents.

nA =
PAV
RT
(8.2)
pBv
nB =
RT
where V is the volume of the mixture and T is the temperature . Combining Eqs . (8.1) and (8.2),
we get
molal humidity, Y = — = —PB = —P — PA—
B
~
(8.3)

Equation (8.3) means that the molal humidity is equal to the ratio of the partial pressure of water
vapour to the partial pressure of dry air. Though the definitions given here and in the following
sections refer to the air-water vapour system, these are equally applicable for all vapour-gas
mixtures.
If the gas is saturated with the vapours, the molal humidity means the molal humidity at
saturation denoted as Ys. It is equal to the moles of water vapour per mole of dry air under
saturation. Since at saturation, the partial pressure of the vapour is equal to the vapour pressure,
the molal saturation humidity can be written as

VS - PA ( 8.4)
P - Pl
where pj is the vapour pressure of water.
The absolute humidity is defined as the mass of vapour present per unit mass of vapour-
free gas. For the air-water vapour system, it is the kilograms of water present per one kg of dry
air. If mA and mB are the weights of the vapour and vapour-free gas, then

absolute humidity, Y' = —tnmB (8.5)

Absolute humidity is related to the molal humidity as:

Y' = mA
mB
= nnA Y MMA Y V MMA- (8.6)
B B B

where MA and MB are the molecular weights of A and B respectively. Combining with Eq. (8.3)
and noting that for air the average molecular weight is approximately 29 and the molecular
weight of water is 18, the absolute humidity of the air-water vapour system can be related to
the partial pressure as
r _ PA x 18 — (8.7)
P PA 29 ~
202 Stoichiometry and Process Calculations

The absolute saturation humidity (7') denotes the kilograms of water vapour that one kg of
dry air can hold at saturated conditions. Analogous to Eq. (8.4), we can write
Ps M
Y:s = p Ap S X MA (8.8)
- A B

At the boiling point of the liquid, the vapour pressure is equal to the total pressure so that the
denominator in Eq. (8.8) reduces to zero. It means that as the boiling point of the liquid is
approached, the saturation humidity tends to infinity. We can see from Eqs. (8.4) and (8.8) that
at a given temperature, the molal humidity at saturation is independent of the nature of the gas
and depends only on the pressure whereas the absolute saturation humidity depends on the
characteristics of the gas as well.
EXAMPLE 8.4 A mixture of acetone vapour and nitrogen gas at 101.3 kPa and 295 K
contains acetone vapour to the extent that it exerts a partial pressure of 15 kPa . The vapour
pressure of acetone at 295 K is 26.36 kPa. Determine the following:
(a) The mole fraction of acetone in the mixture
(b) The weight fraction of acetone in the mixture
(c) The molal humidity
(d) The absolute humidity
(e) The molal saturation humidity
(f ) The absolute saturation humidity
(g) The mass of acetone in 100 m 3 of the mixture.
Solution
(a) The partial pressure of acetone in the gas is 15 kPa .

Mole fraction of acetone =

pressure
=P
_15_ = „14g ,
total pressure 101.3
(b) One mole of the mixture contains 0.1481 mole acetone and the rest (0.8519 mole)
nitrogen. The molecular weight of acetone = 58.048 and the molecular weight of
nitrogen = 28.
Therefore, the weight fraction of acetone in the mixture is
0 1481 X 58 048
= 0.2649
0.1481 x 58.048 + 0.8519 x 28
(c) Molal humidity is the ratio of moles of acetone to moles of dry nitrogen, i.e.

0.1481
0.8519
= 0.1738
( Note : Molal humidity may be calculated as the ratio of partial pressure of acetone to
the partial pressure of nitrogen , i.e.
 Humidity and Humidity Chart 203

15 moles of acetone
Y = 101.3 - 15 = Q 1738 moles of nitrogen 7
(d ) Absolute humidity is the ratio of kilograms of acetone to kilograms of nitrogen. It is
obtained by multiplying the molal humidity by the ratio of the molecular weights

= 0 1738, '°
ki snlms of acetone
T = 0,3603
28 kilograms of nitrogen
(e) The vapour pressure of acetone at 295 K is, Ps = 26.36 kPa
pS
Saturation humidity, ys =
26.36 _ o 3517 moles of acetone
101.3 - 26.36 moles of nitrogen
58.048 kilograms of acetone
(f ) Absolute saturation humidity, YS' = 0.3517 x
= 0.7292 kilograms of nitrogen
28
(g) The number of moles of the mixture in 100 m 3 is
V P T0 100 101.3 273.15
22.414
X
P0
Xy
T 22.414
X
101.3
x
295
= 4.13 kmol
Since the mole fraction of acetone is 0.1481, the number of moles of acetone in the
mixture is
0.1481 x 4.13 = 0.6118 kmol
The mass of acetone in 100 m 3 of the total gas is
0.6118 x 58.048 = 35.5 kg

8.2.2 Relative Humidity and Percent Humidity

The degree of unsaturation of a gas-vapour mixture can be expressed in two ways: the first
is the percent relative saturation and the second is the percent saturation. The percent relative
saturation or percent relative humidity is the ratio of the actual partial pressure exerted by the
vapour to its vapour pressure at the same temperature , which is expressed as a percentage .
Thus,

relative saturation (relative humidity ) = -yxl 00%

^ (8.9)

On the other hand, the percent saturation or percent humidity is the ratio of moles of vapour
present in the gas per mole of dry gas to the moles of vapour present per mole of a vapour-free
gas if it is saturated at the temperature of the system, expressed as a percentage . It is same as
the ratio of kilograms of vapour present per kilogram of dry gas at the given temperature to
kilograms of vapour that would be associated with one kilogram of dry gas if the gas mixture
were saturated with the vapours at the same temperature.
204 Stoichiometry and Process Calculations

Percent saturation (percent humidity ) = - - — —

( VIA lYlfi )saturation
xl 00% (8.10)

The numerator in Eq. (8.10) is the molal humidity and the denominator is the molal humidity
at saturation. Therefore, the percent humidity can be defined as the ratio of the existing humidity
of the mixture to the humidity if the gas mixture is saturated with the vapours .

—Y x 100% = —
Yf
Percent saturation = x 100% (8.11)
*s *s

A percent saturation of 50% means that the water content per one kilogram of dry air is only
half of the water that one kilogram dry air will contain if the air is saturated with water vapour
at the same temperature. On the other hand, the relative saturation of 50 percent means that
the partial pressure of water in the air-water vapour mixture is only half the vapour pressure
of water at the temperature of the system . The relationship between percent saturation (PS)
and percent relative saturation (RS) will be clear by substituting Eqs. (8.3) and (8.4) into Eq.
(8.11).
n
_
P ps
PS = % x
i
PAS
PA P
x 100%
~
— (8.12)

Using Eq. (8.9), the above equation can be modified as

P ~ ps
PS = RS X
P PA
~
^ (8.13)

Since the ratio (P - P/ )I( P - P A ) in Eq. (8.13) is always less than 1, PS < RS.
EXAMPLE 8.5 Calculate the percent saturation and the relative saturation of the vapour-gas
mixture for the conditions given in Example 8.4.
Solution The percent relative humidity is the ratio of the partial pressure of acetone to the
vapour pressure expressed as a percentage, i.e.

RS = % X 100% =— X 1 0 0 = 56.9%
PSA 26.36
The percent humidity is given by Eq. (8.11)

PS = —YsY xl 00% = -0.3517

0 1738
x 100 = 49.42%

EXAMPLE 8.6 Moist air contains 0.0109 kg water vapour per cubic metre of the mixture at
300 K and 101.3 kPa. Calculate the following:
(a) The partial pressure of water vapour
(b) The relative saturation
(c) The absolute humidity of the air
(d) The percent saturation
 Humidity and Humidity Chart 205

(e) The temperature to which the mixture be heated so that its percent saturation becomes
10%.
The vapour pressure of water (in kPa) is approximated by the Antoine equation as

In Ps = 16.26205 - " 37887

T - 46.854
Solution The number of moles of the mixture in one cubic metre at 300 K and 101.3 kPa is
V P T 1 101.3 273.15 AA 1 A C 1
x— x 0
22.414 P0 T
— = 22.414 x 101.3 x 300
= 0.0406 kmolt
/ /

4
0.0109 kg of water = 0.0109/18.016 = 6.05 x 10 “

kmol
(a) The mole fraction of water vapour is
6.05 x 10-4
nw
= 0.0149
n
0.0406
The partial pressure of water vapour is
mole fraction x total pressure = 0.0149 x 101.3 = 1.51 kPa
(b) The vapour pressure at 300 K is calculated using the Antoine equation:
3799.887
In Ps = 16.26205 - => Ps = 3.5 kPa
300 - 46.854
Relative saturation is the ratio of partial pressure to vapour pressure , i.e.

RS = —3.5 x 100 = 43.14%

(c) Absolute humidity can be evaluated by Eq. (8.7):

Y' - PA :: 1 8 - 1.51
X
18
P - p A 29 101.3 - 1.51 29
= 9.39 x 10 3 kg water/kg dry air
(d) Saturation absolute humidity is
s
7s ' = PA X
18
= 0.0222 kg water/kg dry air
P - PAs 29
r x 100
—
Percent saturation (PS) = = 42.27%
(e) When the mixture is heated at constant pressure, its humidity (7') will not change.
However, saturation humidity at the new temperature is different from the earlier value.
Since the percent saturation at the new temperature is given to be 10%, we have
7'
PS = —y r x 100 = 10.0%
2S
206 Stoichiometry and Process Calculations

Y ' 9 39 xl 0-3
Y' — —
= =
0.1 0.1
= 0.0939 kg water/kg dry air
But, by Eq. (8.8),
pS |o
Y' = — - x — = 0.0939 kg water/kg dry air
101.3 - Pj 29

Therefore, Pj = 13.31 kPa . The temperature corresponding to this vapour pressure is

calculated using the Antoine equation. This temperature is 324.8 K.

EXAMPLE 8.7 A fuel gas saturated with water vapour at 300 K and 100 kPa has a heating value
of 25000 kJ/m 3 of the total gas. What will be the heating value in kJ/m 3 of the gas at 295 K
and 105 kPa if its relative saturation is only 50%? The vapour pressure of water at 300 K and
295 K are respectively 3.5 kPa and 2.6 kPa .
Solution Basis: One cubic metre of the saturated fuel gas-water vapour mixture at 300
K and 100 kPa.
The number of moles in the mixture is
V P T0 1 100 273.15
xX xX
22.414 P0 T
X
22.414 101.3
X
300
= 0.0401 kmol
Since the partial pressure of water vapour in the saturated gas is equal to the vapour pressure
of water vapour,
the number of moles of the fuel = total moles x mole fraction
100 3,5
= 0.0401 x = 0.0387 kmol
100
The heat liberated by combustion of one cubic metre of the saturated gas at 300 K and 100 kPa
is the heat liberated by the combustion of 0.0387 kmol of the fuel gas. Therefore , heating value

of the fuel = = 646043 kJ/kmol.

0.0387
Now consider as a basis of one cubic metre of the gas at 295 K and 105 kPa. The total
number of moles present in the gas is
V P T0 1 105 273.15
x x x x = 0.0428 kmol
22.414 P0 T 22.414 101.3 295
The partial pressure of water vapour in the gas is
RS x vapour pressure = 0.5 x 2.6 = 1 . 3 kPa.
The number of moles of the fuel in the gas is
105 1,3
0.0428 x = 0.0423 kmol
105
Since the heating value is 646 043 kJ/kmol, 0.0423 kmol on combustion gives out 0.0423
x 646043 = 27328 kJ. That is, the heat liberated by the combustion of one cubic metre of the
 Humidity and Humidity Chart 207

gas at 295 K and 105 kPa = 27 328 kJ. Therefore , the heating value of the fuel at 105 kPa
and 295 K = 27 328 kJ /m 3.

8.2.3 Dew Point

Let us consider a process in which a given air-water system at certain temperature and
pressure is cooled at constant pressure out of contact with water. For illustration, consider a
mixture of air and water vapour with a relative humidity of 30% at 314 K and atmospheric
pressure. The vapour pressure of water at 314 K is 7.78 kPa . Therefore, the partial pressure
exerted by water in the air is 2.33 kPa and the absolute humidity is 0.0146 kg water vapour
per kg dry air. Suppose that the air is cooled at constant pressure out of contact with liquid
water. On cooling, the humidity or the partial pressure of water vapour will not change initially,
but its relative saturation will increase. This is because the vapour pressure decreases with
decrease in temperature and the relative saturation is measured as the ratio of partial pressure
to the vapour pressure. When the temperature of air drops to, say, 300 K at which the vapour
pressure of water is 3.56 kPa, the relative saturation of air becomes 65%. On further cooling,
a temperature will be reached at which the vapour pressure of water is equal to the existing
partial pressure of water vapour in the air and the air becomes saturated with the water vapour
present in it. This temperature is known as the dew point of the air. From the tables of vapour
pressure data of water, we can see that at 293 K the vapour pressure of water is 2.33 kPa,
same as the existing partial pressure of water vapour in the air. Thus, the dew point of the air
is 293 K. If air is cooled below this temperature, water vapour will condense. Suppose that
the temperature is brought down to 288 K. The maximum partial pressure the water vapour
can exert at 288 K is 1.7 kPa, the vapour pressure of water at 288 K . The humidity corresponding
to this partial pressure can be calculated to be 0.0106 kg water per kg dry air. Since the initial
humidity was 0.0146 kg water per kg dry air, cooling the air by 5 K below the dew point
results in condensation of 0.004 kg water vapour per every kg of dry air in the given sample
of humid air.
Thus, we see that dew point is the lowest temperature to which a gas-vapour mixture can
be cooled without condensation at constant pressure and out of contact with the liquid . Or it
is the temperature at which the vapour begins to condense when cooled at constant pressure .
At the dew point the existing vapour content is sufficient to saturate the gas. Stated differently,
the dew point is that temperature at which the vapour pressure of the liquid is equal to the
partial pressure of vapour in the given vapour-gas mixture. Knowing the dew point, the
humidity of the air is readily evaluated using the vapour pressure data . This is possible because
the saturation humidity at the dew point and the humidity of the given air-water vapour system
are the same. However, to establish the state of the given mixture uniquely, one more specification
such as the temperature, the relative saturation or the percent saturation also is necessary.
Dew point of air can be determined experimentally by cooling a well -polished metal surface
in the presence of air and measuring the temperature at which water vapour begins to condense
and fog appears on the metallic surface. As the dew point is a measure of the humidity, this is
one of the methods for measuring atmospheric humidity.

EXAMPLE 8.8 A mixture of nitrogen and benzene has a dew point of 300 K . The temperature
and the pressure of the mixture are 335 K and 150 kPa respectively. The vapour pressure of
benzene (kPa) is
208 Stoichiometry and Process Calculations

2788.51
In Ps = 13.8858 -
T - 52.36
Calculate the following:
(a) Percent saturation of the mixture
(b) Kilogram of benzene per kilogram of nitrogen
(c) Kilogram of benzene per m 3 of mixture
(d) Dew point of the mixture if the total pressure is 100 kPa
(e) Pressure required to condense 60% of the benzene from the mixture at 300 K.
Solution
(a) Using the Antoine equation , the vapour pressure of benzene at 300 K = 13.811 kPa and
at 335 K the vapour pressure is 55.693 kPa . Since the vapour pressure at the dew point
is equal to the partial pressure of the vapour, the partial pressure of benzene at 335 K
and 150 kPa = 13.811 kPa. Using the partial pressure and the vapour pressure, the
humidity and saturation humidity at 335 K and 150 kPa can be calculated using Eqs.
(8.3) and (8.4):

PA 13.811
Y= = 0.1014 kmol benzene/kmol nitrogen
P - pA 150 - 13.811

Ps 55.693
Ys = P -APj 150 - 55.693
= 0.5906 kmol benzene/kmol nitrogen

Percent saturation = —YYs x 100 = 17.17%

(b) The quantity of benzene per kilogram of nitrogen is
g.Q. 2826 k8 b,nZene
(MA
yx
^
MB
s 0.1014 x
^
28 kg nitrogen
= molecular weight of benzene, MB = molecular weight of nitrogen)
(c) Basis : One cubic metre of the mixture
The number of moles of the mixture is
V P T0 1 150 273:15
xX xX
22.414 P0 T
X
22.414 101.3
X
335
—
= 0.0539 kmol
Since the molal humidity is 0.104 kmol benzene per kmol nitrogen, the mole fraction
of benzene is
Y 0.1014
y= = 0.09206
1 + 7 1.1014
Therefore, the number of moles of benzene in 1 m 3 (i.e., 0.0539 kmol) of the mixture
= 0.0539 x 0.09206 = 4.9623 x 10 3 kmol . Concentration of benzene in kg/m 3 =
“

4.9623 x 10 3 x 78.048 = 0.3873 kg/m 3.

"
 Humidity and Humidity Chart 209

(d) Since the humidity remains the same , the partial pressure of benzene at 100 kPa = mole
fraction x total pressure = 0.0926 x 100 = 9.26 kPa . Using the Antoine equation, the
temperature at which the vapour pressure of benzene is 9.26 kPa , is found out. This
temperature is the dew point at 100 kPa . The dew point = 291.51 K.
(e) The mixture initially contains 0.1014 kmol benzene/kmol nitrogen. When 60% of this
is condensed the humidity becomes 0.4 x 0.1014 = 0.04056 kmol benzene per kmol
nitrogen. At 300 K, if this value is the saturation humidity at a pressure of P kPa,
PA 13.811
Y= = 0.04056 kmol benzene/kmol nitrogen
P ~ PA P - 13.811
Therefore, P = 354.3 kPa.

EXAMPLE 8.9 One cubic metre of a gas at STP is to be dried from a dew point of 300 K
to a dew point of 285 K. (a) How much water must be removed? (b) What will be the volume
of the gas at STP after drying? The vapour pressure of water is 1.4 kPa at 285 K and 3.56 kPa
at 300 K.

Solution Basis: 1 m 3 of gas at STP. Moles of gas = = 0.0446 kmol

(a) For air at a dew point of 300 K, the partial pressure of water in the air is equal to the
vapour pressure of water at 300 K. Since the ratio of partial pressure of water to the
partial pressure of air is the molal humidity, the molal humidity of the given air
3.56
Yi = P PApA = 0.0364 kmol water per kmol dry air
— 101.3 - 3.56
For air at a dew point of 285 K, the molal humidity

Y2 = —
P - pA
= 101.3 - 1.4 = 0.0140 kmol water per kmol dryJ air

Therefore , the moles of water removed per kmol of dry air on drying is
Tx - Y 2 = 0.0364 - 0.0140 = 0.0224 kmol
The number of kmoles of dry air present in 1 m 3 of the sample is

0.0446 x = 0.0430 kmol

1.0364
The amount of water removed is
0.0430 X 0.0224 X 18.016 = 0.0174 kg

(b) After drying, the mixture contains 0.0430 kmol dry air and 0.0430 x —0.0140
-— = 6.02
X 10 “ 4 kmol water vapour. Therefore, the volume at STP is
0.0430 x 1.0140 x 22.414 = 0.9773 m 3
210 Stoichiometry and Process Calculations

8.3 HUMIDITY CHART

Humidity charts or psychrometric charts simplify the calculations involved in operations such
as humidification, drying, condensation of vapours from non-condensable gases and evaporation
of liquids into gas streams, etc. The humidity charts usually refer to air-water vapour systems
although charts for any vapour-gas combination can be constructed . One limitation of these
charts is that they are applicable only for the total pressure for which they are constructed.
For other pressures, separate charts are to be prepared or appropriate correction terms are to be
used. The humidity chart for an air-water system at atmospheric pressure is shown in Figure 8.1.
The ordinate represents the absolute humidity T (kg water vapour per kg dry air) and the
abscissa represents the dry -bulb temperature. The temperature of a gas-vapour mixture that is
measured by an ordinary thermometer immersed in the mixture is called the dry-bulb temperature
( DBT). The absolute saturation humidity at any given temperature can be read from the
100 percent saturation curve: Take the temperature on the horizontal axis and move vertically
up to the 100 percent curve and then horizontally to the humidity axis. To find the humidity of
air of 50 percent saturation at a given temperature, the same procedure is adopted but using the
50 percent saturation curve instead of the 100 percent curve. Note that in some psychrometric
charts, the percent relative saturation curves are plotted instead of percent saturation curves.
The humidity charts for an air-water system can be constructed using the vapour pressure
versus temperature data for water. Refer to Figure 8.2.
To draw the 100 percent saturation humidity curve (BCD), assume a temperature, find the
vapour pressure at that temperature, and calculate the saturation humidity using Eq. (8.8) . For
example, for temperature corresponding to point A, the vertical height AC gives the saturation
humidity. By repeating the calculation at different temperatures below the boiling point of water
at the given pressure, other points on the saturation curve can be marked on the diagram . A
smooth curve drawn through these points establishes the 100 percent saturation curve. Saturation
humidity at the boiling point is infinity and therefore the curve rises asymptotically to infinity
near the boiling point. Other percent saturation curves are drawn by dividing the vertical
distance between this curve and the temperature axis equally into as many divisions as required.
For example, the distance AC can be divided into 4 equal parts, then the curves passing through
these parts can be marked as 25%, 50% and 75% saturation lines as shown in Figure 8.2.
Specifying the dry -bulb temperature and the percent humidity uniquely determines the state
of the air-water vapour system such as the one represented by point P where the dry -bulb
temperature is TB and the percent saturation is 25%. The dew point of the air at point P is
obtained by moving horizontally to point Q on the 100 percent curve and by reading the
corresponding temperature on the horizontal axis. Alternatively if the dew point of the air, say
TD is known, the humidity will be the same as that at Q . Then the state of the system can be
anywhere on the horizontal line passing through Q . Though by specifying the dew point the
humidity is known, to define the state completely one more property need be specified in
addition to the dew point.
 Percent humidity
- 280 100 80 60 40 30 20 10 5 2
0.15 8000
t 0.14 6000

- 240 0.13 4000

0.12 3000 ft[

C /3 Adiabatic sa urauon curve ^ M
J 2000 a
P?
- 200 \ 0.11 c cr
air C/J \ 3 3 -
—
CD \
CL xs
dry ft C I « C~
Volume , dry air
0.10 *
5
m E
ft t
mVkg - 160 3
XT
ca I
aj
y) t c-- -- sE3
O

§! .
I

/
+ i. 1/
/
0.09 TO
3
1000
800
OQ
,
-
O -E / 0.08|
CL
ca
volume -o 120
E
ac
-pa
CD
CL
i

7
7 /
7
7 0.07 Io
600

400
3.

Humid
k
, o
.a; VO 80
CL

p:
H

A
f
/
/
m /
3 /
f
/
/
s
ft
0.06
0.05
^
OQ
CL

p
300

200
/ // /'
6 // 7 /
7 a
«3 0.04 -.
t

o 40
00
//
/
/ /
/ /
/
/

/
/
—
K
0.03
//
/ 0.02
Adiabatic saturation curve
o
-
J 0 0.01
Sa 3
0 20 30 40 30 60 70 80 90 100 110 120 130
&
a
Temperature, °C s
a,
£
S
Figure 8.1 Psychrometric chart for air- water vapour system at 1 std atmosphere . §1

S
a
212 Stoichiometry and Process Calculations

-BPa
a
c
X
Q H
P

*
^4 -s 1

Temperature
Figure 8.2 Construction of psychrometric chart.

EXAMPLE 8.10 The vapour pressure of ^ -hexane in kPa is given by

2697.55
In Ps = 13.8216 -
T - 48.78
Plot the 100%, 75%, 50% and 25% saturation lines for hexane in nitrogen at 100 kPa.
Solution At 100 kPa, the boiling point of hexane is given by the Antoine equation:
2697.55
In 100 = 13.8216 -
T - 48.78 => T = 341.47 K

%
The vapour pressures ( P ) are calculated at different temperatures ranging from 273 K to
341.47 K using the Antoine equation. The saturation humidity at each temperature is calculated
using Eq. (8.8):

Y'
'
-
P* ,- MA -
P*
x
8611
P-P ! MB P - P* 28
The results are tabulated below:

T (K ) 273 280 290 300 310 320 330 340 341.47

Pi (kPa) 5.99 8.63 13.99 21.84 32.95 48.21 68.67 95.46 100.0

v, kg hexane
0.196 0.290 0.500 0.859 1.511 2.863 6.741 64.664 oo
kg nitrogen

A graph is plotted with temperature on the x-axis and humidity Y on the y -axis. The
saturation humidity values at each temperature is marked and a smooth curve is drawn through
these points. This is the 100% saturation curve. The ordinate at each temperature is now
divided into 4 equal parts, representing 25%, 50% and 75% saturation humidity values. Joining
the 25% saturation humidity values by a smooth curve, the 25% saturation curve is established.
 Humidity and Humidity Chart 213

Similarly, the 50% and 75% curves are also drawn. The psychrometric chart so created is
shown in Figure 8.3.

100%

*
00
7
75%

x 5
00
4 f 50%
/

T3
3

25%

0
273 283 293 303 3 3 323 333
Temperature, K
Figure 8.3 Psychrometric chart for nitrogen- hexane system at 100 kPa (Example 8.10) .

EXAMPLE 8.11 An air-water vapour sample at 101.3 kPa has a dry -bulb temperature of 328
K and is 10% saturated with water vapour. Using the psychrometric chart determine the following:
(a) The absolute humidity, kg water vapour per kg dry air
(b) The partial pressure of water vapour
(c) The absolute saturation humidity at 328 K
(d ) The vapour pressure of water at 328 K
(e) The percent relative saturation
(f ) The dew point of the system
Solution
(a) Refer to Figure 8.4. Point P in the psychrometric chart corresponds to 328 K and 10%
saturation. The -coordinate of this point is read from the chart. This is the humidity
^
at this condition. This is equal to 0.012 kg water vapour/kg dry air. Y 7 = 0.012 kg water
per kg dry air.
(b) Partial pressure is calculated using Eq. (8.7) :

7' = — —— —x
P - pA 29
= 0.012
0.0193(P - pA ) = pA where P is 101.3 kPa. Solving this, we get pA = 1.921 kPa.
(c) The saturation humidity at 328 K is obtained directly from the psychrometric chart by
reading the .y-coordinate of point Q where point Q is the point on the 100% saturation
curve corresponding to temperature 328 K . This is found to be 0.115 kg water per kg
dry air. Y ' = 0.115 kg water per kg dry air.
214 Stoichiometry and Process Calculations

I1
0
0.12
/ 1 0.11
/ /
100%
/
/ 10%
/
/
0.10 • P
0.09
0.08
c3

OX)

/ / 0.07
£
3s!
/ / 0.06
/ / 0.05
OX)

/ / 0.04 ap
y/ /
R
\ a
y 0.03
s /

<
—
\
0.02
. ^
V
1
/ i
^ Adiabatic saturation curve
0.01
1 i

0 10 20 30 40 50 60
Temperature, °C
Figure 8.4 Solution of Examples 8.11, 8.12 and 8.13.

(d) Equation (8.8) can be used to calculate vapour pressure :

P* P°
Ys'
p- p
VMA -

pj
y.
lS
% MB p- 29

PSd
0.115 = —
101.3 - Pj
- x 0.6207

Solving this, we get Pj = 15.8 kPa.

( The vapour pressure at 328 K is found to be 15.7 kPa from steam tables, which
compares well with the value calculated above. )
(e) The percent relative saturation is obtained using Eq. (8.9):

RS = %
Pj
x 100% =
15.8
x 100% = 12.16%

(f ) The dew point is obtained by moving from point P horizontally to the saturation curve
and noting the temperature coordinate of point S. The dew point is found to be 290 K.
( The vapour pressure at the dew point should be equal to the partial pressure of water
in the air, which is obtained as 1.921 in part (b ). Using steam tables, the vapour
pressure at 290 K is found to be 1.93 kPa.)

8.4 HUMID HEAT

The heat capacity of the gas-vapour system at constant pressure is designated as the humid
heat ( Cs ). It is the amount of heat required to raise the temperature of one kg of dry gas and
 Humidity and Humidity Chart 215

the accompanying vapour by one degree. If the specific heat of the vapour is C (kJ/kg K) and
that of the dry gas is CB( kJ /kg K), then the humid heat is
^
cs = CB + Y' CA (8.14)
For the air-water vapour system , CA = 1.884 kJ/kg K and CB = 1.005 kJ/kg K . Knowing the
humid heat of the air-water system, the calculation of the heat requirement in operations such
as drying and humidification can be done easily as
Q = GSCSAT (8.15)
In Eq. (8.15) Q is the quantity of heat required for heating Gs kg of dry air and the
accompanying vapour by (A 7) K .

EXAMPLE 8.12 Determine the humid heat of the sample of air in Example 8.11, and
calculate the amount of heat to be supplied to heat 100 m 3 of the air to 373 K .
Solution The humid heat is calculated using Eq. (8.14) : Noting that CA = 1.884 kJ/kg K
and CB = 1.005 kJ/kg K,
Cs = 1.005 + 0.012 x 1.884 = 1.0276 kJ/kg K
PV 101.3 x 100
Number of moles in 100 m 3 of the air = ~
= 3.7147 kmol
RT 8.314 x 328

Number of moles of dry air in 100 m 3 = 3.7147 x —P = 3.7147 x 101.3

= 3.6443 kmol
Weight of dry air = 3.6443 x 29 = 105.68 kg
Heat to be supplied = GSCSAT = 105.68 x 1.0276 x (373 - 328) = 4887 kJ.

8.5 WET- BULB TEMPERATURE

A wet-bulb thermometer such as the one O'
r,w
shown schematically in Figure 8.5 can be
used to measure the humidity of air. The
temperature indicated by an ordinary
thermometer is the dry -bulb temperature
of the air. Temperature indicated by the
wet-bulb thermometer is called the wet- Humidity, Y'w
bulb temperature ( WBT ) . Wet - bulb Temperature, Tw
temperature is the steady -state temperature
attained by a small quantity of liquid
evaporating into a large quantity of
unsaturated gas stream . Let us see what
happens when an unsaturated air stream is
passed across an ordinary thermometer
Gas
Humidity, Y'
Temperature, TG
>
>
m
whose bulb is covered with a wet wick, Figure 8.5 Wet- bulb thermometer.
the end of which is immersed in water as
shown in Figure 8.5.
216 Stoichiometry and Process Calculations

The air film in contact with the bulb of the thermometer will be saturated with water
vapour which exerts a partial pressure equal to the vapour pressure of water. The partial
pressure of water vapour in the air passed across the thermometer is less than the vapour
pressure unless the air is saturated. This results in vaporization of water and diffusion of the
vapour into the air stream . Vaporization requires heat and the heat of vaporization is initially
supplied by the water film surrounding the bulb and consequently the water cools down
lowering the temperature indicated by the thermometer. When the temperature of the water
film falls, heat transfer occurs from the bulk of the air to the thermometer bulb. It means that
there are two opposing processes occurring in the system . One is the simultaneous transfer
of heat and mass to the air stream from the thermometer and the other is the transfer of sensible
heat from the air to the thermometer. Eventually a dynamic equilibrium will be established at
which the rate of sensible heat transfer towards the thermometer and the rate at which the latent
heat of vaporization is lost from the thermometer are equal. Under this condition, the thermometer
indicates a constant temperature that remains unaltered with further passage of air. The
temperature indicated under this steady -state condition is known as the wet-bulb temperature
of the air .
The difference between the dry -bulb and wet-bulb temperature is known as the wet-bulb
depression and is a measure of the humidity of the air stream . If the air were saturated, there
would not be any vaporization and consequent lowering of temperature ; the dry -bulb and wet-
bulb temperature would be the same and wet-bulb depression would be zero. The higher the
wet-bulb depression, the larger the degree of unsaturation of the air.
The wet-bulb temperature can be estimated by equating the rate of loss of latent heat of
vaporization and the rate of transfer of sensible heat. Though the derivation is beyond the scope
of this book, the mathematical equation for estimating the wet-bulb temperature is given below.
Let TG and 7' be the dry -bulb temperature and humidity of the air respectively. Let Tw be the
wet-bulb temperature of the air and 7 be the saturation humidity at the wet -bulb temperature.
Then ^
Tw TG V( V/ )n
( -
~ (8.16)
hG kY
or
Y' ~
1 - Y'
Lw -
( hG / kY )( TG Tw ) (8.17)

Xw = the latent heat of vaporization of water at the wet-bulb temperature , kJ/kg.

hG / kY = ratio of heat-transfer coefficient
to the mass transfer coefficient of air film , also
known as the psychrometric ratio, kJ/(kg dry air K) .
Equation (8.17) can be used to evaluate the humidity of air, given the wet -bulb temperature
and the dry -bulb temperature. The Lewis relation can be used to evaluate the psychrometric
ratio for use in Eq. (8.17). It states that for the air-water system the psychrometric ratio is
approximately equal to the humid heat ( Cs ) , the latter being easily evaluated using Eq. (8.14).
For any given wet-bulb temperature ( Tw), the air-water system can exist in different states each
being represented by a point on the humidity chart with a specific dry -bulb temperature (Ta )
and humidity (7') combination. These points with coordinates TG and 7' should satisfy Eq. (8.17)
and all these points can be marked on the humidity chart and joined by a smooth curve . This
curve is known as the wet-bulb temperature line or the psychrometric line .
 Humidity and Humidity Chart 217

In Figure 8.6, CE is a psychrometric line for the wet-bulb temperature Tc . Several such
lines are drawn on the psychrometric chart. The psychrometric lines facilitate the determination
of humidity of air from the knowledge of dry -bulb and wet-bulb temperatures. Strictly speaking,
these lines are neither straight nor parallel, but by slight modification of the coordinates, they
are rendered straight and parallel on the psychrometric charts . In this way the interpolation of
data is rather simple.

b
T3
E
3
X N

Tc T
*
u
Temperature
Figure 8.6 Determination of humidity using wet- bulb temperature .

To find the humidity and other properties of air, given the wet-bulb temperature and the
dry -bulb temperature Tw and TG , respectively, take the wet -bulb temperature on the temperature
axis and move vertically to the 100 percent saturation curve . Locate point N on the saturation
curve and move along the psychrometric line passing through N downwards to its intersection
(point M ) with the vertical line at the given dry -bulb temperature. This point (M ) determines
the state of the air-water system and the humidity and other properties corresponding to this
point can be read from the chart directly.

EXAMPLE 8.13 For the air-water vapour system of the conditions in Example 8.11, find
the wet-bulb temperature of air.
Solution Refer to Figure 8.4. Locate the psychrometric line passing through point P and
move along this line to the hundred percent saturation curve. Let point R represents the
intersection of the psychrometric line with the saturation curve. The temperature coordinate of
point R gives the wet-bulb temperature . From the chart, the wet-bulb temperature is found to
be 301 K.

EXAMPLE 8.14 Air at 101.3 kPa is blown across the bulb of a mercury thermometer. The
bulb is covered with a wick. The wick is immersed in an organic liquid (MW = 58) . The
reading of the thermometer is 280.8 K . At this temperature the vapour pressure of the liquid
is 5 kPa. Find the air temperature given that the psychrometric ratio is 2 kJ/kg K and the latent
218 Stoichiometry and Process Calculations

heat of vaporization of the liquid is 360 kJ/kg. Assume that the air which is blown is free from
the organic vapour.
Solution Equation (8.16) is used to evaluate the temperature, i.e.

^
„ 4 (v - n
LW - 1 G
(nhG / kY )
v

Wet-bulb temperature Tw = 280.8 K and = 5 kPa

vt _ Pw MA _ 5 58
29 =
X 0 1038 kg vaP ur/kg air
I ^ °
“

0 L3 5
Psychrometric ratio = hG/ kY = 2 kJ /kg K
Latent heat of vaporization = Xw = 360 kJ/kg.
Since the air is free of organic vapour, Y' = 0.
Substituting these values, Eq. (8.16 ) gives
r)
Ta = Tw +
~

( hG / kY )
= 280.8 +
360 X
°2 1038
'

= 299.48 K

EXAMPLE 8.15 An air-water vapour sample has a dry -bulb temperature of 353.2 K and a
wet-bulb temperature of 308 K. Compute the humidity of the sample given that the latent heat
of vaporization of water at 308 K is 2418.0 kJ/kg and the psychrometric ratio is 0.950 kJ/
kg K. Compare the result with the value read directly from the psychrometric chart. The
vapour pressure of water at 308 K is 5.62 kPa .
Solution From the psychrometric chart , the humidity is obtained directly. This is found
to be 0.018 kg water per kg dry air.
Equation (8.17) can be used to calculate the humidity.

v, ~
_v, ( hG / kr )( TG - Tw )
1 1W
Q
'V

Here, YJw =— — x L=
^ 5 62
^ ^
P - Pw MB 101.3 - 5.62 29
= 0.0365 kg water per kg dry air

(0.950)(353.2 - 308)
Y - 0.0365 -
A
= 0.0187 kg water per kg dry air
This compares well with the humidity obtained from the psychrometric chart .

8.6 ADIABATIC SATURATION TEMPERATURE

As we have seen, the wet-bulb temperature is the steady -state temperature attained by a small
quantity of liquid evaporating into a large quantity of unsaturated gas-vapour stream . The gas
 Humidity and Humidity Chart 219

is passed in such large quantities that its temperature and humidity are not changed by evaporation
of the liquid. Now consider the situation where the quantity of unsaturated gas mixture is small
in comparison with the liquid with which it is in contact. The temperature as well as the
humidity of the air changes during the process whereas the liquid temperature is maintained
constant at the equilibrium value by recirculation. Figure 8.7 shows an adiabatic humidification
chamber in which water is sprayed into the unsaturated air-water vapour mixture.
In a continuous operation, water attains the equilibrium temperature and this temperature
is maintained constant by recirculation. The loss of water by evaporation is compensated by
the addition of make-up water also at the equilibrium temperature . The chamber is assumed to
be sufficiently large for equilibrium to be established between the gas stream and the liquid.
The operation is adiabatic, that is, there is no addition to or removal of heat from the chamber.
Air
Temperature, TG
Air
Humidity, 7' Temperature, Tas
< ^ Humidity, Y'as
> <
<

* ;i
Water
Make- up water temperature, Tas
temperature, Tas
Figure 8.7 Adiabatic saturation chamber.

When an unsaturated air stream is brought into contact with water, the air gets humidified
and cooled. Humidification of the gas is achieved by the evaporation of water. Evaporation
requires heat of vaporization. Since the process is adiabatic and water temperature is maintained
at a constant value, the latent heat of vaporization is to be met by the sensible heat removed
from the air and as a result the air gets cooled. Humidification and cooling of the gas continue
till the equilibrium between water and the gas is reached. Under equilibrium , the temperature
of air and water will be equal and humidity of air will be the saturation humidity at the
equilibrium temperature. The equilibrium temperature attained by a gas-vapour mixture when
it is adiabatically humidified in contact with the liquid is known as the adiabatic saturation
temperature, Tas.
An energy balance over the system can be written by equating the heat given out by the
gas stream by cooling from its initial temperature TG to the adiabatic saturation temperature Tas
and the heat required for vaporization of water so that the humidity of the air stream increases
from its initial value T to the final value Y'as. The humidity is the saturation humidity at the
adiabatic saturation temperature Tas. Energy balance gives for one kg dry air circulated

Cs ( TG - Tas ) = (Y;s - Y' ) Xas (8.18)

where Xas is the latent heat of vaporization of water at the adiabatic saturation temperature and
Cs is the humid heat of the air. Equation (8.18) can be rearranged as
220 Stoichiometry and Process Calculations

. ,,
Tm Ta -

dry -bulb temperature TG and humidity Y' .

^ zH (8 9

Equation (8.19) gives the adiabatic saturation temperature of a gas-vapour mixture at the

On the humidity chart, Eq. (8.18) gives a family of curves known as the adiabatic saturation
curves or simply adiabatic cooling curves. The points on an adiabatic cooling line give the
temperature-humidity history of an unsaturated air subjected to adiabatic humidification. When
equilibrium is established, the temperature attained is the adiabatic saturation temperature and
the humidity attained is the saturation humidity at Tas. The adiabatic saturation temperature and
the saturation humidity attained on adiabatic humidification are given by the coordinates of the
point of intersection of the adiabatic cooling line with the hundred percent saturation curve . If
equilibrium is not attained as is usually the case with equipment of finite size, the air leaving
the chamber will be unsaturated and will be represented by a point on the cooling line below
the hundred percent saturation curve. Examination of Eqs. (8.19) and (8.16) reveals that the
adiabatic saturation temperature and the wet-bulb temperature will be identical if the
psychrometric ratio and the humid heat are equal . For the air-water system this is found to be
approximately true according to the Lewis relation. Consequently, the psychrometric lines and
adiabatic cooling lines for the air-water vapour system are identical . Thus the wet-bulb
temperature lines discussed in the previous section represent the humidity-temperature conditions
of air undergoing adiabatic saturation as well.

EXAMPLE 8, 16 The vapour pressure of benzene varies with temperature as

2788.51
In Ps = 13.8858 -
T - 52.36
The specific heat of benzene vapour may be taken as 1.2 kJ/kg K and that of dry air is 1.005
kJ/ kg K. The latent heat of vaporization of benzene at 283 K is 435.4 kJ/kg. Calculate and plot
(a) The saturation curve for the benzene-air system at 101.3 kPa for the temperature range
of 283 K to 313 K with temperature increments of 10 K
(b) The adiabatic cooling line for the adiabatic saturation temperature of 283 K
Solution
(a) The vapour pressures at different temperatures are calculated using the Antoine equation.
The saturation humidity values are determine at each temperature using Eq. (8.8):
,
YS Pl MA _ PSA
y
78 048
,

p - p* MB P - Pj 29
The results are tabulated as follows:

T( K) 283 293 303 313

Pj (kPa) 6.02 9.95 15.80 24.22

r, (kg benzene/kg dry air) 0.17 0.293 0.497 0.846

A graph is plotted with Y on the y-axis and temperature on the x-axis as shown in Figure 8.8.
 Humidity and Humidity Chart 221

0.9
0.8
Ut 100% saturation curve
‘
3 0.7
-o
00
0.6
0.5
§
04
-8ooo Adiabatic cooling line

0
273 283 293 303 313 323
Temperature , K
Figure 8.8 Solution to Example 8.16 .

(b) For each temperature, an adiabatic cooling line can be drawn using Eq. (8.19).
ys (Y'as - n
^ as ^ G -,
/

Here Cs = CB + TCA = 1.005 + 1.27' and Xas = 435.4 kJ/kg K . To draw the adiabatic
cooling line, for 283 K, put Tas = 283 K and Y'as 0.17 in Eq. (8.19) and find the sets
of TG and Y that satisfy the equation. To make the calculations simpler, assume Y' ( Y'
should be lower than Ya's ) and calculate TG that satisfies the equation. For example,
let us assume Y' = 0.15 kg benzene/kg dry air. Then

as + **
Ta° = r„ *
(
*" r> = 283 + 435
~ 4< 017 r > ~

Cs 1.005 1.27' +
435.4(0.17 - 0.15)
= 283 + = 29035 K
1.005 + 1.2 x 0.15
Now let Y' = 0.125, Y ' = 0.10 etc . and repeat the calculations. The results are tabulated
below :

TG (K ) 290.4 300 310.1 320.8

Y ' (kg benzene/kg dry air) 0.15 0.125 0.10 0.075

The above points are marked and a smooth curve is drawn joining these points as
shown in Figure 8.8, which gives the adiabatic cooling line for the adiabatic saturation
temperature of 283 K . The curve passes through (Tas, Y'as ) on the 100% saturation curve.
(These calculations can be repeated for Tas = 293 K, 303 K and 313 K .)

EXAMPLE 8.17 An adiabatic drier is used to dry a wet material . The drying air enters at
380.7 K and 101.3 kPa with a dew point of 298 K . Measurements show that 2.25 kg of water
is evaporated per 100 m 3 of wet inlet air. Calculate using psychrometric chart
222 Stoichiometry and Process Calculations

(a) The humidity of air entering the drier

(b) The exit air humidity and percent humidity
(c) The exit air wet-bulb and dry -bulb temperatures
(d) The volume of exit air per 100 m 3 of inlet wet air
Solution
(a) From the humidity chart, the humidity of air at dry -bulb temperature of 380.7 K and
dew point 298 K = 0.02 kg water/kg dry air.
(b) Basis: 100 m 3 of wet inlet air at 101.3 kPa and 380.7 K
100 273 15
Moles of air entering the drier = x = 3.2011 kmol
22.414 380.7
29
Molal humidity of entering air = 0.02 x —l o
= 0.0322 kmol water/kmol dry air

Moles of dry air entering the drier = 3.201 lx = 3.1012 kmol

1.0322

Weight of dry air in the entering air = 3.201 l x — —

- x 29 = 89.934 kg
1.0322
Mass of water present in the air entering the drier = 89.934 x 0.02 = 1.7987 kg
Mass of water in the air leaving the drier = 1.7987 + 2.25 = 4.0487 kg
4.0487
Exit air humidity = = 0.045 kg water/kg dry air
^
In the psychrometric chart, move along the adiabatic cooling line passing through the
point representing the condition of air entering the drier to the point where the humidity
is 0.045 kg water per kg dry air. The percent humidity at this condition is read from
the chart. It is equal to 55%.
(c) From the humidity chart, the exit air wet bulb temperature = 313.2 K, and the exit air
dry bulb temperature = 322.2 K.
(d) The molal humidity of air leaving the drier is
29
0.045 x —18
— = 0.0725 kmol water per kmol dry air
Since the number of kmoles of dry air entering the drier per 100 m 3 of air is equal to
3.1012 kmol, the number of kmoles of gas leaving the drier is
1.0725
3.1012 x = 3.3261 kmol
1
The volume of exit air (101.3 kPa, 322.2 K) is
322.2
3.3261 x 22.414 x = 87.92 m 3
273.2
 Humidity and Humidity Chart 223

8.7 HUMID VOLUME AND ENTHALPY

8.7.1 Humid Volume
The volume of one kg of dry gas and the accompanying vapour is known as the humid volume
of the vapour-gas mixture. Assuming the ideal gas law to be applicable to the gas-vapour
mixture, for the gas at the dry -bulb temperature TG , pressure P and having humidity 7', the
humid volume VH is calculated using

V = Vnx
0 —p x
T _
To
or
r i r \
101.325 TG
VH =
\
MB
+
MA y
x 22.414 x
P
x (
-— —
273.15
(8.20)

VH is the humid volume in m 3/kg dry air. MA and MB are the molecular weights of the vapour
and dry gas respectively. For the air-water vapour system , Eq. (8.20) gives
r 1 Y' \ T
VH = 8.314 29 18 x PG (8.21)
\ /

where P is in kPa and VH is in m 3/kg dry air. Given the humidity of air, the humid volume at
any temperature can be calculated using this equation. Equation (8.21) gives the specific volume
of dry air ( VD ) if we put 7' = 0 and the humid volume of saturated air ( Vs ) if we put 7' = 7',
the saturation humidity. The former varies linearly with temperature and can be represented by
a straight line on the humidity chart while the latter is shown as a curve that is slightly concave
upwards. For any given temperature , the specific volume of dry air and humid volume of
saturated air can be directly read from the chart, and the humid volume of air of known percent
humidity calculated using a linear interpolation as
PS
rH = vD + 100 ( K - V D ) (8.22)

8.7.2 Enthalpy of Humid Air

Enthalpy of dry air and the accompanying water vapour is determined with reference to an
arbitrarily chosen reference state. The reference temperature chosen for enthalpy calculation is
273.15 K at which water exists as saturated liquid . For the air-water vapour system with
humidity 7' and temperature TG , the enthalpy can be calculated as the heat required for bringing
one kg of dry air and 7' kg of liquid water from the initial temperature T0 to the final state at
TG at constant pressure. Thus the enthalpy of the air
H = CB( TG - T0 ) + T [ Xo + CA( TG - To ) ] (8.23)
where X 0 is the latent heat of vaporization of water at the reference temperature T0 . Using
Eq. (8.14) for the humid heat, Eq . (8.23) can be modified as
H= CS( TG - To ) + Y' Xo (8.24)
Equation (8.24) reveals that the enthalpy can be kept constant in a process where humidity is
increased and temperature is reduced, as is the case with adiabatic humidification operations.
224 Stoichiometry and Process Calculations

Put Y' = 0 in Eq. (8.23) and we get the enthalpy of dry air (HD) which is a linear function
of temperature. This is plotted as a straight line on the psychrometric chart. When Y ' = Y's ,
we get the enthalpy of saturated air (Hs) as a function of temperature . Saturated enthalpy curve
also is shown on the psychrometric chart. For air of known humidity, the enthalpy can be
calculated using Eq. (8.24) or can be obtained from the chart by interpolation as
PS
-
^ 100 H s H d
H =Hd + ( ) (8.25)

EXAMPLE 8.18 Air at 101.3 kPa has a dry -bulb temperature of 303 K and a wet-bulb
temperature of 288 K. It is desired to heat the air in a preheater and then spray water into it
adiabatically so that final air will be saturated at 303 K. Using the psychrometric chart, determine
(a) The humidity of the initial air
(b) The percent humidity of the initial air
(c) The temperature to which the air is to be heated in the preheater
(d) The heat to be supplied per kg of dry air
Solution The process is represented schematically in Figure 8.9.

o3

GO

*
5
”
18%

X
I
A B
0.0045 t

288 303 356.7

Temperature
Figure 8.9 Process in Example 8.18.

(a) The initial condition of air (DBT = 303 K and WBT = 288 K) is represented by point
A on the psychrometric chart. The humidity corresponding to this point is read from the
chart. Humidity Y\ = 0.0045 kg water/kg dry air.
( b) The percent humidity is found to be approximately 18% from the chart.
(c) The condition of air after heating the original air is represented by point B . Point B is
determined in such a way that the air at this condition has the adiabatic saturation
temperature of 303 K (the temperature attained by the air when water is sprayed into
it adiabatically ) and the humidity is the same as the original air. The temperature
corresponding to this point is 356.7 K.
 Humidity and Humidity Chart 225

(d) The humid heat of the original air is found by Eq. (8.14) :

Cs = CB + Y' CA = 1.005 + 0.0045 X 1.884 = 1.0135 AL

kg K
The heat requirement in the preheater to heat the air from 303 K to 356.7 K per
kilogram of dry air is obtained by Eq. (8.15):
Q= GSCSAT = 1 x 1.0135 x (356.7 - 303) = 54.43 kJ

EXAMPLE 8.19 The wet-bulb and dry -bulb temperature of air are 313 K and 333 K respec -
tively. Determine the following using psychrometric chart:
(a) The absolute humidity
(b) The percent humidity
(c) The humid volume
(d) The enthalpy of wet air
Solution

Specific volume
of saturated air .
‘
S 26.5%
1.18
-o 3
m /kg
"J
03
£ 0.94
00
3
Specitic volume m /kg
? 0.04 r A of dry air
B
3

313 333
Figure 8.10 Solution to Example 8.19 .

(a) Obtain point A on the humidity chart such that the psychrometric line at the WBT 313 K
intersects the vertical at the DBT 333 K at points. Refer Figure 8.10. The humidity
at point A is read from the chart and is equal to 0.04 kg water per kg dry air.
(b) The percent humidity at point A is 26.5% from the chart.
(c) At 333 K the volume of saturated air = 1.18 m 3/kg dry air ( Vs).
The volume of dry air at 333 K = 0.94 m 3/kg dry air ( VD ) .
By Eq. (8.22), humid volume is given by
PS
VH = VD + -(VH - Vd )
= 0.94 + 0.265(1.18 - 0.94) = 1.0036 m 3/kg dry air
[Note : Equation (8.21) can be used to calculate the humid volume, i.e.
226 Stoichiometry and Process Calculations

VH, - 8.314 h IP X
TG
129 18, P
Here, Y' = 0.04 kg water per kg dry air, TG = 333 K and P = 101.3 kPa. Substituting
the values, VH = 1.0032 m 3/kg dry air.]
(d) At 333 K the enthalpy of saturated air = 470 J/kg dry air (Hs) . The enthalpy of dry air
at 333 K = 60 kJ /kg dry air (//D).
By Eq. (8.25), the enthalpy of the wet air is
PS
H =HD (H, ~
Hd )
100
= 60 + 0.265(470 - 60) = 168.65 kJ/kg dry air
[ Note : Enthalpy of humid air can be calculated by Eq. (8.24), i.e.
H= CS( TG - T0 ) + Y %o
Cs = 1.005+ 0.04 x 1.884 = 1.08036 kJ/kg K; T0 = 273.15 K; X 0 = 2502.3 kJ/kg;
TG = 333 K; Y ' = 0.04 kg water per kg dry air. Substituting the values in Eq. (8.24),
we get H = 164.75 kJ /kg dry air.]

EXERCISES
Saturation
8.1 The vapour pressure of acetone at 285 K is 16.82 kPa . For a mixture of nitrogen gas
saturated with the vapours of acetone at 285 K and 101.3 kPa , calculate
(a) The mole percent of acetone in the mixture
(b) The percent composition by weight of acetone
(c) The mole ratio of acetone in the mixture
(d) The weight ratio of acetone in the mixture
(e) The amount of vapour in kilograms per m3 of the mixture
8.2 Carbon dioxide gas at 300 K and 100 kPa is saturated with water vapour. The vapour
pressure of water at 300 K is 3.56 kPa. Calculate
(a ) The mole percent of water vapour in the mixture
(b) The percent composition by weight
(c) The mole ratio of water vapour in the mixture
(d) The weight ratio of water vapour in the mixture
(e ) The amount of vapour in kilograms per m3 of the mixture
8.3 A gas holder contains dry nitrogen at 300 K and 101.3 kPa . Water is injected into the
vessel till the gas is saturated . If the temperature after saturation is 300 K and the
vapour pressure of water at 300 K is 3.56 kPa , calculate
(a ) The pressure inside the vessel
( b) The mole ratio of water to nitrogen in the saturated gas
 Humidity and Humidity Chart 227

8.4 A gas holder contains 1000 cubic metres of a gas saturated with water vapour at 300 K
and 105 kPa. The vapour pressure of water at 300 K is 3.56 kPa . How many kilograms
of water are present in the holder?
8.5 A certain exhaust gas consists of benzene vapour mixed with air. The partial pressure
of benzene vapour is 300 Pa at a total pressure of 107 kPa and 298 K . Does this
concentration exceed the ambient air quality stipulation of a maximum hydrocarbon
concentration of 1.60 x 10-7 kg/m 3?
8.6 What is the minimum volume (cubic metres) of dry air at 293 K and 100 kPa necessary
to evaporate 6 kg of ethyl alcohol if the total pressure remains constant at 100 kPa?
Assume that the air is blown through the alcohol to remove it in such a way that the
exit pressure of the air-alcohol mixture is 100 kPa . The vapour pressure of alcohol
(kPa) is given as
3578.91
In Ps = 16.5092 -
T - 50.50
8.7 Dry air at 295 K and 100 kPa is bubbled through benzene. If the saturated air leaves
at 300 K and 100 kPa, how many kilograms of benzene are evaporated per 100 m 3 of
entering air? The vapour pressure of benzene (kPa) is given by
2788.51
In Ps = 13.8858 -
T - 52.36
8.8 10 kg KC103 is decomposed and the oxygen evolved is collected over water at 300 K
and 100 kPa. Determine the weight of saturated oxygen obtained if the vapour pressure
of water at 300 K is 3.5 kPa .
8.9 Dry air is saturated with hexane vapours at 253 K and 101.3 kPa . The vapour pressure
of hexane at 253 K is 1.85 kPa. What is the percent excess air for combustion?
8.10 It is desired to prepare a saturated methanol vapour-air mixture containing 2% methanol
by bringing dry air in contact with methanol kept in a container at 100 kPa . What
temperature should be used to achieve the desired composition? The vapour pressure
of methanol is given by the Antoine equation
3626.25
In Ps = 16.5725 -
T - 34.29
8.11 Air at 303 K and 101.3 kPa is 60 percent saturated with water vapour. If it is desired
that 90 percent of water is to be removed by compression at constant temperature, what
should be the pressure to which it is compressed? The vapour pressure of water at
303 K is 4.24 kPa.

Humidity, percent humidity, dew point

8.12 A mixture containing benzene vapour and nitrogen in the weight ratio 0.1790:1 is found
to have a percent humidity of 40% at 101.325 kPa . What is its relative humidity ?
228 Stoichiometry and Process Calculations

8.13 A mixture of benzene vapour and nitrogen gas at 105 kPa and 330 K contains benzene
vapour to the extent that it exerts a partial pressure of 15 kPa. The vapour pressure
of benzene is given by the Antoine equation
2788.51
In Ps = 13.8858 -
T - 52.36
Determine the following:
(a) The mole fraction of benzene in the mixture
(b) The weight fraction of benzene in the mixture
(c) The molal humidity
(d) The absolute humidity
(e) The molal saturation humidity
(f ) The absolute saturation humidity
(g) The mass of benzene in 100 m3 of the mixture
(h) The percent humidity
(i) The percent relative humidity
8.14 A mixture of benzene vapour and air contains 10% benzene by volume at 300 K and
101.3 kPa. The vapour pressure of benzene at 300 K is 13.8 kPa. Calculate the following:
(a) The partial pressure of benzene in the mixture
(b) The weight fraction of benzene in the mixture
(c) The molal humidity
(d) The absolute humidity
(e) The percent saturation
(f ) The percent relative saturation
(g) The mass of air in 100 m 3 of the mixture
8.15 The percent saturation of a mixture of acetone vapour and nitrogen at 105 kPa and
300 K is found to be 80%. The vapour pressure (kPa) of acetone is given by the
Antoine equation with constants, A = 14.39155, B = 2795.817 and C = 43.198. Calculate
the following:
(a) The molal humidity
(b) The absolute humidity
(c) The partial pressure of acetone
(d) The relative saturation
(e) The dew point
8.16 Moist air contains 0.025 kg water vapour per cubic metre of the mixture at 313 K and
101.3 kPa. Calculate the following:
(a ) The partial pressure of water vapour
(b) The relative saturation
(c) The absolute humidity of the air
(d) The percent saturation
(e) The temperature to which the mixture be heated so that its percent saturation
becomes 10%
 Humidity and Humidity Chart 229

The vapour pressure of water (in kPa) is approximated by the Antoine equation as
3799.887
In P s = 16.26205 -
T - 46.854
8.17 Air at 288 K and 100 kPa contains 1 kg of water vapour. Water is completely removed
by adsorbing on silica gel. The dry air after adsorption measures 1000 m 3 at 108 kPa
and 293 K. What was the relative humidity of air before adsorption? The vapour
pressure of water at 288 K is 1.7 kPa .
8.18 The absolute humidity of a carbon dioxide-water vapour mixture at 310 K and 100 kPa
is measured to be 0.022 kg water per kg dry carbon dioxide. Calculate the following:
(a) The molal humidity
(b) The percent relative saturation
(c) The percent saturation
(d) The temperature to which the gas is to be heated at constant pressure to reduce its
percent saturation to 30 percent
The vapour pressure of water in kPa is approximated by the Antoine equation as
3799.887
In P s = 16.26205 -
T - 46.854
8.19 A fuel gas saturated with water vapour at 288 K and 101.3 kPa has a heating value
of 20000 kJ/m 3 of the total gas. What will be the heating value of the gas in kJ/m 3
of the gas at 295 K and 100 kPa if its relative saturation is only 50%? The vapour
pressure of water at 288 K and 295 K are respectively, 1.7 kPa and 2.6 kPa.
8.20 A mixture of acetone vapour and air contains 8.3% acetone by volume. Determine the
dew point of the mixture if
(a ) The temperature and pressure are 300 K and 100 kPa
( b) The temperature and pressure are 310 K and 90 kPa
The vapour pressure of acetone (kPa) is given by the Antoine equation with constants,
A = 14.39155, B = 2795.817 and C = 43.198.
8.21 The dew point of air at an atmospheric pressure of 101.3 kPa is 300 K. The vapour
pressure of water at 300 K is 3.56 kPa. Determine the mole fraction of water vapour
in the air.
8.22 If the dew point of air at 1.013 bar is 278 K, what will be the dew point at 10 bar?
The Antoine constants of water are A = 16.26205, B = 3799.887, C = 46.854.
8.23 Air at 298 K, 55% saturated with water vapour, is initially at 100 kPa . It is then
compressed to 1000 kPa and cooled to a temperature so that 90% of the water vapour
is condensed. Calculate the following :
(a) The final temperature of the air
(b) The volume of final air per cubic metre of original air
230 Stoichiometry and Process Calculations

The vapour pressure of water (kPa) is given by the Antoine equation as

3799.887
In Ps = 16.26205 -
T - 46.854
8.24 The dew point of a mixture of benzene vapour and dry air at 303 K and 100 kPa is
found to be 288 K. The vapour pressure of benzene at 288 K is 7.8 kPa and at 303 K
is 15.8 kPa. Determine the following:
(a ) The absolute humidity and molal absolute humidity of the mixture
(b) The composition of the mixture in volume percent and weight percent
(c) The relative saturation and the percent saturation
8.25 Methane is completely burned with air. After a portion of the water in the outlet gases
from the burner which contains no oxygen is removed by absorption, the gas is found
to contain 85% nitrogen at a temperature of 328 K and a pressure of 140 kPa . If more
water is to be removed by condensation, determine the following:
(a) The temperature to which this gas must be cooled at constant pressure
(b) The pressure to which the gas must be compressed at constant temperature
The vapour pressure of water in kPa is given by
3799.887
In Ps = 16.26205 -
T - 46.854
8.26 A hydrocarbon fuel is burned with dry air. Determine the dew point of the flue gases
at 533 K and 100 kPa if the dry flue gases analyzed 13.0% C02, 0.05% CO, 2.5%
02 and 84.45% N 2. The vapour pressure of water is given by the Antoine equation with
A = 16.26205, B = 3799.887 and C = 46.854 when pressure is in kPa and temperature
in K.
8.27 Determine the mass of 10 m 3 of air at 300 K and 115 kPa if the relative humidity is
65% and the vapour pressure of water at 300 K is 3.56 kPa .
8.28 In a process in which benzene is used as a solvent, it is evaporated into dry nitrogen.
The resulting mixture at a temperature of 300 K and a pressure of 101.3 kPa has a
relative humidity of 60%. It is required to recover 80% of the benzene present by
cooling to 283 K and compressing to a suitable pressure. The vapour pressure of
benzene at 283 K is 6.02 kPa and that at 300 K is 13.81 kPa . To what pressure should
the gas be compressed?
8.29 Hydrogen saturated with the vapours of water at 101.3 kPa and 305 K is passed
through a cooler in which the temperature of the gas is reduced to 280 K in order to
condense a part of the vapour. The gas leaving the cooler is heated to 293 K . Calculate
(a) The weight of water condensed per kg of moisture-free hydrogen
(b) The percent humidity of the gas in the final state
The vapour pressure of water (in kPa) may be estimated using the equation
3799.887
In Ps = 16.26205 -
T - 46.854
 Humidity and Humidity Chart 231

8.30 Air at 303 K, relative humidity 40% is mixed adiabatically with air at 313 K, relative
humidity 40% in the ratio of 1 kg of the former to 2 kg of the latter on a dry basis.
Find the final temperature and humidity of air. The vapour pressure of water (in kPa)
may be estimated using the equation
3799.887
In Ps = 16.26205 -
T - 46.854
8.31 One cubic metre of a gas at STP with a dew point of 293 K is to be dried to a dew
point of 278 K. How much water must be removed and what will be the volume of
the gas at STP after drying ? The vapour pressure of water is 0.872 kPa at 278 K and
2.337 kPa at 293 K.
8.32 Water is cooled by direct contact with ambient air in cooling towers. In a certain
cooling operation, air enters the tower at 300 K with a partial pressure of water vapour
of 670 Pa and leaves at 294 K with a partial pressure of water 2.2 kPa . The total
pressure is 100 kPa. Calculate the following:
(a) The relative humidity of air-water vapour at the inlet and exit of the tower
(b) The percent composition by volume at the inlet and exit of the tower
(c) The percent humidity of air at the inlet and exit of the tower
(d) The mass of water vapour in kilograms at the inlet and exit per 100 m 3 of dry air
entering the tower
(e) The mass of water vapour in kilograms at the inlet and exit per 100 m 3 of wet air
entering the tower.
The vapour pressure (in kPa) of water is given by
3799.887
In Ps = 16.26205 -
T - 46.854
8.33 A mixture of nitrogen and methanol has a dew point of 313 K. The temperature and
pressure of the mixture are 353 K and 200 kPa respectively. The vapour pressure of
methanol (kPa) is
3626.55
In Ps = 16.5725 -
T - 34.29
Calculate the following:
(a) The percent saturation of the mixture
(b) Kilograms of alcohol per kilogram nitrogen
(c) Kilograms of alcohol per m3 of mixture
(d) Dew point of the mixture if the total pressure were 100 kPa
(e ) Pressure required to condense 60% of the alcohol from the mixture at 300 K
8.34 A mixture of acetone vapour and nitrogen gas at 300 K has a dew point of 283 K . It
enters an evaporator where it picks up acetone vapour. The mixture leaving the evapo-
rator is at 298 K and has a dew point of 293 K. The pressure is kept constant at 100
kPa. Determine the following :
232 Stoichiometry and Process Calculations

(a ) The absolute humidity of the mixture entering and leaving the evaporator
( b) The mass of acetone in kilograms evaporated per kilogram of nitrogen entering the
evaporator
(c) The mass of acetone in kilograms evaporated per 100 m 3 of gas entering the
evaporator
(d ) The volume of gas leaving the evaporator per 100 m 3 of gas entering the unit
The vapour pressure of acetone at 283 K is 15.4 kPa and 24.5 kPa at 293 K.
8.35 A mixture of air and acetone vapour at 303 K and 100 kPa has a dew point of 298 K.
90 percent of acetone in the mixture is to be condensed and removed by cooling and
compression. If the mixture is cooled to 278 K, what should be the final pressure ? The
vapour pressure of acetone (kPa) may be estimated using the Antoine equation
2795.817
In P s = 14.39155 -
T - 43.198
8.36 Air supplied to a drier is at 340 K and 101.3 kPa and has a dew point of 278 K. The
air leaves the drier at 310 K and 100 kPa with a dew point of 298 K. At what rate (m 3
per hour measured at the drier inlet conditions) the air should be admitted to the drier
if it is desired that 100 kg of water is removed per hour? The vapour pressure of water
at 278 K is 0.87 kPa and at 298 K is 3.17 kPa .
8.37 Air at a rate of 25 m 3 per minute is supplied to a drier in which it removes moisture
at a rate of 0.45 kg per minute. The air enters the drier at 333 K and 101.3 kPa with
a percentage humidity of 10 and leaves at 310 K and 100 kPa. The vapour pressure of
water at 310 K = 6.3 kPa and at 333 K = 19.9 kPa .
(a) What is the percent humidity of air leaving the drier ?
( b) At what rate does air leave the drier in m3 per minute ?
8.38 The atmosphere in the afternoon during a humid period is at 313 K and is 70%
saturated. During the night the temperature falls to 303 K. The pressure is 101.3 kPa.
The vapour pressure of water at 303 K is 4.24 kPa and 7.38 kPa at 313 K . What
percent of water in the afternoon air is deposited as dew during the night.
8.39 A room of volume 100 m 3 is to be maintained at 300 K and 60% relative humidity. For
this fresh air from the outside saturated at 260 K is to be admitted to the room at such
a rate that the air is completely renewed each hour. The pressure is 100 kPa . The vapour
pressure of water is 3.56 kPa at 300 K and 0.199 kPa at 260 K . Calculate the weight
of water evaporated in one hour.
8.40 A mixture of air and water vapour has a relative humidity of 80% at 293 K and
100 kPa. It is then cooled and compressed to 283 K and 250 kPa. The vapour pressure
of water is 1.23 kPa at 283 K and 2.34 kPa at 293 K . Determine the following:
(a) Molal humidity of air at initial and final conditions
(b) Kilograms of water condensed per 100 m3 of initial wet air
( c ) Final volume of wet air per 100 m3 of initial air.
8.41 A gas mixture at 300 K and 100 kPa contains acetone vapour such that the percentage
saturation is 70%. The vapour pressure of acetone in kPa is given as
 Humidity and Humidity Chart 233

2795.817
In Ps - 14.39155 -
T - 43.198
If it is desired that 40% of the acetone is to be removed by condensation, to what
temperature the gas must be cooled at constant pressure?
8.42 A mixture of nitrogen gas and benzene vapour at 300 K and 100 kPa has a percent
saturation of 70%. It is desired that 80% of the benzene is to be removed by cooling
and compression. If the gas is cooled to 273 K, what should be the pressure to which
it is compressed? The vapour pressure of benzene at 273 K is 3.5 kPa and 13.8 kPa
at 300 K.
8.43 An acetone vapour-nitrogen gas mixture at 310 K and 101.3 kPa with a partial pressure
of acetone of 1.5 kPa is passed over a solution containing acetone as part of a solvent-
recovery operation. Acetone is to be recovered from the solution at a rate of 25 kg per
hour by evaporating into the gas stream. If the gas stream leaves the unit at 287 K and
100 kPa with a percent saturation of 85%, calculate the volumetric rate at which the
gas is admitted in m 3 per hour. The vapour pressure of acetone at 287 K is 8.86 kPa.

-
Wet bulb temperature and adiabatic saturation temperature
8.44 For an air-water vapour mixture with a dry -bulb temperature of 335 K and a wet-bulb
temperature of 308 K , determine the humidity of air at 101.3 kPa The latent heat
of vaporization of water at 308 K is 2419 kJ /kg and the psychrometric ratio is
0.950 kJ / kg K. The vapour pressure of water at 308 K is 5.62 kPa.
8.45 An air-water vapour sample has a dry -bulb temperature of 333 K and a wet-bulb
temperature of 313 K. Compute the humidity of the sample given that the latent heat
of vaporization of water at 313 K is 2407 kJ/kg and the psychrometric ratio is
0.950 kJ / kg K. Compare the result with the value read directly from the psychrometric
chart. The vapour pressure of water at 313 K is 7.37 kPa .
8.46 A mixture of air and benzene vapour containing 0.7 kg benzene per kg dry air is to be
cooled from 343 K to 288 K in a tubular cooler condenser. The specific heat of dry air
is 1.005 kJ/kg K and the specific heat of benzene vapour is 1.1 kJ/kg K. The vapour
pressure of benzene in kPa is given as
2788.51
In Ps = 13.8858 -
T - 52.36
The psychrometric ratio and the latent heat of vaporization of benzene in the range of
interest may be taken to be constant at 1.7 kJ/kg K and 250 kJ/kg, respectively. The
pressure is 101.3 kPa.
Determine the following:
(a ) The wet-bulb temperature of the inlet stream
( b) The humidity of the exit stream
( c ) The total amount of heat to be transferred per kg dry air
234 Stoichiometry and Process Calculations

8.47 The vapour pressure of benzene varies with temperature as

2788.51
In Ps = 13.8858 -
T - 52.36
The latent heat of vaporization of benzene at 293 K is 435.4 kJ/kg and the psychro-
metric ratio is 1.717 kJ /kg K. Calculate and plot the following:
(a) The saturation curve for the benzene-air system at 101.3 kPa for the temperature
range 283 K to 313 K with temperature increments of 10 K
(b) The psychrometric line for the wet-bulb temperature of 293 K
8.48 A toluene-air mixture at 330 K and 101.3 kPa contains 0.05 kg toluene vapour per kg
dry air. The Antoine equation for vapour pressure of toluene is
3096.52
In Ps (kPa) = 13.9987 -
T - 53.67
The specific heats of toluene vapour and air are, respectively, 1.256 kJ/kg K and 1.005 kJ/
kg K. Assume a constant value of 404 kJ/kg for the latent heat of vaporization of toluene.
(a) Estimate the adiabatic saturation temperature.
(b) If the psychrometric ratio for toluene-air system is 1.842 kJ/kg K, estimate the
wet-bulb temperature.
8.49 The vapour pressure and the latent heat of vaporization of carbon tetrachloride as
function of temperature is given below:

T (K ) 278 300 322 333 344 350

Ps (kPa) 5.6 16.4 39.3 57.3 84.7 101.3
X (kJ/kg) 215.7 206.3 197.5 193.1 188.6 186.4

The specific heat of dry air and that of CC14 vapour may be assumed constant. They
are respectively, 1.005 kJ /kg K and 0.942 kJ/kg K . For a pressure of 101.3 kPa,
calculate following:
(a) The adiabatic saturation temperature for dry air at 350 K
(b) The adiabatic saturation temperature for air at 350 K and having a humidity of
1.5 kg vapour per kg dry air.
8.50 The vapour pressure of chloroform (kPa) is given as
2696.79
In Ps - 13.9582 -
T - 46.16
Plot the 100%, 50% and 25% saturation curves for chloroform in air at 101.3 kPa.
Humidity chart
8.51 An air-water vapour sample at 101.3 kPa has a dry -bulb temperature of 333 K and an
absolute humidity of 0.01 kg water vapour per kg dry air. Using the psychrometric
chart, determine the following:
(a ) The percent saturation
 Humidity and Humidity Chart 235

( b) The partial pressure of water vapour

(c ) The absolute saturation humidity at 333 K
(d ) The vapour pressure of water at 333 K
(e ) The percent relative saturation
(f ) The dew point of the system
( g) The humid heat
(h) The wet-bulb temperature
8.52 The wet-bulb and dry -bulb temperature of air are 313 K and 333 K respectively.
Determine the following using the psychrometric chart:
(a) Absolute humidity
(b) Molal humidity
(c) The percent humidity
(d) The humid volume
(e) The dew point
(f ) The enthalpy of wet air
8.53 The dry -bulb temperature and the dew point of air are 343 K and 308 K respectively.
Estimate the following using the psychrometric chart:
(a) Absolute humidity
(b) Molal humidity
(c) The percent humidity
(d) The humid volume
(e) The wet-bulb temperature
(f ) The enthalpy of wet air
8.54 Moist air at 313 K and 50% saturation is heated to 362 K at a constant pressure of
101.3 kPa. Using the psychrometric chart, determine the heat added per cubic metre of
initial air.
8.55 An air stream at 101.3 kPa and 333 K is 25% saturated with water vapour. Determine
the humid volume and enthalpy of the air. If the air is adiabatically humidified to 70%
saturation, what will be its enthalpy in the final state ?
8.56 Air with a dry bulb temperature of 363 K and a wet-bulb temperature of 308 K is
passed over a wet material in a drier. The rate of evaporation is found to be 0.015 kg
water per kg dry air. Assuming the process to be adiabatic, calculate the following
using the psychrometric chart:
(a ) The absolute humidity, molal humidity and percent saturation of air entering the
drier.
( b) The dry -bulb temperature , the wet-bulb temperature, the absolute humidity and the
percent saturation of air leaving the drier.
8.57 The dry -bulb temperature and dew point of an air sample at 101.3 kPa are 328 K and
308 K respectively. Calculate the following using psychrometric chart:
(a ) The absolute humidity, molal humidity and percent saturation
( b) The partial pressure of water vapour and relative saturation
236 Stoichiometry and Process Calculations

( c ) The wet bulb temperature

(d) The humid heat, humid volume and total enthalpy
8.58 Construct a psychrometric chart for an acetone-air system in the temperature range
of 260 K to 330 K which includes the following details.
(a ) 25%, 50%, 75% and 100% saturation curves
(b) Specific volume of dry air and humid volume of saturated gas
(c) Enthalpy of dry and saturated gas in kJ/kg dry air referred to liquid acetone and
dry air at 260 K
(d ) Adiabatic cooling line for an adiabatic saturation temperature of 300 K
(e ) Psychrometric line for a wet-bulb temperature of 300 K
The vapour pressure (kPa) of acetone is given by the Antoine equation with constants,
A = 14.5463, B = 2940.46 and C = 49.19. The specific heat of acetone vapour and air
are 1.47 kJ/kg K and 1.005 kJ /kg K respectively. The latent heat of vaporization of
acetone at 300 K is 544 kJ/kg and the psychrometric ratio for air-acetone system is
1.7 kJ/kg K.
Adiabatic saturation in spray chambers
8.59 Air at 313 K dry -bulb temperature and 295 K wet-bulb temperature is admitted to a
spray chamber where water is sprayed into it adiabatically. If the exit air is at 300 K,
determine, using the psychrometric chart, the quantity of water added per kg dry air.
8.60 It is desired to maintain the temperature of air entering a building at 308 K and humidity
at 60%. This is achieved by humidifying air available at 305 K with 65% percent
humidity to saturation adiabatically in a spray chamber and by heating the gas leaving
the chamber to the desired final condition. Assume the pressure to be atmospheric.
Using the psychrometric chart, determine the following:
(a ) The temperature of air leaving the spray chamber
( b) The amount of water picked up by one kg dry air passing through the chamber.
8.61 Air at 303 K and with 75% saturation is to be prepared from a supply of warm summer
air at 310.7 K and 35% humidity. This is achieved by spraying water to the inlet air
and by heating the saturated air leaving the spray chamber to 303 K . Assume all the
operations are at atmospheric pressure . Using the psychrometric chart, determine the
following:
(a ) The temperature of the air leaving the chamber
( b) The amount of water evaporated per 1000 m3 of air entering the chamber
8.62 An air stream at 101.3 kPa and 333 K is 26.5% saturated with water vapour. It is sent
to a spray chamber where it is adiabatically humidified . The temperature of the air
leaving the chamber is 5 K above the adiabatic saturation temperature. Determine the
following:
(a) The absolute humidity of the initial air
( b) The wet-bulb temperature of the air
( c ) The dew point of the initial air
 Humidity and Humidity Chart 237

(d ) The percent saturation of the air leaving the spray chamber

(e) The humidity and temperature of the air leaving the chamber
(f ) The quantity of water picked up by 100 m 3 of wet air admitted to the chamber
8.63 Air at 101.3 kPa has a dry -bulb temperature of 303 K and a wet-bulb temperature of
293 K. It is desired to heat the air in a preheater and then spray water into it adiabatically
so that final air will be saturated at 308 K . Using the psychrometric chart, determine
the following:
(a ) The humidity of the initial air
(b) The percent humidity of the initial air
(c) The temperature to which the air is to be heated in the preheater
(d ) The heat to be supplied per kg of dry air.
8.64 Air is dehumidified by spraying into it water whose temperature is below the dew point
of the air. Air with a dew point of 294 K and a percent humidity of 40% enters a
dehumidifier and leaves at 287 K and with a dew point of 285 K . How much water is
removed per kg dry air? How much heat is removed per kg dry air ? Solve using
psychrometric chart.
8.65 10000 kg/h of air at 326 K and 20% humidity is to be produced from air at 301 K
and 20% humidity by first heating, then humidifying adiabatically to the desired humid-
ity and finally reheating the air to 326 K . The air leaves the adiabatic humidification
chamber with 95% saturation. Using the psychrometric chart, calculate the following:
(a) The temperature to which air is preheated
(b) The temperature of the air leaving the humidification chamber
( c ) The heat required in the preheater
(d ) The heat required in the preheater
8.66 Air with a dry -bulb temperature of 310 K and a wet-bulb temperature of 302.5 K is
passed into an evaporator. The air leaves the evaporator at 325 K with a wet-bulb
temperature of 320 K. The pressure is constant at 101.3 kPa . Calculate the following
using psychrometric charts:
(a ) The molal humidity, percent saturation and dew point of the initial air
( b) The molal humidity, percent saturation and the dew point of the final air
( c ) The amount of water evaporated per 100 m3 of wet air entering the evaporator
8.67 It is desired that the air entering a building be at 308 K and 30% saturated with water
vapour. This is achieved by passing air at 298 K and 30% saturated, through a series
of water sprays where it is cooled and saturated . The air emerging from the spray
chamber is then heated to 308 K. The water and air leave the chamber at the same
temperature. Using psychrometric chart, calculate the following:
(a) The temperature of water
(b) Humidity of air entering the building
( c ) The quantity of water condensed or evaporated in the spray chamber per kg
moisture free air.
238 Stoichiometry and Process Calculations

Adiabatic saturation in drying operations

8.68 A wet material containing 70% moisture is to be dried at a rate of 500 kg/h to 5%
moisture in a counter current drier, both moisture content being on a wet basis. The air
enters the drier at 333 K with a partial pressure of water of 1.0 kPa and leaves at 313 K
and 70% saturated. Calculate the air circulation rate in kg/h. The total pressure is
100 kPa and the vapour pressure of water at 313 K = 7.38 kPa.
8.69 A drier is to be designed for removing 100 kg/h of water from a wet material. The
following conditions are expected for the air:
Inlet: temperature = 340 K , pressure = 101.3 kPa, dew point = 278 K
Exit: temperature = 310 K, pressure = 100.0 kPa, dew point = 298 K
Vapour pressure of water = 0.872 kPa (278 K), 3.166 kPa (298 K)
At what rate air must be admitted (m 3/h) at the inlet conditions?
8.70 Air at 333 K and pressure of 100 kPa, 10% saturated with water vapour is sent to a
drier at a rate of 20,000 m 3/h where it picks up moisture from the solids at a rate of
25 kg/h. If the air leaves at 308 K and 98 kPa calculate the following:
(a) The percent saturation of the air leaving the drier
(b) The volume of air leaving the drier per hour
The vapour pressure of water is 5.62 kPa (308 K), 19.92 kPa (333 K).
8.71 A wet material is being dried by removing water at a rate of 100 kg in a drier. Water
evaporates into an air stream entering the drier at 350 K and 101.3 kPa with a dew point
of 278 K. The air leaves the drier at 308 K and 100 kPa with a relative humidity of
90%. The vapour pressure of water at 278 K and 308 K are respectively 0.87 and
5.62 kPa. Determine the following :
(a ) The rate at which air is admitted, m3/h
( b) The rate at which air leaves the drier, m3/h
8.72 Air at 365 K, 101.32 kPa and a dew point of 283 K is supplied to a drier which
operates adiabatically. Determine the following using psychrometric charts :
(a ) The minimum temperature to which the air gets cooled in the drier
(b) On the basis of 10 m 3 of air entering the drier, the maximum quantity of water
evaporated in the drier
( c ) The volume of air leaving the drier for the conditions in part (b)
8.73 Air enters a drier at 388 K, 101.3 kPa and with a dew point of 286 K. The drier
operates adiabatically. If the air leaves the drier saturated with water vapour, how many
kilograms of water will be evaporated per 100 m 3 of air entering? Solve using
psychrometric charts.
8.74 Air is supplied to a drier at a dry -bulb temperature of 305 K and a wet-bulb temperature
of 298 K. It is heated to 363 K before admitting to the drier. The drier is operated
adiabatically. Air leaves the drier fully saturated . Using the psychrometric chart, determine
the following:
 Humidity and Humidity Chart 239

(a ) The humidity, percent humidity and the dew point of the initial air
(b) The heat to be supplied in the heater per 100 m 3 of initial air
(c) Water evaporated per 100 m 3 of air entering the drier
(d ) The temperature of air leaving the drier
8.75 An adiabatic drier is used to dry paper. The drying air enters at 371 K and 101.3 kPa
with a dew point of 298 K. Measurements show that 2 kg of water is evaporated per
100 m 3 of wet inlet air. Calculate the following using psychrometric chart:
(a) The exit air wet-bulb and dry -bulb temperatures
(b) The exit air percent humidity
( c ) The volume of exit air per 100 m 3 of inlet wet air
8.76 A rotary drier operating at 101.3 kPa dries 500 kg/h of wet grain at 295 K from 10%
moisture to 1% moisture. Air-flowing counter current to the wet material enters at
380 K dry -bulb and 316 K wet-bulb temperature and leaves at 325 K dry -bulb temperature
saturated with water vapour. The grains leave the drier at 316 K and its specific heat
is 0.75 kJ/kg K. Using the psychrometric chart, determine the following:
(a) The humidity of the air entering and leaving the drier
(b) Water removed in kg/h
( c ) The heat input to the drier
8.77 Air, with a dry -bulb temperature of 311 K and a wet-bulb temperature of 300 K, is
scrubbed with water to remove dust. The water is maintained at 298 K . The air leaving
the scrubber is in equilibrium with water. It is then heated to 366 K in an air pre -heater
and admitted to an adiabatic rotary drier. The air leaves the drier at 322 K . The material
to be dried enters and leaves the drier at 319 K. The material losses moisture at a rate
of 0.05 kg of water per kg of product. The total product is 1000 kg/h. Using the
psychrometric chart, determine the following :
(a ) The humidity and percent humidity of the initial air, air after scrubbing, after
preheating and air leaving the drier
( b) The total weight of dry air used per hour
( c ) The total volume of air leaving the drier
8.78 Wet material is spread over trays stacked one above the other. Air containing 0.005 kg
water/ kg dry air is heated to 323 K and passed over the lower tray. It leaves the tray
at 60% humidity and is then reheated to 323 K and passed over the upper tray after
which the air leaves the drier. On the assumption that material on each tray has reached
the wet-bulb temperature and that heat losses from the drier can be neglected, determine
(a) The temperature of the material on the trays
(b) The amount of water removed in kg/h if 1000 m 3/h of moist air leaves the drier
(c) The temperature to which the air is to be preheated, if the final condition of air
is to be achieved in the first tray itself.
8.79 A laboratory drier produces 50 kg of dry solid containing 6 weight percent water from
a wet feed material containing 20.5% water. The drier operates adiabatically, with the
wet solid entering the drier at the wet-bulb temperature of the dryer air. A total of
240 Stoichiometry and Process Calculations

500 m 3/h of hot air at 365.7 K and 101.3 kPa with a dew point of 303.2 K is supplied
to the drier. Calculate the following:
(a) The temperature of the air leaving the drier
( b) The percent humidity of the air leaving the drier
8.80 Air at 101.3 kPa enters an adiabatic drier at 372 K with a dew point of 287 K and
leaves at 80% humidity. Wet paper enters the drier with 25% moisture and leaves with
5% moisture. Determine the following:
(a) The temperature of air leaving the drier
(b) Water evaporated in kilograms per 100 cubic metres of air entering
( c ) Kilograms of finished product per 100 cubic metres of air entering
8.81 It is required to evaporate 100 kg/h of water from a wet solid . The drying is carried
out in an adiabatic drier. Air is available at 101.3 kPa and 295 K at 70% humidity. Its
temperature is raised by passing through a preheater to such a value that that the air
leaving the drier is at 311.7 K and 90% saturated . Calculate the following:
(a ) The adiabatic saturation temperature of air leaving the drier
( b) The temperature of air leaving the preheater
( c ) The rate of circulation of moist air (kg/h)
(d ) The volume of moist air before preheating
 9 Material Balance in
Unit Operations

Material balance calculation is an essential part of the solution of many complex chemical
engineering problems. Material balance assists in the planning and design of processes, in the
economic evaluation of the proposed and existing processes, in process control, and in process
optimization. In chemical process industries, it is possible to produce a given end product from
different raw materials. For an appropriate choice of a process, it is very essential to compute
the material requirement for these different routes. A properly listed material balance enables one
to estimate the material requirement for an existing process or for a process which is being
planned. For instance, in the extraction of oil from oil seeds, it predicts the amount of solvent
required for treating a given quantity of seeds. It can evaluate the quantity of water to be
evaporated from an aqueous NaOH solution to produce a concentrated solution of given strength.
Such information can be used in the design of equipment, in the search for alternative processes
or in the evaluation of the economics of the process. Material balance can assist in the simulation
of processes based on which certain financial decisions can be made. For existing processes, if
direct measurements were made of the weight and compositions of various streams entering and
leaving a process, and of the change in material inventory in the system, no material balance
calculations would be necessary. As this is not always feasible, the calculation of unknown
quantities will always be necessary. Thus, material balance can be used in the hourly and daily
operating decisions to be made for running the process efficiently and economically.

9.1 BASIC MATERIAL BALANCE PRINCIPLES

Material balance is an expression of law of conservation of mass. The law of conservation of
mass states that the mass can neither be created nor destroyed, but may undergo phase
changes, i.e. transformation or transfer from one phase to another and also chemical changes.
In an industrial process, material balance provides an exact accounting of all the materials that
enter and leave and of the changes in the inventory of the material in the course of a given
interval of time of operation.
241
242 Stoichiometry and Process Calculations

The material balance for processes with or without chemical reaction can be written in the
following form :
material input material output ( material generation material consumption
to the system from the system ) \ within the system within the system
accumulation of material
(9.1)
within the system
Material balances can be written on mass basis or on mole basis.

9.1.1 Total and Component Balances

Total material balance refers to a balance written for the total mass involved in the process and
the component balance establishes the quantitative relationship between the individual chemical
compounds or atomic species involved in the process. When a total material balance is written
on mass basis, the generation and consumption terms are zero, whether chemical reaction
occurs or not. This is because, for all ordinary processes, the transformation of mass into
energy can be neglected and the law of conservation of mass is universally valid . The general
material balance equation reduces to
Input - Output = Accumulation (9.2)
Equation (9.2) is valid when the component balance is written on mass basis for any compound
whose quantity is not changed by chemical reaction. For substances undergoing chemical
transformation, the component mass balance should take into account the generation and
consumption terms in Eq. (9.1). For writing component balance for any chemical element,
Eq. (9.2) is applicable whether or not it has participated in the chemical reaction.
If mole basis is used, Eq. (9.2) is valid for writing the total material balance for processes
involving no chemical reaction. On the other hand, if chemical reaction occurs within the system,
the material balance equation [Eq . (9.2)] is not applicable on molar units either for total balance
or for component balances. The consumption and generation terms are to be taken into account,
and Eq. (9.1) would be the proper choice. However, Eq. (9.2) is still valid if the balance is written
for the atomic species. Applicability of material balance equations are summarised in Table 9.1.
Table 9.1 Choice of Material Balance Equation

Basis Material balance Chemical reaction Applicability of Eq. (9.2)

Mass basis ) Eq. (9.2) is applicable

Total material balance
Mole
Mass
basis j
basis )
^ Eq .
Eq .
(9.2)
(9.2)
is
is
applicable
applicable
Component balance
Mole basis j Without chemical reaction Eq . (9.2) is applicable
Mass basis ) Component balance for Eq . (9.2) is applicable
Mole basis j elements/atomic species , Eq . (9.2) is applicable
Mass basis ) Total material balance Eq . (9.2) is applicable
Mole basis j Not applicable . Use Eq . (9.1)
Mass basis ) Component balance Not applicable . Use Eq . (9.1)
Mole basis j With chemical reaction Not applicable . Use Eq . (9.1)
Mass basis ) Component balance for Eq. (9.2) is applicable
Mole basis ) elements/atomic species . Eq . (9.2) is applicable
 Material Balance in Unit Operations 243

With the chosen basis, write the overall material balance and the individual balances for the
components. For problems involving chemical reactions, it becomes necessary to develop
material balances based on chemical elements or radicals constituting the species that undergo
chemical transformation. However, for compounds or substances that are not decomposed,
altered or formed in the process, nothing is gained by writing material balance for the elements
present. For these substances and for problems involving no chemical reactions, material
balance can be established in terms of the chemical compounds or substances with distinct
characteristics and fixed compositions like the ash present in coal and the inert gangue present
in mineral ores. For problems involving no chemical reactions, the weight units such as the
kilograms can be used for calculations, whereas for problems involving chemical reactions,
molar units (mol or kmol) are preferred.

9.1 .2 Steady -state and Unsteady- state Processes

For material balance purposes, industrial processes may be classified as steady-state or
unsteady-state processes and as batch or continuous processes . A steady -state process is
one in which there is no change in conditions (pressure , temperature , composition) or rates
of flow with time at any given point in the system . All other processes are unsteady state
processes. (See Figure 9.1.)

Material balance
problems

i
Processes involving no Processes involving
chemical reactions chemical reactions

Steady-state Unsteady -state

i
Steady- state Unsteady -state

Figure 9.1 Classification of material balance problems.

One simple example of an unsteady -state process is differential distillation or simple

distillation. Refer to Figure 9.2.
A liquid mixture consisting of two or more components is slowly vaporized in a closed
container. The resulting vapour is condensed and stored in another tank . Because of the
difference in volatilities, the vapour will have a composition different from the liquid from
which it is produced. The liquid will become depleted in more volatile components as more and
more vapour is produced. The amount of the liquid remaining in the container as well as its
composition change with time. When the vapour is condensed and collected as distillate,
the quantity and composition of the distillate product in the receiver change continuously
with time.
244 Stoichiometry and Process Calculations

Condenser

Still Product (Distillate )

Heater

Residue
Figure 9.2 Simple distillation.

9.1 .3 Batch and Continuous Processes

In a batch process, a given quantity of material is placed in a container and a change is made
to occur by physical or chemical means. All batch processes are unsteady -state processes. In
contrast, in a continuous process, feed streams are continuously admitted into a piece of
equipment and the products are continuously withdrawn. For example , consider a continuous
nitration plant producing nitrobenzene. The reactant feed consists of benzene, nitric acid ,
sulphuric acid and water. The total mass of products obtained at the end of the nitration
reaction will be equal to the mass of the feed, although the proportion of various components
has changed as per chemical equilibrium. A continuous process may or may not be a steady -
state process. For continuous and steady -state process the accumulation of material is zero.
Then the material balance equation is
input = output (9.3)

9.1 .4 Tie Element

The tie element or key component is the material which enters and leaves the system in a single
stream or one which enters and leaves without any change. An element, compound or an
unreactive mass like the ash present in coal can be treated as a key component. Proper choice
of key components makes the calculation of the quantitative ratio of the two streams easier.
Consider, for example, absorption of ammonia from a mixture of air and ammonia by contacting
it with pure water as the solvent . Assume that 100 kmol of the gas mixture containing 10%
ammonia is treated to reduce the ammonia content to, say, 1%. The quantity of the final gas
leaving the absorber is easily obtained by taking ammonia-free air as the tie element . Since air
 Material Balance in Unit Operations 245

is insoluble in water, all the air in the entering stream , that is 90 kmol, should be present in
the exit gas as well. Since the air in the exit gas constitute 99.0% of the exit stream, the total
exit gas would be 90/0.99 = 90.91 kmol.
Though the solution of material balance problems are very much simplified through the use
of tie element concept, it is not always necessary that certain component be present as key
component for solving material balance problems. Also, in complex processes more than one
key component will be necessary for solution.

EXAMPLE 9.1 Coal contains 85% carbon and 15% ash. The cinder formed in the combustion
of coal contains 80% ash and 20% carbon. Determine the weight of cinder formed by the
combustion of 100 kg of coal and the percent of fuel value that is lost.
Solution Basis: 100 kg of coal (refer to Figure 9.3)
Air for combustion

Coal : 100 kg Flue gases

Carbon: 85% Coal burner (Products of
Ash: 15% Combustion)

Cinder: w kg
Carbon: 20%
Ash: 80%
Figure 9.3 Combustion of coal (Example 9.1) .

Ash enters the system in a single stream, that is, with the coal fired . It leaves the system
in a single stream without any change, with the cinder formed by the combustion. Therefore,
ash can be used as a key component for getting the quantity of cinder formed .
The weight of ash entering the system is

—
100
X 100 = 15 kg
Let w be the weight of cinder formed.
The weight of ash leaving is
80
wx kg
Too
Taking an ash balance, we get
\
15 = w x f 80 => w = 18.75 kg
,Too /
Hence, 18.75 kg cinder is formed by the combustion of 100 kg coal .
Since 20% of cinder is carbon, weight of carbon that is lost unbumed when 100 kg of
coal is charged is equal to (20/100) x 18.75 = 3.75 kg. As the coal originally contained 85 kg
of carbon, the percent fuel value that is lost in the cinder is
(3.75/85) x 100 = 4.41%
246 Stoichiometry and Process Calculations

9.1 .5 Basis for Calculation

In complex problems involving a number of different materials and quantities, the choice of a
basis is critical for simplifying the solution. Usually, a certain quantity of one of the pertinent
components is chosen as the basis. This may be the quantity of one of the streams entering
or leaving the process, the quantity of one of the active components entering or leaving the
process, or the quantity of one of the inert components entering or leaving the process. In
Example 9.1 we have used 100 kg of coal burned as the basis for calculation which was an
obvious choice for solving that problem . We could have used 100 kg of carbon in the coal as
the basis and obtained the same result as above; but the solution will not be that easy as the
one provided above. In many situations the statement of the problem makes the choice of the
basis quite obvious. Consider, for example , 1000 kg/h of 40% NaOH solution being concentrated
to 5% by evaporation. How much water is to be evaporated? The basis to be chosen is one
hour operation or 1000 kg/h feed to the evaporator.
Depending upon the choice of the basis, the final answer to the problem may require
multiplication of the values obtained by a scale factor. It is preferable to choose as basis a
quantity which gives the answer directly. But this may lead to more tedious calculations in some
situations. The following guidelines may be useful in selecting a basis.
(a) For streams which are mixtures of gases and whose analyses are given on volume
percent, the problem can be handled best by choosing 100 mol or kmol as a basis. Note
that the volume percent is equal to the mole percent for gases.
( b) For solid streams 100 kg or 1 mol (or 1 kmol) of a pure component solid can be
chosen as a basis. For solid streams containing substances like ash , gangue, inert cake,
etc. the weight basis should be used for computation. Liquid streams also can be
handled by choosing 100 kg or 1 mol as a basis.
( c ) If the problem demands answers as a time rate , as for example the production rate in
kg/h or the flow rate in cubic metres per hour, it would be convenient to make the
computation on the basis of the quantity of material flowing in unit time.
(d) In processes like drying and humidification operations, unit weight (or unit mole) of
dry gas (air) and the accompanying vapour will serve as a good basis for material
balance calculations.

EXAMPLE 9.2 Wood containing 40% moisture is dried to 5% moisture . What mass of water
in kilograms is evaporated per kg of dry wood?
Solution Basis: 1 kg of dry wood in the feed to the drier (Figure 9.4)
Water evaporated : w kg

Wood Dried wood

Dry wood: 60% (=1 kg ) Drier Dry wood : 95 % (=1 kg )
Moisture: 40% Moisture: 5 %
Figure 9.4 Drying of wood (Example 9.2) .
 Material Balance in Unit Operations 247

The entering material contains 40/60 = 2/3 kg water per kg dry wood and the leaving
material contains 5/95 kg water per kg dry wood . If w be the weight of water evaporated, then
water balance about the drier yields

lx —60 = w + 95
— => w= —60 - 95
— = 0.614 kg
The amount of water evaporated per kg dry wood is 0.614 kg.
If we were required to find the amount of water evaporated per kilogram of wet wood
entering the drier, the basis of 1 kg of dry wood could still be chosen for solving the problem .
Knowing that 1 kg of dry wood is associated with 100/60 kg of wet wood, the water
evaporated per kg of wet material is

0.614 x —
100
= 0.368 kg

EXAMPLE 9.3 The liquid effluent from a processing unit is discharged into a stream . The
flow rate and BOD of the stream before the discharge point are respectively 6 m 3/ s and
3 x 10-5 g/ L. The measurements made immediately below the discharge point indicated a BOD
of 5 x 10-3 g/L. If the plant discharges the effluents at a rate of 16 x 103 m 3/day, what is the
BOD of the effluent from the plant? (Note: Biochemical Oxygen Demand, BOD, is a measure
of the oxygen utilized by microorganisms during the oxidation of organic materials. BOD is a
direct measure of oxygen requirement and is directly proportional to the amount of organic
waste which has to be broken down.)
Solution Basis: One hour of operation (Figure 9.5)
Effluent
Flow: 16 x 103 m /day
3

BOD: ?

Upstream
Downstream
Flow : 6 m /s - 3
5 BOD: 5 x 10 g / L
BOD: 3 x 10 g /L
Figure 9.5 Effluent discharge (Example 9.3) .

The rate of discharge of effluent is

16 x 10
= 666.67 m 3/h (= 666.67 X 103 L/h)
24
Let x be the BOD expressed in g/L . Consider the BOD balance at the point where the
discharge from the plant joins the stream .
5
6 x 103 x 3600 x 3 x 10 "

+ 666.67 x 103x = (21600 + 666.67) x 103 x 5 x 10 “

3

Solving this we get x = 0.1660. Hence, the BOD of the effluents = 0.1660 g/L.
248 Stoichiometry and Process Calculations

9.1.6 Independent Material Balance Equations and Degrees of Freedom

The total material balance and the component balances provide a set of equations which can
be solved to determine the unknown quantities. Before attempting the solution, check whether
the number of unknowns and the number of equations formulated are equal. The number of
unknown quantities cannot exceed the number of independent material balance equations.
Otherwise, the problem is indeterminate . If the number of independent equations exceeds the
number of unknown quantities, the choice of the equations to be used for solving the problem
is left to one’s judgement. However, some guidelines will make this choice easy. If all the
analytical data used for formulating the balance equations are free from errors, it is immaterial
on which data we base our calculations. If the data are of doubtful accuracy, the equations
based on components that are present in larger proportions may be selected for solving the
problem .
The recognition of the maximum number of truly independent equations is important . Any
material balance equation that can be derived from other equations already written cannot be
regarded as an additional independent equation. For example, consider evaporation of water
from a 10% NaOH solution to concentrate the solution to say, 40% NaOH. Assuming F kg to
be the amount of solution admitted to the evaporator, w kg be the amount of water evaporated
and P kg be the amount of final concentrated solution obtained (Figure 9.6), the following
material balance equations can be written.
Vapour, w kg

Dilute Concentrated
solution *• Evaporator solution
(Feed ), F kg (Product), P kg

Figure 9.6 Evaporation operation .

Total material balance:

F = w + P (9.4)
NaOH balance:
OAF = OAP (9.5)
Water balance:
0.9F = w + 0.6P (9.6)
We can see that only two of the above three equations are independent, as one of them
is obtained by algebraic manipulation and combination of the other two. For example, Eq. (9.6)
is the resultant when Eq. (9.5) is subtracted from Eq. (9.4).
If two or more substances exist in a fixed ratio with respect to one another in each stream
where they appear, only one independent material balance equation may be written with respect
to these substances. Although a balance may be written for any one substance in question, it
is best to combine the substances appearing in constant ratio into a single entity and establish
a balance equation on this item . Before attempting a solution, we should be sure that the set
of equations has a unique solution.
 Material Balance in Unit Operations 249

Certain points regarding the number of independent equations may be noted . In general, for
processes involving no chemical reaction, the number of independent equations is equal to the
number of chemical compounds present, and for processes involving chemical reactions, the
number of independent equation is equal to the number of atomic species present. The difference
between the number of unknown variables and the number of equations is known as the
number of degrees of freedom . If the number of degrees of freedom is positive it means that
the number of variables is more than the number of equations, and we should try to get
additional equations or variable specifications to get a unique solution to the problem . If the
number of degrees of freedom is negative, we have too many equations than there are variables.
This may arise if we have overlooked to include some variables in the flow diagram . If the
number of degrees of freedom is zero, it means that the material balance problem is properly
specified, and we can proceed to solve the equations for evaluating the unknown variables.

EXAMPLE 9A In the azeotropic distillation of an ethanol-water solution, a feed mixture

containing 95.6% alcohol is mixed with pure benzene and distilled . The benzene forms a ternary
azeotrope with alcohol-water with a composition of 74.1% benzene , 7.4% water and 18.5%
alcohol, which is distilled over as the overhead product. Absolute alcohol is obtained as the
residue product. Determine the quantity of benzene required for producing 100 kg of absolute
alcohol.
Solution Let us first try to solve this problem by the direct and most obvious method,
i.e. by taking a basis of 100 kg of absolute alcohol product.
Basis: 100 kg of absolute alcohol
Let the feed be F kg of the mixture of 95.6% alcohol and pure benzene . The overhead product
is D kg and the bottom is W kg . Here W = 100 kg . Let the weight fractions of alcohol, water
and benzene in the feed be respectively wF a,, wFw and wF b.
> >

We can now formulate the balance equations. The overall material balance is
F = D + W => F = D + 100 (A)
Alcohol balance:
FwFa = 0.185D + W => FwFa = 0.185D + 100 (B)

Distillate, D kg
Benzene: 74.1%
£ Water: 7.4%
Alcohol: 18.5%

Feed, F kg
Ethanol-water
solution ( 95.6% *
Alcohol, 4.4% water )
+
Benzene

Residue, W kg
* (Absolute alcohol )
W = 100 kg
Figure 9.7 Distillation (Example 9.4) .
250 Stoichiometry and Process Calculations

Water balance:
FWFW = 0.074D (C)
Benzene balance:
FwFb = 0.741Z) (D )
Since the sum of the weight fractions is unity, we have
F,a .
+ WF w + WF,b = 1 (E )
Examination of Eqs. (A) through (E) reveals that not all of them are independent. Combining
together Eqs. (B) through (E) gives Eq. (A). Thus we have only four independent equations—
Eqs. (B) through (E)— in five unknown quantities. Since the feed is formed from 95.6%
alcohol, the weight fractions wFa and wFw are related as
WTJ 95 6
—
wF ,w
= —4.4 = 21.7273 =* wFa = 21.7273WFW ( F)

Since the weight fractions of alcohol and water in the feed are interrelated as given by Eq. (F),
the number of independent variables to be determined reduces to four. These four variables can
be determined by the solution of the four equations. Combining Eqs. (B), (C) and (F), we get
D = 70.28 kg. Using this in Eq. (D), the amount of benzene in the feed = FwFb = 52.08 kg.
The problem can be solved more easily by taking a basis of 100 kg of distillate.
Basis: 100 kg of overhead product
D = 100 kg. Choose water as the key component. Let x be the weight of 95.6% alcohol in
the feed. Then, water balance gives

—
100
x = 7.4 => x = 168.1818 kg

The amount of absolute alcohol is obtained from alcohol balance.

168.1818 x 0.956 = 18.5 + W
W = 168.1818 x 0.956 - 18.5 = 142.28 kg
When 142.28 kg of absolute alcohol is produced, benzene used is 74.1 kg. Therefore, for 100 kg
of absolute alcohol, benzene required is
/
74.1 ]
100 = 52.08 kg
v 142.28 j

9.1 .7 Steps for Solving Material Balance Problems

We can summarize the various points we made above into the following step-by -step procedure
for the solution of material balance problems.
1. Read the entire problem carefully.
2. Draw a sketch of the equipment/unit.
 Material Balance in Unit Operations 251

3. Label the flow of each stream and associated composition with symbols.
4. List all the available data on composition and stream flows in the picture. Calculate
additional compositions from the given data as necessary.
5. Establish the key component or tie element.
6. Select a suitable basis for calculation.
7. With the chosen basis, write the overall material balance and the individual balances for
the components.
8. Before attempting to solve, check whether the number of unknowns and the number
of equations formulated are equal. The number of unknown quantities cannot exceed
the number of independent material balance equations. Otherwise, the problem is
indeterminate. If the number of independent equations exceeds the number of unknown
quantities, the choice of the equations to be used for solving the problem is left to your
judgement.
9. Solve the equations.
10. Check the answers by substituting them , or at least some of them into the material
balances.

EXAMPLE 9.5 1000 kg of mixed acid of composition 40% H 2S04, 45% HN03 and 15% H20
is to be produced by strengthening waste acid of composition 30% H 2S04, 36% HN03 and
34% H20 by weight. Concentrated sulphuric acid of strength 95% and concentrated nitric acid
containing 80% acid are available for this purpose . How many kilograms of spent acid and
concentrated acids are to be mixed together?
Solution Let W kg of waste acid, S kg of concentrated sulphuric acid and N kg of
concentrated nitric acid are mixed together to produce M kg of mixed acid . The streams in
quantities and compositions are indicated in Figure 9.8.
Sulphuric acid , S kg Nitric acid , N kg
95% H 2S04 80 % HNO 3
5% H 20 20 % H,0

Waste acid , W kg Mixed acid , M kg

30% H 2S04 40 % H 2 S04
Mixing operation
36% HN03 45 % HNO3,
34% H 20 15 % H 20
Figure 9.8 Fortification of waste acid (Example 9.5) .

Basis: 1000 kg of mixed acid. M = 1000 kg.

—
We can write four material balance equations one total material balance , three component
balances, one each for H 2S04, HN03 and H20.
Total material balance:
W + S + N = 1000 (A)
H 2S04 balance :
0.3W + 0.95S = 0.4 x 1000 (B)
252 Stoichiometry and Process Calculations

HN03 balance:
036 W + 0.8A = 0.45 x 1000 (C)
H 20 balance:
034W = 0.05S + 020N = 0.15 x 1000 (D )
There are only three independent material balance equations as Eq. (D) can be obtained by
adding together Eqs. (B) and (C) and subtracting the sum from Eq . (A) . The number of
unknown quantities is three. They are W , S and N . Equations (A), (B) and (C) are solved
simultaneously to determine the quantities W , S and N . We get W = 70.22 kg, S = 398.88 kg,
N = 530.90 kg.
Quantities to be mixed are:
Waste acid = 70.22 kg
Concentrated H2S04 = 398.88 kg
Concentrated HN03 = 530.90 kg

9.2 MATERIAL BALANCE WITHOUT CHEMICAL REACTIONS

In chemical process industries, we employ a large number of chemical and physical operations
for transforming matter from inexpensive raw materials to highly desired products. The physical
operations are generally treated in chemical engineering parlance as unit operations . These
involve the addition or removal of some form of energy in the contacting, transport, and
conditioning of materials mainly by physical means. Unit operations in chemical engineering
practice can be broadly classified as fluid flow operations, heat transfer operations, mass
transfer operations and mechanical operations involving particle handling and conditioning. The
mass transfer operations include various separation techniques such as distillation, gas absorption,
liquid-liquid extraction, leaching, crystallization, adsorption, ion -exchange, humidification
operations, drying, etc. Also included in this category are several membrane separations such
as osmosis, reverse osmosis, dialysis, electrodialysis, etc. Mechanical operations include size
reduction operations, sedimentation, filtration, mixing and blending, centrifugation, etc.
Material balance calculations are very important in the design and analysis of various
separation operations. There is hardly any process industry which does not require a preliminary
treatment of the raw materials before they are taken to the reaction vessels. The products
leaving the reaction vessel require treatment for their purification, separation and for recovery
of by -products. Separation techniques are also employed to give definite properties to the
products, to render the products in a form suitable for packaging and handling and to reduce
the cost of transportation of the products. The material balance problems encountered in the
separation operations are discussed in this chapter as these operations are purely physical in
nature, and no chemical conversions are involved . Before we embark on the solution of the
material balance problems, we will briefly discuss the salient features of some of the important
separation methods which are quite in order for a better understanding of the material balance
systems. The present discussion is limited to the systems that are important from a material
balance point of view.
 Material Balance in Unit Operations 253

9.2.1 Evaporation
Evaporation is used in industries for concentrating aqueous solutions by vaporizing the solvent
water and removing it as vapour. Typical industrial applications of evaporation include
concentration of cane-sugar juice in a sugar factory, concentration of ammonium sulphate in
a fertilizer unit, and concentration of spent soap lye to produce glycerine in a soap industry.
Depending upon the mode of providing heat energy to the liquid being concentrated, evaporators
fall into different types. Evaporators heated by direct fire , evaporators with heating medium in
jackets and steam heated tubular evaporators are common in industries. Among the tubular
evaporators, short-tube vertical evaporators, long-tube evaporators, climbing film and falling
film evaporators, etc. are some industrially important ones in use. A schematic sketch of a
standard short-tube evaporator is shown in Figure 9.9.

>
Vapour, l\

©
©
>V

Feed , F

Steam

Condensate to
steam trap 4
Thick liquor, Lx
(Concentrated product )
Figure 9.9 Schematic sketch of a short-tube vertical evaporator.

The feed solution is admitted as shown. The solution flows up through the inside of the
tubes and is heated by steam condensing in the steam chest, outside the tubes. The heat
liberated by the condensing steam is transferred through the tubes to the liquid . The vapour
space of the evaporator is maintained at a lower pressure. When the temperature of the liquid
reaches the boiling point of the solution at this reduced pressure, the liquid boils. The vapour
generated is taken out through the vapour outlet which is condensed and discarded . The
concentrated solution known as thick liquor is withdrawn as product from the bottom of the
evaporator.
Let F be the feed rate in kg/h and xF be the mass fraction of the solute in the feed . Let
the thick liquor be withdrawn at a rate of Lx kg/h and the concentration of the solute in the
final product be xv Let V 1 be the quantity of vapour produced in kg/h. The overall material
balance can be written as
254 Stoichiometry and Process Calculations

F = Vx + Lx
Since the vapour produced is free of solute, the solute balance gives
FXF = Lxxx
Simultaneous solution of these two equations provide answer to the material balance problems
on single-effect evaporators.
In a single-effect evaporator, with one kilogram of steam condensing in the steam chest,
roughly only one kilogram of vapour is produced . The cost of steam consumption is therefore
the major cost of operation of the evaporator unit. To reduce the steam consumption, several
evaporators can be connected in series to form a multiple-effect evaporator system . The vapour
produced in the first effect is used as the heating medium in the second effect and the vapour
from the second is the heating medium for the third and so on. Thus by one kilogram of steam
condensing in the first effect, approximately N kilograms of vapour can be produced , where
N is the number of effects provided . A triple -effect forward -feed evaporator is shown in
Figure 9.10.
To vacuum system

v2 V3

I ITT
Feed , F kg
> )

Steam

Condensate
Thick liquor
L2 (Product ) , L3 kg

Figure 9.10 Forward-feed triple effect evaporator.

The overall material balance for a triple -effect evaporator is

F = V 1 + V 2 + V3 + L 3
where Vh V 2, and V 3 are the amounts of vapour produced in the first, second and third effect
respectively, in kg/h, and L 3 is the product rate in kg/h. Let xh x2, and x3 be the concentration
of the liquid leaving each effect. The solute balance for the combined system is
FXF = L 3X 3
The following solute balance equations can be written for each effect .

FXF = Llxl
L\X\ = L2x2
= L3X 3
^ 2X 2
 Material Balance in Unit Operations 255

The total material balance for individual effects are

F = Vi + Li
L\ = V 2 + L2
L2 = V 3 + L 3

EXAMPLE 9.6 A triple effect evaporator (Figure 9.11) is used to concentrate 1000 kg of
aqueous solution from a concentration of 20% solute to 80% solute. Assuming an equal amount
of vaporization in each effect, calculate the composition and weight of the solution entering the
second and third effects.

Vapour Vapour Vapour

V 4
V V

1000 kg feed . I II III

Aqueous — -> -
*
solution , 20 %
solute 4- 4- 4- Steam

A u
>
Final
solution , L 3,
Condensate Condensate Condensate 80 % solute
Figure 9.11 Triple effect evaporator for Example 9.6 .

Solution Basis: 1000 kg feed to the first effect

Let Lh L2 and L3 be the rate at which the concentrated solution is leaving each effect, xh
x2 and x3 respectively be the concentrations of solute in these effects. Let V be the amount of
vapour produced in each effect. Consider the combined system consisting of all the three
effects. The total material balance yields
1000 = 3V + L3 (A)
The solute balance is
1000 x 0.2 = L3X 3
200 = 0.8L 3 (B)
Solving Eqs. (A) and (B), we get L 3 = 250 kg and V = 250 kg.
Now we can write the material balance equation for the first effect.
Total balance:
1000 = Lx + V= Lx + 250 (C)
Solute balance:
1000 x 0.2 = L 1x 1 (D )
From Eq. (C), Lx = 750 kg. Substituting this in Eq. (D), we get xx = 0.2667 .
256 Stoichiometry and Process Calculations

For the second effect, the corresponding equations are

Li = L2 + V => 750 = L2 + 250 ( E)
Lpci = L2X 2 => 750 x 0.2667 = L 2x 2 ( F)
From Eqs. (E) and (F), we get L2 = 500 kg and x2 = 0.4.
The results of material balance calculation for the triple -effect evaporator system are summarized
as follows:

Effect Feed (kg ) Products (kg) Liquid concentration (% )

Liquid Vapour Feed product
I 1000 750 250 20 26.67
II 750 500 250 26.67 40
III 500 250 250 40 80

9.2.2 Crystallization
Crystallization is the process in which solid particles are formed from liquid solution by
evaporating and/or cooling of a saturated solution. Crystallization is important as a separation
and purification technique as well as a means of marketing materials in crystalline form . Tank
crystallizers, agitated batch crystallizers, Swenson-Walker crystallizer, vacuum crystallizers and
Krystal crystallizers are typical industrial equipment used for crystallization. Figure 9.12 shows
a crystallizer of the circulating liquid type. The liquid is drawn through the tubes of a steam

Vapour to
the condenser ^

Feed

Steam / / /// / / /
/ / // / / / /
// / / / / / /
// s/ / / / / /
// / / / / / / /
// / / / // / /
/ / / / //// / / / //// / /
'J / / / / / / / / ' / // / / / / /
/ / /// / / /.
ta / / // / / / / . '
/// / / / //
// / / / ///

=
f / / / / / / / / / / / // // /
<L> / / / / / / / / / s/ /// / / /
// //// / / / /// / / / /
' / // / / / / / .
' /// / / ///
/// / / / //
/ / / / ////,
'
'////////
/ / / / / / / /
/ / / / / / / /
/ / / / // / /
/ / /// / / / ..
/ /// / / / /4
/// / / / // / / / / / / / /*
/ Ac
/
/ / /
//
// // r
/\
< / / /
// /
S / / / S\( / / / ‘ZW
l'
T sf ^.
/ / / / / /
\ / / / / r y / / */
ii

/-
>^v
/ / / // / / / /
/ / /y/yv / /
/

c
Crystals and
mother liquor
Figure 9.12 Evaporator crystallizer.
 Material Balance in Unit Operations 257

heated exchanger where it is heated to sufficiently high temperatures without evaporation. The
heated liquid then flows into the vapour space where flash evaporation occurs leading to the
supersaturation of the solution. The supersaturated liquid is made to flow down through the
downcomer and then up through the bed of crystals which grows in size . The saturated liquid
leaving the bed joins the fresh feed solution before entering the heater.
Crystallization occurs when the solution is concentrated and usually cooled until the solute
concentration becomes greater than its solubility at that temperature. Equilibrium is said to be
attained when the solution is saturated.
In general, in industrial crystallization processes, equilibrium is attained between the solution
(mother liquor) and the crystals, and hence the mother liquor leaving the process is a saturated
solution at the final temperature of crystallization. The yield of crystals can be calculated
knowing the initial concentration of the solute , final temperature and the solubility at this
temperature. The material balance calculations are straightforward when the solute crystals are
anhydrous. Simple water and solute balances are sufficient. When the crystals are hydrated,
some of the water in the solution is removed with the crystals as a hydrate.
Let Wi kg of hydrated crystals are formed in which the weight fraction of solute is xx
from F kg of solution containing xF weight fraction of solute. Let x2 be the solubility of the
solute in weight fraction of solute, and W 2 and W 3 be the weights of mother liquor remaining
after crystallization and the weight of water evaporated during crystallization operation (see
Figure 9.13), respectively.
W 3 kg water
evaporated

F kg solution
Evaporator- Wl kg hydrated
(Feed ), weight of crystals, x 1 weight
cum -crystallizer
fraction of solute fraction

W 2 kg mother liquor,
x, weight fraction of
solute
Figure 9.13 Crystallization operation .

The material balance for the crystallization operation yield the following equations:
Total balance:
F= Wx + W2 + W3
Solute balance:
FXF = Wlx1 + W 2x 2
Solvent balance:
F( 1 - xF ) = Wx( 1 - xj) + W 2( 1 - x2 ) + W3
258 Stoichiometry and Process Calculations

EXAMPLE 9.7 A crystallizer is charged with 100 kg of a solution containing 25% Ba(N03) 2
in water. On cooling 10% of the original water present evaporates. Calculate the yield of crystals
when the solution is cooled to 283 K. The solubility at 283 K is 7.0 kg Ba (N03) 2/100 kg total
water.
Solution Basis: 100 kg of feed solution
Let W 1 be the weight of crystals, F the weight of feed, and xF weight fraction of solute
in the feed. Let x2 be the solubility of the solute in weight fraction of solute , and W 2 and W 3
be the weights of mother liquor remaining after crystallisation and the weight of water evaporated
during crystallization operation (see Figure 9.14).
7.5 kg water
evaporated

100 kg solution,
Evaporator- Wl kg crystals, xx
0.25 weight > weight fraction
cum -crystallizer
fraction Ba(N03)2 Ba (N03)2

IV 2 kg mother liquor,
0.0654 weight
fraction Ba(N03)2
Figure 9.14 Crystallization operation in Example 9.7 .

F = 100 kg, Xp = 0.25, x2 = 7/107 = 0.0654, W 3 = 0.75 x 100 x 0.1 = 7.5 kg

Total material balance
F = W 1 + W 2 + W3
That is, 100 = Wx + W 2 + 7.5 Wx + W 2 = 92.5 (A)
Solute balance
FXF = W 1 x 1 + W 2 x2
100 x 0.25 = W 1 x 1.0 + W 2 x 0.0654 => Wx + 0.0654 JT2 = 25
(B)
Solving Eqs. (A) and (B) simultaneously, we get W 1 = 20.28 kg.

EXAMPLE 9.8 An aqueous solution of Na 2C03 contains 15% carbonate by weight. 80% of
the carbonate is recovered as Na 2CO310H 2O by evaporation of water and subsequent cooling
to 278 K. The solubility of Na 2C03 at 278 K is 9.0% (weight) . On the basis of 100 kg of
solution treated, determine the following :
(a ) The quantity of crystals formed
( b) The amount of water evaporated
 Material Balance in Unit Operations 259

Solution Basis: 100 kg solution treated

See Figure 9.13. Let W 1 be the weight of hydrated crystals, xx the weight fraction of
Na2C03 in the crystals, F the weight of feed and xF the weight fraction of Na 2C03 in the feed.
Let x2 be the solubility of Na2C03 in weight fraction Na2C03, and W 2 and W3 be the weights
of mother liquor remaining after crystallization and the weight of water evaporated during
crystallization operation.
Total material balance:
F = Wx + W 2 + W 3 (A)
Na2C03 balance:
FXF = Wlx 1 + W 2x 2 (B)
Here F = 100 kg, xF = 0.15, the molecular weight of Na 2C03 = 106 and the molecular
weight of Na 2CO310H 2O = 286.
(a) The weight fraction of Na 2C03 in the crystals is
106
Xi = 286 = 0.3706
The mass of Na2C03 recovered in the crystals is
Wxxx = 0.8FXF = 0.8 x 100 x 0.15 = 12 kg
Therefore, the quantity of crystals formed is
12
wx = 0.3706 = 32.28 kg
(b) Substituting the values in Eq. (B). we get,
100 X 0.15 = 12 + W 2x 2
The mass of Na 2C03 in the mother liquor is
W 2x 2 = 15 - 12 = 3 kg
The weight fraction of Na 2C03 in the mother liquor = x2 = 0.09 (from solubility )
The weight of mother liquor is

X2
—x3 = 0.09
2
3 100
= 3 kg t

From Eq. (A), we get

W 3 = F - ( WX + W 2 )
= 100 - (32.38 + 33.33) = 34.29 kg
Hence, the amount of water evaporated = 34.29 kg

EXAMPLE 9.9 An aqueous solution containing 60% Na 2S203 and 1% soluble impurities is
diluted with water and fed to a crystallizer where it is cooled in order to crystallize Na 2S203 5 H20.
The crystals carry 0.05 kg of solution (excluding impurities) per kg of crystals . The free
water present in the adhering solution is removed on drying the crystals. The final dried
260 Stoichiometry and Process Calculations

product contains not more than 0.1% impurity. The solubility of the pentahydrate is 1.5 kg
Na 2S203 5 H20/ kg free water. On the basis of 100 kg of 60% solution, calculate the following:
(a) The amount of water in kilograms added before cooling
( b) The amount of crystals formed
( c ) The percentage recovery of the Na 2S203 in the dried hydrated crystals
Solution Basis: 100 kg 60% solution
Refer to Figure 9.15. Let W kg pure water is added to the original solution. Wh W 2 and
W 3 are the weights of Na 2S203- 5 H20 crystallized, the mother liquor obtained and the solution
carried away by the crystals, respectively. The impurities present in the feed get dissolved in
the free water and is present in the products in association with W 2 kg mother liquor and W 3
kg adhering solution. When the crystals are dried, the impurities in the adhering solution gets
deposited on the crystals, the concentration of which in the final dried crystals being limited
to 0.1%.

Wx kg Na 2S2035H20
crystals, xx weight
100 kg solution Evaporator-
(Feed ), 0.6 weight fraction Na 2S 203
cum -cry stall izer
fraction solute >• W 3 kg solution
adhering to crystals
W kg water
^ f

W 2 kg mother liquor,
x2 weight fraction solute
Figure 9.15 Crystallization operation in Example 9.9 .

The molecular weight of Na 2S203 = 158 and the molecular weight of Na 2S203- 5 H20 = 248.
Since no water is lost by evaporation, all the free water present in the combined feed will be
248
present in the mother liquor. 60 kg of anhydrous salt forms 60 x
= 94.117 kg of pentahydrate,
158
the free water present in the system is 100 + W - 1 - 94.177 = W + 4.823 kg. Therefore,
1
the concentration of impurity in the mother liquor is xx = W + 4.823 kg of impurity /kg of free

water. Now consider the material balance over the crystallizer.

Total (impurities-free) balance:
1 0 0 - 1 + W = W 1 + W 2 + W3
That is, W 1 + W2 + W3 - W = 99 (A)
Na2S203 balance:
r 1.5 1.5\ 158
60 = W1 + W2 x + W3 x X
v Z5 Z 5 / 248
which simplifies as
Wx + 0.6W 2 + 0.6 JV3 = 94.177 (B)
 Material Balance in Unit Operations 261

Since each kilogram of crystals carry 0.05 kg solution, W3 = 0.05 IF). Substituting this in Eqs.
(A) and ( B), we get
+ w2 - W = 99 (C)
1.05
^
1.03 IF) + 0.6 W 2 = 94.177 (D )
Impurity in the adhering solution is
1 1
W3 x x kg
2.5 If + 4.823
Substituting W 3 = 0.05 IF), the amount of impurity in the adhering solution is
0.05Wx
g
2.5 QV + 4.823)
However, this should not be more than 0.1% of the final weight of crystals. The final weight
of impurity -free crystals is

ffr + W, —2.5 = W + 0.05IF, —2.5 = 1.03^

*

Therefore,
weight of impurities in the crystals _
weight of pure crystals ^
_ 0.050 / 2.5(W + 4.823) _ 0.0194
"

^ 1.030)
~

W + 4.823
Solving the above equation, we get W = 14.577 kg . Substituting this in Eq. (C), we get
1.05Wx + W 2 = 113.577 ( E)
Solving Eqs. (D) and (E), we get Wx = 65.08 kg, W2 = 45.25 kg and, W3 = 0.05 = 45.25 kg
(a) The amount of water added before cooling = 14.58 kg. ^
( b) The amount of Na 2S203- 5 H20 crystals formed = 65.08 kg
( c ) Na 2S203 in the adhering solution gets deposited on the crystals on drying. Therefore,
total anhydrous Na2S203 produced
158 1.5 158 ^
Wx x 248 h W3 x = 42.701 g
Trr
x
2.5 248
42.70
The percentage recovery of Na 2S203 = x 100 = 71.2%

9.2.3 Leaching
Leaching is the separation of the components of a solid mixture by selectively dissolving the
soluble components of the solid in a liquid solvent . Recovery of minerals from naturally
occurring ores, oils from oilseeds, tannin from wood barks, vitamins and pharmaceutical
products from plant leaves and roots, sugar from sugar beets, etc. are some of the industrial
262 Stoichiometry and Process Calculations

applications of leaching. A Bollman extractor (Figure 9.16) is a typical industrial unit used for
leaching oil from seeds.
Solids are moved in perforated baskets attached to a chain conveyor. As the solids move
downwards, solvent (half miscella) moves in parallel flow. The perforations on the basket
permit passage of liquid from basket to basket. The strong solution of oil (full miscella) collects
at the bottom and is removed . The leaching is completed when the solids move upward
countercurrent to the fresh solvent which is admitted at the top as shown in the figure.
Consider a leaching operation such as the recovery of oil from oilseeds by treating with
an organic solvent like hexane. Let C be the component that is being transferred from the solid
phase to the liquid phase. The inert insoluble components in the feed is denoted as B . A is the
solvent used for leaching . In the present example, A is hexane, B is insoluble materials in the
feed , and C is oil . The streams entering and leaving a leaching unit are shown in
Figure 9.17. After the solute has been transferred into the liquid, the mixture is allowed to settle.
On settling, a clear solution known as overflow (R) containing the solute C dissolved in the
solvent and an underflow which is a slurry of leached solids B suspended in the solution (E )
that is not removed as overflow are obtained .
Fresh solvent ( o'
Feed

Half
miscella

LAJ

•••
....
....

.. .. -•

Hopper for
..... leached solids
Conveyor
r >
Basket
. .. >
o
Chain conveyor
for baskets
uom Pump

© Full miscella
Figure 9.16 Bollman extractor.

Feed is a mixture of B kg inert solids and F kg solute. S is the mass of solvent added.
The overflow is R kg solution consisting of A and C. Underflow is B kg inert solids suspended
 Material Balance in Unit Operations 263

in E kg clear solution. Concentration of inert material in any stream can be represented as

weight ratio of B on 5-free basis and is denoted by N . Concentration of solute is represented
as the weight ratio of solute on £-free basis , x represents solute concentration in overflow
solution and y represents solute concentration in underflow solution. Thus, x and .y are calculated
as the ratio of C to ( A + C) in a mixture and N is calculated as the ratio of B to ( A + C) in
the mixture. For the leaching system shown in Figure 9.17, we can write the inert balance as
B = NfF = NE
where NF and N are the inert concentration in the feed and underflow on an inert-free basis.
The solution ( A + Q balance can be written as
F + S = E+R

Feed: Overflow:
F kg solute C R kg solution ( A + C)
B kg inerts B x
» Ab-
Leaching unit

Underflow ( leached
solvent: solids):
S kg ( A + C ) E kg solution ( A + C)
ys B kg inerts B
y, N
Figure 9.17 Streams in a leaching operation .

The component-C (solute) balance is

FyP + Sys = Ey + Rx

EXAMPLE 9.10 A tannery extracts certain wood barks which contains 40% tannin, 5%
moisture, 23% soluble non-tannin materials and the rest insoluble lignin. The residue removed
from the extraction tanks contain 50% water, 3% tannin and 1% soluble non-tannin materials.
What percent of the original tannin remains unextracted?
Solution Basis: 100 kg of bark
The feed to the leaching unit contains 100 - 40 - 5 - 23 = 32 kg of lignin. Since lignin
is insoluble in the solvent used for leaching, all this will be present in the residue. Therefore,
lignin can be treated as the key component for material balance. Let the residue left after the
leaching operation be W kg. The weight percent of lignin in the residue = 100 - 50 - 3 - 1
= 46%. Take a balance on the key component lignin:
32 = W x 0.46
which gives
32
W=
0.46
= 69.57 kg
264 Stoichiometry and Process Calculations

Since the residue contains 3% unextracted tannin, the percentage of the tannin in the bark that
is unextracted is
69.57 x 0.03
x 100 = 5.2% .
100 x 0.40

EXAMPLE 9.11 Oilseeds containing 49% oils, 40% pulp, 3% mineral salts and the rest
moisture are leached with hexane as the solvent. The underflow from the leaching operation
contains 25% hexane, 2.5% salts, 15% oil and 7.5% moisture. The overflow contains 25% oil
which is distilled to recover the entire hexane in pure form leaving behind the oil, water and
salt. The underflow is subjected to steam distillation which recovers 95% hexane. For treating
100 kg seeds, calculate the following:
(a ) The kilograms of hexane used
( b) The percent of hexane used that is recovered from the underflow
( c ) Percent recovery of oil
Solution Basis: 100 kg oil seeds charged to the leaching unit

Feed: 100 kg Overflow:

R kg solution

Leaching unit

Underflow ( leached
Solvent hexane: /
S kg
^ solids):
U kg (solids + solution )
Figure 9.18 Streams in a leaching operation .

See Figure 9.18. Let S be the kilograms of hexane used for leaching. The underflow from
the operation contains all the insoluble pulp present in the feed in addition to the unextracted
oil, salt and moisture. Hexane dissolves some oil, salt and moisture . A portion of this solution
is adhering with the insoluble solids in the underflow and let U be the combined weight of the
underflow solids and solution adhering to it. The other portion forms the clear solution ( R ).
(a) Total balance:
100 + S = U + R (A)
The feed contains 49 kg of oil, oil concentration in the underflow is 15% and that in
the overflow is 25%. Hence, the oil balance :
49 = U x 0.15 + R x 0.25 (B)
The feed contains 40 kg of pulp. The percentage of pulp in the underflow is 100 -
25 - 15 - 2.5 - 7.5 = 50%. Therefore , the inert balance :
40 = 0.5U (C)
The insoluble pulp is the tie element in this problem as it is entering in a single stream
and leaves as a single stream. The inert balance [Eq. (C)] gives
U = 80 kg
 Material Balance in Unit Operations 265

Substituting U = 80 kg in Eq. (B), we get

R = 148 kg
Substituting U and R in Eq. (A), we get S = 128 kg. Thus the amount of solvent used
for extraction = 1 2 8 kg.
( b) The hexane in the underflow = 0.25U = 20 kg. The amount of hexane recovered by
steam distillation is 0.95 x 20 = 19 kg. This constitutes only

—
128
X 100 = 14.84%

( c ) Oil recovered in the clear solution is

—49 X 100 = 75.51%

9.2.4 Adsorption
Components of a gas or liquid mixture can be adsorbed on the surface of a solid adsorbent.
Two types of adsorption phenomena exist: physical adsorption occurring due to the intermolecular
forces and chemisorption occurring due to the chemical interaction between the solid and the
fluid. Physical adsorption is utilized as a separation method . The solid used for adsorption is
known as adsorbent, and the fluid adsorbed on the surface is the adsorbate . The adsorption
of organic vapours on activated charcoal, decolourization of cane-sugar solution by adsorbing
the colouring matter on activated carbon, drying of gases by adsorbing water on silica gel, etc.
are examples to cite a few. The adsorbed constituent can be removed from the solid and
thereby separation can be completed and the adsorbent regenerated for further use . Fuller ’s
earth, activated clays, activated charcoal, bone char, bauxite , alumina , silica gel, etc . are some
important adsorbents. Adsorption of a fluid on the surface of a solid occurs till equilibrium is
attained. The adsorption equilibrium is a relationship between the concentration of solute in the
fluid and the quantity adsorbed per unit weight of adsorbent. This relationship for a constant
temperature is known as adsorption isotherm.

9.2.5 Drying
Drying is usually one of the last operations in a process industry. Drying operation is unavoidable
and an integral part of the process in industries such as paper industries, whereas it is done
in other processes to reduce the cost of transportation of the product, to give some useful
properties to the product like the free flowing nature of salt, and to prepare the product in a
form that is suitable for handling and use. In drying, a wet solid or slurry is contacted with
dry gas (usually air or flue gas) so that water is vaporized from the solid and is carried away
by the gas. When the vapour pressure exerted by the moisture in the solid equals the partial
pressure of water in the gas exposed to the solid, the solid is said to have attained its
equilibrium moisture content, and drying stops. Depending upon the characteristics of the solid
being dried, several types of driers are in common use. Tray driers (for pasty materials and
lumpy solids), rotary driers (for granular and free flowing solids), freeze driers (for foodstuffs
266 Stoichiometry and Process Calculations

and pharmaceuticals) and spray driers (for slurries and pastes) are typical driers in use . The
continuous driers are smaller in size in relation to the quantity being dried, and the dried product
has a uniform moisture content. A rotary continuous drier is shown in Figure 9.19 and a general
flow diagram is shown in Figure 9.20.
Drier shell
Feed Air heater
Air outlet Drive gear

Steam
4
inlet
k
I&2C5) Steam
condensate
Discharge
fan Dry solids
discharge
Figure 9.19 Counter-current direct heated rotary drier.

Q, heat added
or lost
Solid feed , Ss kg / h,
X ] kg water /kg dry solid
Solid discharge, Ss kg /h,
X2 kg water / kg dry solid
Air in , Gs kg/h dry air,
,
F kg water /kg dry air
Drier
Air in, Gs kg /h dry air,
Y2 kg water / kg dry air

Figure 9.20 Continuous counter-current drying.

The drier is a long cylinder installed at a slight inclination with the floor to facilitate the free
flow of the material to be dried that is introduced at one end . The cylinder is made to rotate
at a very low speed. The drying gas, which may be hot air or dry flue gas is admitted at the
other end, flows counter current to the solid, the gas being pulled through the drier by means
of exhaust fans.
Let Ss kg/h be the mass flow rate of dry solid in the wet material admitted to the drier and
let it be dried from an initial moisture content of Xx to a final moisture content of X 2 , the
moisture content being expressed as kilograms of moisture per kilogram of dry solid . The gas
flow rate is Gs kilograms of dry gas per hour and it receives the moisture evaporated from the
solid . The humidity of the gas stream increases from Y 2 to Yx kg moisture per kilogram of dry
gas. A moisture balance on the drier yields
S&i ~ X2) = Gs( Yl - Y2)
 Material Balance in Unit Operations 267

EXAMPLE 9.12 A drier is fed with wet solid to reduce the moisture content from 80% to
15%. The product leaving the drier is admitted into an oven which further brings down the
moisture to 2%. If the drier can handle 1000 kg of wet solid per day, calculate
(a) The weight of products leaving the drier and the oven per day
( b) The percentage of the original water that is removed in the drier and the oven
Solution Basis: 1000 kg of wet solid admitted to the drier
Let V 1 kg and V 2 kg be the amount of water removed in the drier and the oven respectively.
Let xx and x2 be the weight fraction of moisture in the solid leaving the drier and the oven
respectively. Let F be the amount of wet material fed to the drier and xF be the moisture content
in the feed. The total material balance for the drier is
Water evaporated, Water evaporated,
V\ kg /h F2 kg /h

Dry solid , Sl
,
kg /h , x =
Product, S2
Wet solid, 0.15
F = 1000 kg/h , Drier Oven kg / h, x2 =
xF = 0.80 0.02

Figure 9.21 Drying operation in Example 9.12 .

F = Sl + Vl (A)
The corresponding moisture-free solid balance is
F(1 - xF ) = Sx { \ - *0 (B)
Similarly for the oven we can write
Si = S2 + V 2 (C)
Si ( l - x 0 = S2( 1 - x2 ) (D )
Here, F = 1000 kg, xF = 0.80, xx = 0.15 and x2 = 0.02. Equations (B) and (D) are balances
— —
for the tie element moisture free solid and substituting the given values, they give Sx =
235.29 kg and S2 = 204.08 kg.
Substituting the value of Sx in Eq. (A), we get V 1 = 764.71 kg.
Substituting the values of Sx and S2 in Eq. (C), we get V2 = 31.21 kg.
(a) The weight of products leaving the drier = Sx = 235.29 kg.
The weight of products leaving the oven = S2 = 204.08 kg.
( b) The percentage of original water that is removed in the drier is

- B- x 100 = 764 71 X 100 = 95.6%

FXF 800
The percentage of original water that is removed in the oven is
v 3 i ?1
-2- x 100 =
FXF 800
^
—
x 100 = 3.90%
268 Stoichiometry and Process Calculations

EXAMPLE 9.13 Air at 101.3 kPa enters an adiabatic drier at 87.5°C with a dew point of
20°C and leaves at 70% humidity. Wet paper enters the drier with 25% moisture and leaves
with 5% moisture. Determine the following:
(a) Water evaporated in kilograms per 100 cubic metres of air entering
( b) Finished product in kilograms per 100 cubic metres of air entering.
Solution The operation is schematically represented as shown in Figure 9.22.
The drying air enters with a dry -bulb temperature of 87.5°C and a dew point of 20°C.
From the humidity charts for the air-water system at 101.3 kPa, we can see that these
conditions correspond to a humidity of 0.015 kg water/kg dry air (72) . In an adiabatic drier,
air absorbs moisture from the wet solid, and the humidity and temperature of the air change
along the adiabatic cooling line passing through the point on the psychrometric chart that
represents the condition of the inlet air. By moving along the adiabatic cooling line to 70%
saturation, we see that the final humidity of the drying air (7 is 0.035 kg water/kg dry air.
Solid feed, Ss kg/ h,
^
Solid discharge, Ss kg / h,
Xl = 0.333 kg water/kg dry solid X2 = 0.0526 kg water /kg dry

>
- <
Air out, Gs kg/h dry air, Drier Air in, Gs kg / h dry air,
7j = 0.035 kg water /kg dry air Y2 = 0.015 kg
water/ kg dry air

Figure 9.22 Drying in Example 9.13.

Since the amount of dry solid present in the product stream remains the same as that in
the feed stream, and the amount of dry air present in the gas stream also remains constant,
it is better to do the material balance on a dry basis. Let Ss kg/h be the mass flow rate of dry
solid in the wet material admitted to the drier and it is dried from an initial moisture content
of X 1 to a final moisture content of X 2 on a dry basis.
25
Xj = —75 = 0.333 kg water/kg dry solid

v _ 5
A 2 = 0.0526 kg water/kg dry solid
Basis: 1 kg of dry air passed through the drier
The moisture balance for the drier is
SsXx + 72 = SsX 2 + 7!

Ss (X, - X2) = ,
Y - Y2 => S5
XI
-Y
= YI - X2
2

0.035 - 0.015
'
= 0.0713 kg of dry solid
0.333 - 0.0526
That is, with 1 kg of dry air and accompanying water, the moisture associated with 0.0713 kg
of dry solid can be reduced by the desired extent.
 Material Balance in Unit Operations 269

(a) 100 m 3 air enters the drier at 101.3 kPa and 87.5°C (360.65 K).
Moles of wet air entering the drier is
100 101.3 273.15
X X
22.414 101.325 360.65
= 3.3782 kmol
Moisture content in the air admitted = 0.015 kg water/kg dry air, i.e.
0.015 29
1
x
18
—
= 0.0242 kmol water/kmol dry air
Moles of dry air present in 100 m 3 of air admitted is

3.3782 x = 3.2984 kmol

1 + 0.0242
Mass of dry air is 3.2984 x 29 = 95.65 kg
Since the moisture content of the air increases from 0.015 kg water/kg dry air to
0.035 kg water per kg dry air, the total moisture evaporated is
95.65(0.035 - 0.015) = 1.913 kg
( b) Since 1 kg of dry air is needed for treating 0.0713 kg of dry solids, 95.65 kg of dry
air can treat 0.0713 x 95.65 = 6.82 kg of dry solid . Since the product contains 0.0526
kg of moisture per kg of dry solid, the quantity of finished product is
1.0526
6.82 x = 7.18 kg
I
9.2.6 Liquid-Liquid Extraction
The process of separation of the components of a liquid mixture by treating with an immiscible
liquid solvent in which the constituents are differently soluble is known as liquid liquid extraction .
-

The liquid-liquid extraction operation involves bringing the feed liquid in intimate contact with
an immiscible or partially miscible solvent, allowing the solute to get distributed between the
phases and finally allowing the phases to separate from each other. The resulting solvent-rich
phase is called the extract and the residual solution from which the solute is extracted is known
as the raffinate . The mutually insoluble extract and raffinate phases are then separated from
one another by settling and gravity separation. For example , aqueous acetic acid solution is
mixed with isopropyl ether solvent in order to extract the acid into the ether phase. A single -
stage extraction operation may be represented as shown in Figure 9.23.

Feed, F kg/h Extract, E kg / h

y , weight fraction C
xF , weight fraction C

Solvent, S kg/h Raffinate, R kg/ h

ys, weight fraction C x, weight fraction C
Figure 9.23 Extraction operation.
270 Stoichiometry and Process Calculations

Consider a simple case in liquid-liquid extraction in which solute C to be extracted is

present in the feed in association with solvent A . A solvent B is used for extraction of C from
the feed. B is either insoluble in A or is partially miscible with A . When the solvent is contacted
with the feed, the solute gets transferred to the solvent. The products leaving the extraction
unit are an A -rich phase known as raffinate and a #-rich phase known as extract. The solute
C will be present in the raffinate and extract phases. If A and B are partially miscible, traces
of B will be present in the raffinate and traces of A will be present in the extract. In a most
general extraction operation, therefore, we have to deal with ternary mixtures as raffinate and
extract phases. Denoting the weight fraction of solute in the raffinate and extract phases by
x and y respectively, that in the feed and solvent by xF and ys respectively, and the mass flow
rates of feed, solvent, raffinate and extract phases by F , S, R and E respectively, the total
material balance and component-C balance can be written as
F + S = E + R
FXF + Sys = Ey + Rx
Gravity settlers, mixer-settler cascades, sieve -tray columns, packed columns, spray towers,
rotating-disk contactors, etc. are the common types of extraction equipment. Figure 9.24
shows a rotating-disk extractor schematically.
For good mass transfer rates, one liquid should be thoroughly dispersed in the other and
the liquid dispersion is facilitated in rotating-disk contactors by mechanical means. The mechanical
agitation is provided by high-speed rotating disks.
Variable speed drive

* *£9
Light liquid outlet

a 9

Heavy liquid inlet ilrriO

Rotor disk

Stator ring

Light liquid inlet

3 Heavy liquid outlet

Figure 9.24 Rotating-disk contactor.
 Material Balance in Unit Operations 271

EXAMPLE 9.14 Isopropyl alcohol and water can be separated by extraction with ethylene
tetrachloride (C 2C14). 100 kg of a solution containing 30% (weight) isopropyl alcohol and the
rest water is mixed with the solvent ethylene tetrachloride. After extraction, the raffinate phase
analyzed 71% water, 28.1% isopropyl alcohol and 0.9% ethylene tetrachloride. The extract
phase analyzed 94% ethylene tetrachloride, 5.2% isopropyl alcohol and the rest water. Calculate
the following:
(a) The amount of solvent
( b) The quantities of raffinate and extract phases
( c ) The percent extraction of isopropyl alcohol
Solution Basis: 100 kg of feed
The extraction operation is schematically represented in Figure 9.25.

Feed, 100 kg Extract, E kg

(30% Isopropyl (94% ethylene tetrachloride,
alcohol, 70% water ) 5.2 % isopropyl alcohol,
0.8% water )

Solvent, S kg Raffinate, R kg
(Ethylene (71% water,
tetrachloride ) 28.1 % isopropyl alcohol,
0.9% ethylene tetrachloride )
Figure 9.25 Extraction operation in Example 9.14 .

Let R kg be the amount of raffinate (water-rich phase) and E kg be the amount of extract
(solvent-rich phase). Let xA , xB and xc be the weight fractions of water, ethylene tetrachloride
and isopropyl alcohol, respectively, in the raffinate. Let yA , yB and yc the corresponding values
in the extract. Let S be the amount of solvent used.
Total balance:
R + E = 100 + S (A)
Isopropyl alcohol balance:
0.28 IR + 0.052E = 30 (B)
Ethylene tetrachloride balance:
0.0097? + 0.94E = S (C)
Simultaneous solution of the above equations gives S = 45.10, E = 47.04 and R = 98.06.
(a) The amount of solvent used = S = 45.10 kg.
( b) The amount of extract = 47.04 kg; the amount of raffinate = 98.06 kg.
( c ) The amount of isopropyl alcohol extracted is
Eyc = 47.04 x 0.052 = 2.45 kg
The percent extraction of isopropyl alcohol is
2 45
——— x 100 = 8.17%
30
272 Stoichiometry and Process Calculations

9.2.7 Absorption
In absorption, soluble constituents of a gas mixture are separated by absorbing in a suitable
—
liquid solvent. The reverse process the removal of certain constituents of a liquid mixture by
—
contacting with a gas phase is known as desorption or stripping. Ammonia is absorbed from
a mixture of ammonia and air by contacting the gas with water in equipment known as
absorption columns. Benzene vapours present in coke-oven gases can be absorbed in hydrocarbon
oils and hydrogen sulphide can be absorbed from gas mixtures using ethanolamine solutions.
The essential difference between absorption and distillation is that in absorption, the liquid phase
used for effecting separation is a foreign substance introduced as a solvent whereas in distillation,
the vapour and liquid phases are produced from the feed material by boiling.
The rate at which a gaseous constituent of a mixture is absorbed in a liquid depends upon
the equilibrium solubility of the gas in the liquid at the given temperature, which in turn depends
upon the partial pressure of the gas in the mixture. For example, the equilibrium solubility of
ammonia in water is 25% (weight) ammonia for a partial pressure of 30.3 kPa at 293 K and
46.9 kPa at 303 K. Therefore, if a gas mixture with a partial pressure of ammonia greater than
30.3 kPa is in contact with a 25% aqueous ammonia solution at 293 K, ammonia will be
absorbed in the liquid.
As absorption is a gas-liquid contact operation like distillation, the equipment for absorption
and distillation are similar. Plate towers and packed columns are commonly employed for gas
absorption and distillation operations. A packed column for gas absorption is shown in
Figure 9.26.
Gas out

P3L

Liquid inlet Liquid distributor

Packed section

Gas in
<-
Liquid ~
outlet ^
Figure 9.26 Packed bed absorption column .
 Material Balance in Unit Operations 273

Packed columns are vertical columns filled with some packing materials. Tower packings
are devices of large surfaces, low weight per unit volume, and they provide a large free cross
section for flow of fluids. Random packings such as Raschig rings, Lessing rings, Berl saddles,
Intalox saddles, etc. and regular packings such as wood grids, stacked Raschig rings, etc. are
used for this purpose. The liquid is distributed over and trickles down through the packing. Gas
is admitted from the bottom and flows counter -current to the liquid . The gas is in contact with
the liquid throughout the column unlike in a plate column where the gas is in contact with the
liquid only intermittently. The mass transfer occurs and compositions of the gas and liquid
change continuously in a packed column.
Consider absorption of solute A from a gas mixture into a liquid solvent. Let G and L
represent the flow rate of the gas and liquid in kmol/h, and x and y the mole fraction of A in
the liquid and gas, respectively. The flow rates as well as the concentrations vary throughout
the column. The conditions at the bottom of the column are represented by suffix 1 and
conditions at the top of the column are indicated by suffix 2. Then the total material balance
for the column is
Gi + L2 = G 2 + Li
Liquid in, L 2 mol/h A Gas out, G2 mol/h,
x2 mole fraction solute y2 mole fraction solute

Liquid out, Lx mol/h Gas in, Gx mol/h

xxmole fraction solute yx mole fraction solute
Figure 9.27 Absorption operation .

The solute balance is

Glyl + L 2 x2 = G 2 y2 + Lxxx (9.7)
The material balance can be written in another way if the flow rates and compositions are
expressed on a solute-free basis. In an absorption operation though the total flow rate of gas
decreases from Gx to G 2 due to absorption of A, the flow rate of non -diffusing gas is unaltered
and let this be Gs kmol/h. Similarly, while the molar flow rate of the liquid phase increases from
L2 to Lx the flow rate of pure solvent is constant at, say, Ls kmol/h . Let X and Y represent
the mole ratio of solute in the liquid and gas respectively. Then
274 Stoichiometry and Process Calculations

_ moles of A in the liquid _ x

moles of solvent 1- x
_ moles of A in the gas y _
moles of solute free gas 1 - y
The number of moles of solute present in a gas stream can be determined as the product of
Gs and 7, and the number of moles of solute in a liquid stream can be obtained as the product
of Ls and X . Thus,
G\ Ti = GSYX and G 2 y2 = GSY 2
L\ xx = L$ Xx and L2 x 2 = L$ X 2
where Xx and X 2 are the mole ratio of solutes in the liquid at the bottom and top of the column,
and Yx and Y 2 are the mole ratio of solute in the gas stream at the inlet and the exit of the gas.
Substituting these values in Eq. (9.7) we get,
Gs ( Yi ~ Y2) = Ls ( Xx - X2) (9.8)

EXAMPLE 9.15 Acetone is recovered from an acetone-air mixture containing 25% (volume)
acetone by scrubbing with water. Assuming that air is insoluble in water, determine the percent
of acetone in the entering gas that is absorbed if the gas leaving the scrubber analyzes 5%
acetone.
Solution Basis: 100 kmol gas admitted to the absorption column
Let Gx and G 2 be the molar flow rate of the gas at the inlet and the exit of the absorber
respectively, and i be the mole fraction of acetone at the inlet andy2 that at the exit (Figure 9.28).
^
The air being insoluble in water, the entire quantity of air in the entering stream will appear in
the gas stream leaving the absorber. An air balance therefore leads to
Gi( l - yx ) = G2( l - y2 ) => 100 x 0.75 = G2 x 0.95
Therefore, G2 = 78.95 kmol
L‘i2 mol/h water, Gas out, G2 mol /h
x2 0 y2 = 0.05

Water out, Lj mol/h, Gas in, Gx = 100 kmol/h

xx mole fraction solute -
yx 0.25
Figure 9.28 Absorption operation in Example 9.15 .
 Material Balance in Unit Operations 275

The amount of acetone in the gas leaving is

Gjy2 = 78.95 x 0.05 = 3.9475 kmol
The amount of acetone in the gas entering is
G\yx = 100 x 0.25 = 25 kmol
Acetone absorbed is
25 - 3.9475
x 100 = 84.21%
25

EXAMPLE 9.16 A gas mixture consisting of 65% N2 and 35% S03 by volume is admitted
to an absorption column at a rate of 4500 kg/h . It is contacted with a stream of 50% H 2S04
flowing counter-current to the gas stream at a rate of 5000 kg/h. The gases leave at 101.3 kPa.
Water lost with the exit gases exerts a partial pressure of 25.0 kPa . If the concentrated acid
leaving the bottom of the column contained 75.0% H2S04, what percent of the entering S03
is absorbed and converted to acid?
Solution Basis: One hour operation
The absorption operation of this example is shown schematically in Figure 9.29.
The average molecular weight of gas entering the column = 0.65 x 28 + 0.35 x 80 = 46.2.
The molar flow rate of gases entering the absorber is
4500 .
„

= 97.40A 1kmol/1 /hr

46.2
Therefore, the moles of nitrogen entering is
97.4 x 0.65 = 63.31 kmol
Moles of S03 entering = 97.4 x 0.35 = 34.09 kmol
Let W kg be the mass of 75% H 2S04 produced and x be the moles of S03 that leaves with
the exit gases unabsorbed.

5000 kg/h Gas out, G2 mol/h

50% H 2S04 P u p = 25 kPa

A
Gas in, 4500 kg /h
75% H2S04 out
y1 = 0.35
Figure 9.29 Absorption operation of Example 9.16 .
276 Stoichiometry and Process Calculations

Since no nitrogen is absorbed, the gases leaving will contain 63.31 kmol nitrogen, x kmol
S03 and water vapour, which exerts a partial pressure of 25 kPa . Let y be the moles of water
vapour present in the gases. Then
25 y
~
101.3 63.31 + x + y
which means that
y = 0.32765x + 20.744 (A)
Total balance:
Kilograms of H 2S04 (50%) entering + kilograms of gas mixture entering
= kilograms of gas leaving + kilograms of con. H 2S04 (75%) leaving
That is,
5000 + 4500 = (63.31 x 28 + x x 80 + j/ x 18.016) + W
=> W + 80x + 18.016y = 7727.32
Substituting Eq. (A) into the above the total material balance reduces to
84.9174x + W = 7352.68 (B)
Since the molecular weight of H2S04 is 98.016, 98.016 kg of sulphuric acid contains 80 kg
of S03. Now consider an S03-balance for the absorber:
Kilograms of S03 entering with 50% H2S04 + kilograms of S03 in the feed gas
= kilograms of S03 in the gas leaving + kilograms S03 in the 75% H2S04 leaving
80 80
5000 x 0.5 x + 34.09 x 80 = 80 x + 0.75 JT x
98.016 98.016
The above equation reduces to
80x + 0.6121W = 4767.68 (C)
Solving Eqs. (B) and (C), we get x = 9.74 kmol. Therefore, the amount of SO3 absorbed =
34.09 - 9.74 = 24.35 kmol.
The percent of S03 that is absorbed is
24 35
x 100 = 71.43%
34.09

9.2.8 Distillation
Distillation is used to separate liquid mixtures into component parts by boiling and is one of the
major operations in chemical and petroleum industries . The basic requirement for a separation
by distillation is that the composition of the vapour be different from the composition of the
liquid with which it is in equilibrium . Distillation differs from evaporation in that in the latter
vapour produced on boiling is a pure fluid, whereas in the former all the components constituting
 Material Balance in Unit Operations 111

the liquid will be present in the vapour but in different proportions. The vapour will be richer
in the more volatile components compared to the liquid with which it is in equilibrium . The
products obtained on distillation are commonly referred to as distillate (or top product), which
is rich in more volatile components and residue (or bottom product), which is rich in less
volatile components.
When a liquid mixture at a high temperature and pressure is subjected to a sudden reduction
in pressure by passing through a valve, the liquid gets partially vaporized . The resulting liquid-
vapour mixture is separated into the distillate and the bottom products as shown in Figure 9.30.
The process is known as flash distillation or flash vaporization. The flash distillation is an ideal
single-stage operation in which the distillate and bottom products have equilibrium compositions.
The products will have an appreciable difference in their compositions only if the volatilities of
the constituents are appreciably different. Therefore, it is generally impossible to obtain pure
products by a single-stage flash vaporization.
Distillate, D
* mol/ h, yD mole
fraction solute

Heat
exchanger

Feed , F mol / h , Liquid-vapour

xF mole fraction
solute
p
w XI
Valve
>
separator

Residue, W mol/h,
xw mole fraction solute
Figure 9.30 Equilibrium flash distillation .

The vapour produced in a single -stage flashing operation can be enriched in the more
volatile component by bringing it in contact with a liquid phase with which the vapour is not
in equilibrium . The liquid phase known as reflux is obtained by condensing the vapour and
recycling a part of the condensate. The distillation carried out in this fashion is known as
rectification or fractionation . The fractionation can be carried out as a multi-stage operation
in a plate column or as a continuous contact operation in a packed column. Distillation using
a plate column is schematically represented in Figure 9.31.
A fractionating column is a cylindrical vertical tower which is divided into a number of
sections by means of plates or trays. Different designs for trays are available, the simplest one
being a sieve tray. Sieve trays are flat plates with a large number of small perforations that
permit upward flow of vapour. The liquid flows across the plate and run over an overflow weir
through the downcomer in the plate to the plate below. The vapour issuing through the
278 Stoichiometry and Process Calculations

perforations provides turbulence in the pool of liquid present on the tray, thereby facilitating
mass transfer on the plate. On each plate more volatile components are vaporized and transferred
to the vapour and the less volatile components are condensed and transferred to the liquid.
Thus, the vapour leaving the tray is richer in more volatile components than the vapour coming
to that tray. The liquid leaving the tray is leaner in more volatile components compared to the
liquid entering the tray, it is still capable of enriching the vapour coming to the lower plate.
Vapour to condenser

t f Liquid reflux

t t
TT
t t
t t -
S
p
i T3

T T 2-
O
Q
3
P
cr

Feed in -
L
r
T t
TT
LT
LT

*0* Vapour from reboiler

I
> Liquid to reboiler
I
Figure 9.31 A plate column for fractionation .

In the fractionation column, the feed liquid is admitted almost centrally on the feed plate
where it gets partially vaporized. The vapour flows upwards through the perforations and
comes in contact with the liquid reflux on each plate. The vapour issuing from the top plate
is taken to a condenser. The vapours are condensed by exchange of heat with a coolant, the
most frequently used cooling medium being water. A part of the condensate is returned to the
column as reflux and the other part is withdrawn as distillate or top product. The ratio of the
moles of liquid recycled as reflux to the moles of distillate product is known as reflux ratio.
The bottom of the column is equipped with a reboiler which receives the liquid flowing
downwards from the feed plate and vaporizes it partially. The vapour so produced is sent back
 Material Balance in Unit Operations 279

to the bottom plate. This vapour when comes in contact with the liquid flowing downwards
strips away more volatile components from the liquid and as a result the bottom product can
be made to be almost free of more volatile components. Steam is used as the heating medium
in the reboiler. The liquid leaving the reboiler is collected as the residue or the bottom product .
Consider the distillation of a binary mixture of components A and B in which A is the more
volatile component. Let F , D and W be the molar flow rates of the feed, distillate and residue
respectively, and let xF , xD and xw be their compositions expressed in terms of mole fractions
of A . Considering the column as a whole, the total material balance and the component-
balance may be written as
^
F = D + W (9.9)
FXF = DXD + Wxw (9.10)

Let R denotes the reflux ratio for the column, and let L be the reflux in kmol/h. Then, L = RD.

EXAMPLE 9.17 A continuous distillation column is used to regenerate solvent for use in a
solvent extraction unit. The column treats 200 kmol/h of a feed containing 10% (mol) ethyl
alcohol and the rest water. The overhead product is 89% (mol) alcohol and the bottom product
is 0.3% (mol) alcohol. The overhead is sent to the extraction unit and the bottom is wasted.
What is the daily requirement of make -up alcohol in the solvent extraction unit?
Solution Basis: 200 kmol/h feed
Let F, D and W be the flow rates of the feed, distillate and residue respectively, and xF ,
xD and xw be the mole fraction of ethanol in the feed, distillate and residue respectively. F =
200 kmol/h, xF = 0.10, xD = 0.89 and xw = 0.003.
The total material balance:
F = D + W
Alcohol balance:
FXF = DXD + Wxw
Substituting the given values in these equations, we get
D + W = 200
0.89D + 0.003 IT = 200 x 0.10 = 20
Solving the above equations, we get D = 21.87 kmol and W = 178.13 kmol.
Alcohol wasted = alcohol present in the residue
= Wxw = 178.13 x 0.003 = 0.5344 kmol/h
Therefore, the make-up alcohol required per day = 0.5344 x 24 x 46 = 589.98 kg

EXAMPLE 9.18 An aqueous solution of methanol containing 20% (weight) methanol is to be

separated into a distillate product containing 97% (weight) methanol and a bottom product
containing 2% (weight) methanol. For treating 100 kg of feed with a reflux ratio of 3.5 on a
weight basis, calculate the following :
280 Stoichiometry and Process Calculations

(a) The amounts of distillate and bottom products

( b) The amount of vapour condensed in the condenser per kg of distillate
( c ) The amount of vapour condensed in the condenser per kg of feed.
Note : The reflux ratio is defined as the ratio of the amount of condensate recycled to the
amount of condensate withdrawn as distillate product.
Solution Basis: 100 kg feed
The distillation operation of this example is represented schematically in Figure 9.32.

Vapour, G kg /h
»
Condenser

t
Distillate, D kg/h
^
Reflux. L = RD kg /h = 097

Feed, F = 100 kg /h
>
xF = 0.20

«
-

Residue, W kg /h
-* * xw = 0.02
Reboiler
Figure 9.32 Distillation operation of Example 9.18.

(a) The total material balance:

F=D + W
Alcohol balance:
FXF = DXD + Wxw
Substitute xF = 0.20, xD = 0.97 and = 0.02 in Eq. (9.10) and eliminate W using
Eq. (9.9), we get
0.20F = 0.97D + 0.02(F - D )
Put F = 100 and solve the above equation for D. We get D = 18.95 kg/h. Putting values
of F and D in Eq. (9.9), we get W = 81.05 kg/h .
( b) Take a total material balance around the condenser.
G = L + D
 Material Balance in Unit Operations 281

Since the reflux ratio R = 3.5, the reflux L = RD = 3.5Z), and the above equation gives,
G = 4.5D. For 1 kg distillate product, the amount of vapour condensed, G = 4.5 kg.
( c ) For one kg of feed, the distillate obtained is D = 0.1895 kg [from part (a)]. Therefore,
the amount of vapour condensed per kg of feed is
4.5 x 0.1895 = 0.853 kg

EXERCISES

Basic material balance principles

9.1 Wet sewage sludge enters a continuous thickener at a rate of 100 kg per hour and
dehydrated sludge leaves the thickener at a rate of 75 kg per hour. Determine the
amount of water removed in the thickener in one hour, assuming steady -state operation.
9.2 Air is dehumidified at a constant pressure of 101.3 kPa . The partial pressure of water
in the air admitted to the dehumidifier is 7 kPa and the temperature is 350 K. The partial
pressure of water in the air leaving is 1.5 kPa. How much water (in kilograms) is
removed from 100 cubic meters of air admitted?
9.3 Urea, phosphoric acid and potassium chloride are mixed together to obtain a mixed
fertilizer having NPK content 10 : 26 : 26 as %N, %P205 and %K 20 by weight, balance
being the weight of filler materials. Calculate the quantities to be mixed to get 1000 kg
of mixed fertilizer.
9.4 Formulate the independent material balance equations for determining the flow rate of
benzene in the feed under the following circumstances. An aqueous acetic acid solution
containing 80% acetic acid and the rest water is charged into a still along with pure
benzene. 400 kg/h pure acetic acid is withdrawn as product from the still. The top
product leaving the still consists of 11.0% acetic acid, 21.5% water and the rest
benzene.
9.5 A soap plant produces raw soap containing 50% moisture . This is to be dried to 20%
moisture before it is pressed into cakes for sale. How many 100-g soap pieces can be
obtained from 1000 kg of original raw soap?
9.6 A weak acid containing 12.5% H2S04 and the rest water is fortified by adding 500 kg
of concentrated acid containing 80% H2S04. Determine the amount of the solution
obtained if it contains 18.5% H2S04.
9.7 A cellulose solution contains 5.0% cellulose by weight in water. It is to be diluted to
4.0% using a 1.0% solution of cellulose in water. Determine the kilograms of 1.0%
solution required to dilute 100 kg of the 5.0% solution.
9.8 One hundred kilograms of a dilute waste acid containing 30.0% sulphuric acid is to be
fortified to 50.0% sulphuric acid using concentrated sulphuric acid of strength 96.0%.
How many kilograms of concentrated sulphuric acid are required for this process?
282 Stoichiometry and Process Calculations

9.9 Waste acid from a nitrating process contains 25% HN03, 55% H 2S04 and 20% H20
by weight. This is to be concentrated to get fortified acid containing 27% HN03, 60%
H 2S04 and 13% water. This is done by adding concentrated H 2S04 of strength 93%
H 2S04 and concentrated HN03 of strength 90% HN03 in suitable quantities to the
waste acid. If 1000 kg fortified acid is to be produced, calculate the kg of the various
solutions mixed.
9.10 The liquid effluent from a processing plant having a BOD of 0.15 g/L is discharged
at a rate of 4000 cubic metres per day into a stream flowing at a rate of 0.3 cubic
metres per second and having an initial BOD of 5 x 10 3 g/L. Determine the BOD in
~

the stream immediately below the discharge point?

9.11 It is decided to measure the flow rate of a pure air stream by injecting pure C02 at
a rate of 10 mol/ h into the flowing stream . The resultant mixture analyzed 8.6% C02
on a mole basis. What is the flow rate of air?
9.12 Pure oxygen at 120 kPa and 300K is injected into an ammonia pipeline at a rate of
0.02 m 3/s. The concentration of oxygen in the pipeline at a point far removed from
the point of injection is found to be 10% (volume). What is the flow rate of ammonia
through the pipe in kg/h?
9.13 Two tanks which are connected to each other is initially sealed off from one another
by means of a valve. Tank I initially contains 1 m 3 of air at 600 kPa and 343.2 K.
Tank II contains a mixture of oxygen and nitrogen containing 95% (mole) nitrogen at
1200 kPa and 363.2 K. The valve is now opened and the contents of the tanks are
allowed to mix. After complete mixing, the tanks contained 85% (mole) nitrogen.
Calculate the volume of tank II.
9.14 It is desired to produce a gas mixture analyzing 40% methane , 35 % ethane and
25% propane by blending the following three gas mixtures in suitable proportions.

Constituent Mixture I Mixture II Mixture III

CH4 25 35 55
C2H6 35 20 40
C3H8 40 45 5

Determine the proportion in which the gases are to be mixed .

9.15 A process stream of given flow rate is obtained by mixing together two separate
streams. In order to determine the ratio in which the streams are mixed, a soluble salt
is added to one of the streams at a steady rate. The concentration of salt in the stream
is determined to be 5% (W) and that in the combined stream is found to be 0.45 %
(W). Determine the ratio in which the streams are mixed .
9.16 A laundry can purchase soap containing 30% by weight water at a rate of ?14 per kg
f.o. b. factory. The same manufacturer offers a soap containing 5% water by weight.
If the freight rate is ?1.40 per 10 kg, what is the maximum price that the laundry can
pay the manufacturer for the soap containing 5% water ?
 Material Balance in Unit Operations 283

9.17 Rubber latex containing 15% (weight) rubber solids is to be coagulated by treating with
66°Be H 2S04. If the ratio of the weights of acid to latex solids is 1: 50, determine the
following:
(a ) Cubic metres/hour of 66°Be acid required for treating 1000 kg/h of latex
( b) How many kilograms of solution to be removed per hour for recovering the solids
9.18 A company has drawn a contract for the purchase of paper at a price of ?10 per kg
of paper containing 5% moisture by weight and to adjust the price if the moisture
content varies, so that the price of bone dry paper is constant. Also if the moisture
content exceeds 5%, the additional freight charge incurred due to the excess moisture
will be deducted from the total cost. The freight charge is ?2 per kg of paper. Calculate
the following:
(a ) The total amount to be paid for 10000 kg of paper containing 3% moisture
( b) The total amount to be paid for 8000 kg of paper containing 9% moisture.
9.19 A water sample taken from a stream contained 200 ppm Na2S04. To measure the flow
rate of the running stream, 5 kg Na 2S04 is added to the stream uniformly over a one -
hour period. The analysis of water taken from the stream from a spot down stream
from the point of addition of the salt showed 350 ppm Na 2S04. What is the rate of
flow of water in the stream?
9.20 Ion-exchange process shown in Figure 9.33 is used for water purification.
Brine
Feed
water
*

x
^p
1

1 2 3
:
j
s.
.
-J .
R
a

Waste Brine

Pure water
Figure 9.33 Ion-exchange process (Exercise 9.20) .

Here, cations such as Ca ++ and Mg++ are exchanged with Na + ions in the ion-exchange
resin, resins subsequently regenerated with concentrated brine . The process data for
the unit is given below:
Feed water Tolerable limit in Fresh brine Waste brine
(ppm) pure water (ppm) (ppm) (ppm)

Ca^ 400 10 500 41500

Mg++ 250 15 300 25000
Na+ 60 800 ~2 x 105 ~2 x 105
284 Stoichiometry and Process Calculations

At any given time when one bed purifies hard water, one is engaged in the regeneration
of the used-up bed and the third one is kept idle as a standby unit. Determine the
average brine consumption per 1000 kg of process water being treated.
Evaporation
9.21 In a process for producing caustic (NaOH), 4000 kg/h of a solution containing 10 wt%
NaOH is evaporated in the first evaporator, giving a 20% NaOH solution. This is then
fed into a second evaporator, which gives a product of 50% NaOH . Calculate the
following:
(a ) The amount of water removed from each evaporator
( b) The feed to the second evaporator, kg/h
( c ) The amount of product, kg/h
9.22 An aqueous solution containing 15% NaOH and 0.5% NaCl is concentrated at a rate
of 100 kg/min in an evaporator. The concentrated solution is then mixed with 2000 kg
of aqueous NaOH solution in a mixer. At the end of one hour a sample is collected from
the mixer and analyzed. The analysis shows 40% NaOH and 0.8571% NaCl. Calculate
the following:
(a ) The concentration of the aqueous solution in the mixer
( b) The composition of the concentrate from the evaporator
( c ) The mass of water (in kilograms) evaporated in one hour
9.23 A 50% NaCl solution is to be concentrated in a triple-effect evaporator (Figure 9.45).
Equal amount of water is evaporated in each effect. Determine the composition of the
outlet stream from effect II.
9.24 A crude salt when dissolved in water yields brine whose composition is 15% by weight
of NaCl, 1% NaBr and 3% MgCl 2. Some water is evaporated and 40% of salt (NaCl)
crystallises in pure form . On evaporation, brine looses 70% water. For 100 kg of
original brine, calculate (a) weight % of MgCl2 and NaBr in the concentrate and
(b) The composition of cake if all the water is evaporated .

Vapour VaP°ur Vapour

Feed, 50000 kg /h
I II ill
50% NaCl solution
fr -fr -
-fr

4 Steam

-fr
35,000 kg /h
Condensate Condensate product
Condensate
Figure 9.34 Triple-effect evaporator in Exercise 9.24 .
 Material Balance in Unit Operations 285

9.25 An evaporator is fed continuously with 50000 kg/h of a solution containing 10%
NaOH, 10% NaCl, and the rest water by weight. During evaporation, water is removed
as vapour and salt NaCl precipitates as crystals and is removed by filtration. The
concentrated liquor leaving the evaporator contains 50% NaOH, 2% NaCl, and the rest
water. Determine
(a) the mass of water evaporated per hour;
(b) the mass of salt precipitated per hour;
(c) the mass of concentrated liquor produced per hour

Crystallization
9.26 0.05 kg of a slightly soluble salt is mixed with 0.1 kg of water. The undissolved salt
is removed by filtration. The filter cake weighed 0.045 kg as obtained and 0.040 kg
after drying. What is the solubility of the salt in water expressed in kg salt/100 kg
water? What assumptions are inherent in the solution?
9.27 Fifty kilograms of dry sodium bicarbonate is to be crystallized and removed from
1000 kg of a saturated solution at 333 K. To what temperature the solution be cooled,
if the solubility data is as follows?

Temperature (K ) 333 323 313 303 293 283

r
Solubility ^
kg bicarbonate
16.4 14.5 12.7 11.1 9.6 8.2
v 100 kg water j

9.28 200 kg of a 15% and 100 kg of 5% solutions of sodium sulphate by weight are mixed
in a crystallizer and crystallization takes place. If 50 kg Na 2SO410H 2O crystals are
formed, compute the composition of the magma .
9.29 One hundred kilograms of a mixture of Na 2CO310H 2O and Na 2SO410H 2O is heated
to drive away the water of hydration. The anhydrous salt mixture weighed 39.335 kg.
What is the mole ratio in which the two salts are present in the mixture?
9.30 A 10-kg mixture of Ca(N03)2 - 4 H20 and CuS04 5 H20 is heated to drive off the water
of hydration. The residue weighed 6.5591 kg. Determine the percent composition of
the mixture of hydrated salts.
9.31 A saturated solution of calcium chloride in water is to be prepared by dissolving
CaCl 2 6 H20 in 100 kg water at 293 K . If the solubility of calcium chloride in water
*

at 293 K is 75 kg of anhydrous salt per 100 kg of water, what mass of hydrated

crystals is required?
9.32 If 0.1 kg of Na 2S04 is dissolved in 0.2 kg of water and the resulting solution is cooled
until 0.1 kg of Na 2SO410H 2O crystallizes out. Determine
(a ) The composition of the mother liquor
( b) The amount of anhydrous crystals obtained per 0.1 kg original solution
9.33 What will be the yield of hypo (Na 2S203- 5 H20) if 100 kg of a 50% solution of Na 2S203
is cooled to 293 K. The solubility at 293 K is 70 parts Na 2S203 per 100 parts water.
286 Stoichiometry and Process Calculations

9.34 After a crystallization process, a solution of CaCl2 in water contains 62 kg of salt per
100 kg of water. Calculate the weight of solution necessary to dissolve 250 kg of
CaCl 2- 6 H20 at 298 K. The solubility at 298 K is 7.38 kmol CaCl2 in 1000 kg of water.
9.35 A saturated solution of barium nitrate is to be prepared from 100 kg of the salt at
373 K.
(a ) Determine the amount of water required .
( b) If this solution is cooled to 273 K, how much Ba(N03) 2 crystals will be obtained
if the precipitated crystals carry 4 kg of water per 100 kg of dry crystals?
The solubility data of Ba(N 03)2 in water : at 273 K, 5.0 kg/100 kg water; at 373 K,
34 kg/100 kg water.
9.36 A saturated solution of sodium chloride is prepared at 373 K using 100 kg of salt.
(a ) How much water is required?
( b) If the solution is cooled to 273 K, how much salt is precipitated out of the
solution ? Solubility of sodium chloride is 39.8 kg/100 kg water at 373 K and 35.7
kg/100 kg water at 273 K.
9.37 A batch of 1000 kg of KC1 is dissolved in sufficient water to make a saturated solution
at 363 K (solubility is 35 wt% KC1 in water). The solution is cooled to 293 K, at which
its solubility is 25.4 wt%.
(a ) What is the weight of water required for solution and the weight of crystals of
KC1 obtained?
( b) What is the weight of crystals obtained if 5% of the original water evaporates on
cooling?
9.38 A salt solution weighing 10000 kg with 30 wt% Na 2C03 is cooled to 293 K. The salt
crystallizes as decahydrate.
(a ) What will be the yield of Na 2CO310H 2O crystals if the solubility is 21.5 kg of
anhydrous Na 2C03/100 kg of total water if no water is evaporated?
( b) What will be the yield if 3% of total weight of the solution is lost by evaporation
in cooling?
9.39 A hot solution of Ba(N03)2 from an evaporator contains 30.6 kg of Ba(N03) 2 per 100 kg
of water and goes to a crystallizer where the solution is cooled and Ba(N03) 2 crystallizes.
On cooling 10% of the original water present evaporates. For a feed solution of
100 kg, calculate the following:
(a ) The yield of crystals if the solution is cooled to 290 K, if the solubility is 8.6 kg
Ba(N03) 2/100 kg total water at 290 K
( b) The yield if cooled to 283 K, if the solubility is 7.0 kg Ba(N03) 2/100 kg total water
at 283 K
9.40 A solution of sodium sulphate in water is saturated at a temperature of 313 K. Calculate
the weight of crystals and the percentage yield obtained when cooling 1000 kg of this
solution to a temperature of 278 K. At 278 K decahydrate is the stable crystalline form .
The solubility at 313 K is 32.6% and at 278 K is 5.75% Na 2S04.
 Material Balance in Unit Operations 287

9.41 A saturated solution containing 1500 kg of potassium chloride at 360 K is cooled in

an open tank to 290 K. If the specific gravity of the solution is 1.2, the solubility of
KC1 per 100 parts of water is 53.55 at 360 K and 34.5 at 290 K, calculate
(a ) The capacity of the tank required
( b) The weight of crystals obtained neglecting the loss of water by evaporation
9.42 Sodium carbonate is recovered as decahydrate from 1000 kg of a 5% solution of
sodium carbonate in water. If it is desired that 95% of Na 2C03 is to be recovered as
decahydrate by cooling to 278 K, determine the following:
(a ) The mass of water evaporated
( b) The mass of crystals obtained
The solubility of Na 2C03 in water at 278 K is 9.0% (weight).
9.43 One thousand kilograms of a 30% solution of Na 2C03 in water is cooled slowly to
293 K. During cooling, a portion of water is evaporated and removed . 700 kg of
Na2CO310H2O crystals are formed in the process. What percent of total water in the
feed is evaporated? The solubiltiy of anhydrous Na2C03 at 293 K is 21.5 kg/100 kg of
water.
9.44 An aqueous solution of Na2C03 contains 12% carbonate and small amounts of soluble
impurities. 80% of the carbonate is recovered as Na 2CO310H 2O by evaporation of
water and subsequent cooling to 278 K. The solubility of Na 2C03 at 278 K is 9.0%
(weight). On the basis of 100 kg solution treated, determine the following:
( c ) The amount of water evaporated
(d ) The quantity of crystals formed
9.45 In the recovery of glycerine from spent soap lye, 10000 kg/h of lye containing 10.5%
glycerine and 11.5% salt (NaCl) is concentrated by evaporation. The concentrated
solution leaving the evaporator contained 80% glycerine and 5% salt. Entrainment loss
is estimated to be 2% of the glycerine in the charge. Calculate the quantity of
(a) The water evaporated per hour
( b) The salt crystallised per hour
9.46 A solution containing 25% MgS04 and 75% water is cooled so that MgS04- 7H20
crystals are obtained on crystallization. During this process, 6.5% of the total water
present in the feed is lost due to evaporation. The solubility of anhydrous MgS04 in
water at this temperature is such that 35% of the anhydrous salt is present in the
saturated solution. For treating 1000 kg of solution, calculate the following:
(a) The weight of MgS04 - 7H20 crystals obtained
( b) The solubility of anhydrous salt in water (kg salt/100kg water)
9.47 The solubility of NaN03 in water is 1.76 kg/kg water at 373 K and 0.88 kg/kg water
at 293 K. A 25% (weight) solution of NaN03 in water is concentrated to saturation by
evaporation at 373 K . It is then cooled to 293 K. The crystals formed are separated .
It is found that each kilogram of crystals so removed carries with it 0.1 kg of solution.
288 Stoichiometry and Process Calculations

When the crystals are dried, NaN03 in the adhering solution gets deposited on the
crystals. For 1000 kg of the original dilute solution, calculate the following:
(a ) The amount of water evaporated for attaining saturation at 373 K
( b) The weight of dry crystals obtained
9.48 A dilute salt solution containing 6% salt is fed to an evaporator at a rate of 10000 kg/
h for a trial run. Crystals formed along with the saturated solution adhering with them
are sent to a centrifuge for the recovery of the solution. 60% of the adhering solution
is recovered. It is found that the saturated solution that is withdrawn from the evaporator
is 850 kg and that is recovered by centrifuging is 200 kg. The crystals are dried to
drive off the remaining water. The dry crystals obtained weighed 360 kg. Determine
the following:
(a ) The solubility of the salt in kg salt/100 kg water
( b) The mass of salt crystallized in the evaporator
( c ) The amount of water evaporated in the evaporator
(d ) The amount of water removed in the drier
9.49 An aqueous solution containing 60% Na2S203 and 1% soluble impurities is diluted with
water and fed to a crystallizer where it is cooled to 283 K in order to crystallize
Na2S203- 5 H20. The crystals carry 0.06 kg of solution (excluding impurities) per kg of
crystals. The free water present in the adhering solution is removed on drying the
crystals. The final dried product contains not more than 0.1% impurity. The solubility
of the pentahydrate is 1.4 kg of Na 2S203- 5 H20/kg free water. On the basis of 100 kg
of 60% solution, calculate the following:
(a ) The mass of water added before cooling
( b) The percentage recovery of the Na 2S203 in the dried hydrated crystals
Leaching
9.50 Oilseeds containing 40% oil and the rest inert insolubles are extracted with hexane to
recover oil. Oil is dissolved in the solvent and is removed as a clear solution. The
underflow sludge analyzed 10.53% oil and 26.32% hexane. Identify the key component.
Determine the percent recovery of oil.
9.51 Tannin is extracted from certain wood bark which contains 6% moisture , 11.0%
tannin, 8.0% soluble non-tannin materials and the rest insoluble lignin. After tannin is
extracted, the solid residue analyzes 1% tannin and 0.25% soluble non-tannin on a dry
basis. What is the percent extraction of tannin?
9.52 Black ash containing 45% Na2C03, 5% water soluble materials and 50% inert insolubles
is extracted with water to recover soda ash. The solid residue leaving the extraction
unit contains 5% Na 2C03, 0.5% water soluble materials, 85% insolubles and the rest
water. Calculate per 1000 kg of black ash treated
( b) The mass of residue produced
(a ) The mass of sodium carbonate extracted
9.53 Oil is extracted from seeds by leaching with organic solvents. Soybean seeds containing
20% oil, 65% inert solids and 15% water are leached with hexane and after extraction
 Material Balance in Unit Operations 289

the solid residue is removed from the solution of oil in hexane. The residue analyzed
1.0% oil, 88% inert cake and 11% water. What percent of oil in the seeds is recovered?
9.54 A counter-current extractor is employed to extract oil from a solid meal using ethyl
ether as the solvent. The fresh meal is charged to the unit at a rate of 1000 kg/h and
contains 25.0% (weight) oil. Pure solvent enters the bottom of the extractor. The
overflow from the unit contains 60% (weight) oil. The underflow contains 0.25 kg of
solution per kg of oil-free solids and the concentration of oil in the underflow is 12%.
Calculate the following:
(a ) The solvent requirement
( b) The percentage oil recovery
9.55 100 kg of an ore containing 70% solute and 30% inert solid is to be extracted by
washing it twice with 50 kg of batches of fresh water by a simple multiple contact
method. The underflow retains 0.6 kg of solution per kg of inert solid . Calculate the
following:
(a ) Concentration of solute in the final underflow
( b) Concentration of the solute in the combined extract
( c ) Percentage recovery of the solute after two washings
Drying
9.56 Soap as produced contains 50% moisture on a wet basis. Before it can be pressed into
cakes for sale, the moisture should be reduced to 20%. How many 100 g cakes can
be pressed from 1000 kg of wet soap?
9.57 A wet paper pulp containing 70% water is dried in order to remove 60% of the water
present. Determine the following:
(a ) The mass of water removed per 100 kg of wet pulp
( b) The composition of the dried pulp
9.58 A wet granular material containing 80% water is dried in a rotary counter-current drier.
The charge is admitted at one end and hot dry air is passed from the other end . In
a typical operation, it is found that 100 kg of water is removed from the material giving
a dry product containing 40% water. What is the weight of the wet material charged
to the drier?
9.59 Wood containing 40% moisture is dried to 20% moisture, both moistures expressed on
a wet basis. Determine the quantity of water evaporated per kilogram dry wood.
9.60 A batch of leather leaving a drier weighs 1000 kg and contains 5% moisture. During
drying the leather loses 50% of its original weight. Determine the following:
(a ) The moisture content of the leather entering the drier on a dry basis
( b) The amount of moisture removed per kg of bone dry leather
( c ) Water removed as percent of the original water present
9.61 A drier is fed with wet solid to reduce the moisture content from 90% to 20%. The
product leaving the drier is admitted to an oven which further brings down the
moisture to 2%. If the drier can handle 1000 kg of wet solid per day, calculate the
following:
290 Stoichiometry and Process Calculations

(a ) The weight of products leaving the drier and the oven per day
( b) The percentage of the original water that is removed in the drier and the oven
9.62 Air supplied to an adiabatic drier is at 101.3 kPa and 369.15 K with a dew point of
301.15 K. 2.0 kg of water is evaporated per 100 cubic metres of wet air entering the
drier. Calculate the following:
(a ) The exit air wet-bulb temperature and dry -bulb temperature
( b) The exit air percent humidity
( c ) The volume of exit air per 100 cubic metres of inlet air
9.63 A laboratory drier produces 50 kg of dry solid containing 6% (weight) water from a
wet-feed material containing 20.5% water. The drier operates adiabatically, with the
wet solid entering the drier at the wet-bulb temperature of the drier air. A total of 500 m 3/
h of hot air at 365.7 K and 101.3 kPa with a dew point of 303.2 K is supplied to the
drier. Calculate the following :
(a ) The temperature of the air leaving the drier
( b) The percent humidity of the air leaving the drier
9.64 Air at 101.3 kPa enters an adiabatic drier at 372 K with a dew point of 287 K and
leaves at 80% humidity. Wet paper enters the drier with 25% moisture and leaves with
5% moisture. Determine the following:
(a ) The temperature of air leaving the drier
( b) Water evaporated in kilograms per 100 cubic metres of air entering
( c ) The mass of finished product (in kilograms) per 100 cubic metres of air entering.
9.65 Wet lumber (5% moisture) is dried to 1% moisture in a hot-air drier. Air fed to the drier
contains 0.5% water. The moist air leaving the drier contains 2% (weight) water. How
much air is required to dry 2000 kg/h of lumber ?
9.66 1000 kg/h of precipitated chalk slurry containing 10% CaC03 is to be filtered and dried
continuously. The filter cake is expected to carry 0.8 kg of water per kg of chalk. Hot
air would enter the adiabatic drier at 350 K and 1 bar and 5% humidity. At the exit the
air would be saturated. The dried chalk would contain only 5% water on a wet basis.
Calculate on an hourly basis the following:
(a ) The weight of filtrate
( b) The weight of the cake after dying
( c ) The weight of air at the drier inlet
9.67 CaC03 slurry is to be dried. The drier is designed to remove 100 kg of moisture per
hour. Air at 293 K and 40% relative humidity enters the drier, and leaves at 338 K and
65% relative humidity.
(a ) What is the weight in kilograms of bone dry air required per hour ? The atmospheric
pressure is 103 kPa.
( b) If the humidity of the air entering the drier can be varied , what will be the
minimum amount of dry air required? The constants for the Antoine equation for
vapour pressure of water in kPa may be taken as A = 16.26205 , B = 3799.887
and C = -46.854.
 Material Balance in Unit Operations 291

9.68 A solid material wet with toluene is dried in an adiabatic drier to recover toluene and
to produce dry solids. The drier is fed with 100 m 3/h of an air -toluene mixture at
101.3 kPa and 333 K with a wet-bulb temperature of 305 K. The gases leave the drier
at 310 K DBT with relative saturation of 95%. The vapour pressure of toluene is given
by the Antoine equation
3096.52
In Ps = 13.9987 -
T - 53.67
where pressure is in kPa and temperature is in K . The latent heat of vaporization is 404
kJ/kg and the psychrometric ratio for the toluene-air system is 1.88 kJ/kg K . Determine
the following:
(a ) The toluene evaporated in the drier, (kg/h)
( b) The volume of gases leaving the drier, (m3/h)

Extraction
9.69 Two liquids A and 5 are only partially miscible. At a certain temperature, 41 kg of A
and 59 kg of B are mixed well and the mixture is allowed to settle. The mixture
separates into two immiscible phases, one rich in A and the other rich in B . The A -
rich phase analyses 90% A and the 5-rich phase analyzes 80% B . What are the weights
of the v4 -rich and 5-rich phases?
9.70 A mixture of phenol and water under certain conditions of temperature and composition
forms two separate layers, one rich in phenol and the other rich in water. At 300 K,
the composition of the upper and lower layers are 70% and 9% by weight of phenol
respectively. If 40 g of phenol and 60 g of water are mixed and the layers are allowed
to separate at 300 K, what will be the weights of the two layers?
9.71 Acetic acid is extracted from an aqueous solution containing 42.86% (weight) acetic
acid using benzene as the solvent. The mutual solubility of benzene and water may be
neglected. When equal weights of benzene and the aqueous solution are mixed and the
phases separated, the aqueous phase analyzed 16.25% acetic acid . On the basis of
100 kg of the aqueous solution being treated, calculate the following:
(a ) The masses of the aqueous phase and benzene phase
( b) The percent recovery of acetic acid into benzene
9.72 Toxic impurities A and 5 present in an oil is to be removed before it is subjected to
hydrogenation. 1000 kg of oil is being charged . A portion of this oil containing 3% A
and 2% 5 is sent through a purifier where it is treated with a mixture of two solvents
St and S2. 100 kg of Sx can dissolve a maximum of 15.0 kg of A and 2 kg of 5
whereas 100 kg of S2 can dissolve a maximum of 3 kg of A and 12 kg of 5. The
solvent mixture containing dissolved impurities is then separated from the oil. The oil
free of impurities is mixed with a portion of the original feed that has bypassed the
purifier and sent to the hydrogenation unit . The feed to the hydrogenator should contain
A and 5 not more than 0.1% each. Calculate the following:
(a ) The amounts of solvents Sx and S2 required
( b) The amount of oil bypassed the purifier
292 Stoichiometry and Process Calculations

9.73 A mixture containing 30% acetone and 70% chloroform is extracted with a mixed
—
solvent containing acetic acid and water. The two immiscible phases the raffinate and
—
extract phases that result after extraction had the following analysis :
Extract: acetone 7.5%, chloroform 6.06%, acetic acid 31.88% and water 54.56%
Raffinate: acetone 20.0%, chloroform 67.0% acetic acid 10.0% and water 3.0%
For the basis of 100 kg of the mixture extracted, determine the following:
(a ) The composition of the mixed solvent on a weight basis
( b) The quantities of raffinate and extract phases
( c ) The amount of mixed solvent used

Absorption
9.74 Ammonia is recovered from a gas mixture containing 25% (volume) C02 and 75%
(volume) NH3 by scrubbing with water. Assuming that C02 is insoluble in water,
determine the percent of ammonia in the entering gas that is absorbed if the gas leaving
the scrubber analyzes 35% NH3.
9.75 Air at 540 K and 101.3 kPa is dried from a partial pressure of 7000 Pa of water vapour
to a partial pressure of 1500 Pa of water vapour at constant total pressure. How much
water in kilograms is removed per cubic metre of wet air entering?
9.76 A stream of gas at 302 K and 100 kPa , 50% saturated with water vapour is passed
through a drying tower where 90% of the water vapour is removed . For 100 cubic
metres of gas admitted through the tower, how many kilograms of water are removed?
The vapour pressure of water at 302 K is 4.0 kPa .
9.77 One hundred kilograms per hour of 98% (weight) sulphuric acid is used for the
absorption of S03 in the contact sulphuric acid plant. If 20% oleum is the product
leaving the absorption tower, what mass of S03 is absorbed per hour?
9.78 A gas mixture at 300 K and 1 bar analyzing by volume 20% N 2 and 80% CH 4 is
subjected to liquefaction at a rate of 1500 kg/h. It is found that only 30% (weight) of
the entering gas is liquefied and the concentration of N2 in the liquid is 60% by weight.
The unliquefied gas leaves the unit at 273 K and 1 bar. Determine (a) the volume of
unliquefied gas, m 3/h (b) the composition of the gas leaving expressed as volume %.
9.79 Hydrogen sulphide is absorbed from a gaseous mixture containing 26% H 2S and 74%
inerts by a solution in a tower. The tower operates at 4 bar, and 330 K. The gases leave
the tower with an H 2S content of 8%. Assuming that H2S is alone removed and nothing
is added as the gases pass through the tower and if the feed to the tower is 3000 m 3/
h, calculate
(a ) The amount of H2S recovered from the gas
( b) The percentage recovery of H2S
9.80 A gas mixture consisting of 60% N 2 and 40% S03 is admitted to an absorption column
at a rate of 100 kmol/h. It is contacted with a stream of 50% H 2S04 flowing counter -
current to the gas stream at a rate of 6000 kg/h. The gases leave at 101.3 kPa . The
water lost with the exit gases exerts a partial pressure of 26.66 kPa . If the concentrated
 Material Balance in Unit Operations 293

acid leaving the bottom of the column contains 74.73% H2S04 what percent of the
entering S03 will be absorbed and converted to acid?
9.81 In the preparation of cooking liquor for a sulphite pulp mill, an absorption column is
used to absorb S02 in a weak liquor. The weak liquor enters the top of the column
at a rate of 1.5 m 3/min with S02 concentration of 0.5% (weight) and leaves with S02
concentration of 1.0% (weight). The gas stream entering the bottom of the column and
passing in the counter-current direction to the liquid stream contains 15% S02. When
the gas leaves the top of the column, 80% S02 is absorbed . The pressure in the column
is 1.5 bar and the temperature is 310 K . Assuming that the liquor has a specific gravity
of 1.0, determine the following :
(a ) The amount of S02 absorbed per minute
( b) The molar flow rate of gas entering the absorber
( c ) The percentage of S02 in the gas leaving the column
(d ) The volumetric flow rate of gas leaving the absorber
9.82 Figure 9.35 represents the flow sheet for the recovery of acetone from air. All
compositions are on a weight basis. Make a material balance and determine the quantities
of the following streams:
(a ) Water added in the absorber
( b) Acetone-free air leaving the absorber
( c ) Aqueous solution of acetone leaving the absorber
(d ) Distillate product
(e ) Bottom product

Air (99.5% air, Condenser

Water 0.5% water )
1% water

Distillate, 99%
« acetone
Absorber
Distillation column

1400 kg/h gas

(95% air, Bottom product
3% acetone, 4% acetone,
2% water) Acetone, 19% 96% water
Water, 81%
Figure 9.35 Recovery of acetone from air (Exercise 9.82) .
294 Stoichiometry and Process Calculations

Distillation
9.83 A mixture of benzene and toluene containing 10% by mole benzene is continuously
distilled at a rate of 1000 kmol/h in a distillation column. 95% of the benzene in the
feed is recovered as distillate product which contains 98% benzene and 2% toluene.
Calculate the following:
(a ) The moles of bottom product
( b) The composition of the bottom product
9.84 An aqueous solution of ethanol containing 10% by weight ethanol is continuously
distilled at a rate of 1000 kg/h in a distillation column. Ten percent of the feed is
recovered as distillate product which contains 60% ethanol and 40% water. Calculate
the following:
(a ) The weight of alcohol lost in the bottom product
( b) The composition of the bottom product
9.85 A distillation column is charged with aqueous solution of ethanol containing 35%
ethanol by weight. The concentrated alcohol is withdrawn as the distillate containing
85% alcohol. The bottom product (residue) contains 5% ethanol. Determine the following:
(a ) The mass of distillate per 100 kg of feed
( b) The ratio of the mass of the distillate to mass of the residue
9.86 A continuous distillation column is used to regenerate solvent for use in a solvent
extraction unit. The column treats 100 kmol/h of a feed containing 15% (mol) ethyl
alcohol and the rest water. The overhead product is 89.43% alcohol and the bottom
product is 0.5% alcohol. The overhead is sent to the extraction unit and the bottom
is wasted. What is the daily requirement of make -up alcohol in the solvent extraction
unit?
9.87 A benzene-toluene solution containing 40% (weight) benzene is fed into the distillation
column. A distillate product which is rich in benzene leaves the top of the column and
a residue which is rich in toluene leaves the bottom of the column. The distillate
contains 97% (weight) benzene and the bottom product contains 95% (weight) toluene .
Calculate the following:
(a ) The composition of the feed, distillate and the bottom product in mole percent
( b) The moles of distillate and bottom product obtained by separating 100 moles/hour
of the feed
9.88 One thousand kilograms per hour of a hydrocarbon mixture consisting of 40% benzene,
40% toluene and 20% xylene is admitted to the first column of a series of two
distillation columns. The top product from this column contains 99% benzene and 1%
toluene. The bottom product enters the second column in the series where it is
subjected to further purification . The distillate leaving the second column is 95%
toluene and 5% benzene and the bottom product is 90% xylene and 10% toluene.
Calculate (a) the quantity and (b) the composition of the bottom product from the first
column. All concentrations are on a weight basis.
 Material Balance in Unit Operations 295

9.89 One hundred moles of a hydrocarbon mixture consisting of 20% ethane , 40% propane
and 40% butane is admitted to the first column of a series of two distillation columns.
The top product from this column contains 95% ethane , 4% propane and 1% butane.
The bottom product enters the second column in the series where it is subjected to
further purification. The distillate leaving the second column is 99% propane and 1%
butane and the bottom product is 8.4% propane and 91.6% butane . Calculate (a) the
quantity and composition of the bottom product from the first column and (b) the
quantity of the distillate from the second column.
9.90 The feed to a distillation column is separated into net overhead product containing
nothing with a boiling point higher than that of isobutane and bottoms containing
nothing with a boiling point below that of propane. The composition of the feed is

Component mol%
Ethylene 2.0
Ethane 3.0
Propylene 5.0
Propane 15.0
Isobutane 25.0
w-Butane 35.0
w-Pentane 15.0

The composition of isobutane in the overhead is 5.0 mol%, and the concentration of
propane in the bottom is 0.8 mol%. Calculate the composition of the overhead and
bottom streams per 100 moles of feed .
9.91 Refer to Figure 9.36. Feed enters the first column of the two-stage unit with a flow
rate of 100 kg/s. The top product from this column is withdrawn at a rate of 40 kg/s.

D, 95% ^4 , 5%
(B + C ) F , 5% A , 95%
f f * (B+ C )

Feed, 40% ,4 , (1 ) (2 )
60% ( B + C )

* G * H , 100% C

Figure 9.36 Operation in Exercise 9.91 .

Streams D and F contain B and C in the ratio 10 : 1 by weight. All percentages are
on a weight basis. Determine the following:
296 Stoichiometry and Process Calculations

(a ) Flow rates of streams F , G and H

( b) Percent of B and C in the feed, D and F
9.92 Oxygen is produced by liquefying air and distilling it at low temperatures. Liquefied air
(21% 02, 79% N 2) is sent to a distillation column where it is separated as stream 1
(60% N 2, 40% 02) leaving as bottom and stream 2 (96% N 2, 4% 02) leaving at the
top. Both streams are then fed to another column. Nitrogen-rich product (98% N 2, 2%
02) is withdrawn as distillate and oxygen-rich product (99.5% 02, 0.5% N 2) is
withdrawn as the bottom product. Refer to Figure 9.37.
Product nitrogen,
98% N' ,2
Stream 2, ’
96% N2, 2% O 2
4% O.

Air ( liquid ),
79% N2,
21% O'2

Product oxygen,
0.5% N',2
’
99.5% O2
Stream 1, 60% N2,
40% O'2 -
Figure 9.37 Air separation in Exercise 9.92 .

Calculate the following:

(a ) The percent recovery of oxygen in the oxygen-rich product
( b) The flow rate of stream 1 in mol/s for the production of oxygen-rich product at
a rate of 3.2 kg/s.
 10 Material Balance with
Chemical Reaction

We have already seen that the general material balance equation can be written in the following
form:
material input material output material generation material consumption
+
to the system from the system within the system within the system

accumulation of
material within ( 10.1 )
the system
In the absence of generation and consumption of materials, the above equation reduces to
input - output = accumulation ( 10.2)
Under steady state, there is no accumulation and the terms on the right-hand sides of both the
above equations reduce to zero. For processes with chemical conversion , Eq. (10.2) is not
universally valid. Consider, for example, a process in which 1 kmol (100.09 kg) CaC03 is
subjected to calcination reaction in a kiln. The following reaction takes place.
CaC03 -> CaO + C02
Assume that only 90% of the feed is converted. Then the quantities of the reactants and
products in mass and molar units are given as follows:

Material Input Output

Mass (kg) Moles (kmol) Mass (kg) Moles (kmol)
CaC03 100.09 1 10.01 0.1
CaO 0 0 50.47 0.9
C02 0 0 39.61 0.9
Total 100.09 1 100.09 1.9
297
298 Stoichiometry and Process Calculations

We can see that Eq. (10.2) is satisfied for the total material balance written on the mass basis,
but is not satisfied if the balance is considered on molar units. When writing component
balances for individual chemical species, Eq. (10.2) is not applicable either on a mole basis or
on a mass basis. In this case the balance equation Eq. ( 10.1) should be used taking the
generation and consumption terms into account. However, Eq. (10.2) is still valid on a mole
or mass basis if the balance is written for atomic species. Thus, the amounts of carbon entering
and leaving the calciner are the same irrespective of whether the amount is expressed on a mole
basis or mass basis.

10.1 COMBUSTION OF SOLID, LIQUID AND GASEOUS FUELS

The consumption of energy by chemical process industries is quite large in comparison with
other industries. At present almost all the process energy requirement is met by the combustion
of fossil fuels. The fossil fuels consist chiefly of carbon and hydrogen, with small amounts of
oxygen, nitrogen, sulphur, mineral matter and moisture. The composition of the fuels varies
widely depending upon the type and source of the fuels.
During combustion the chemical energy stored in the fuels is released as heat energy. The
combustion process is the rapid chemical reaction of oxygen with materials and is used generally
for the purpose of liberating heat energy. The combustion of coal, fuel oil or natural gas is the
main source of heat energy in process industries. The combustion process is generally carried
out in furnaces and the heat liberated may be utilized for the production of steam for power
generation and for heating purposes in the plant. Combustion calculations are carried out to relate
quantities and composition of the fuel to those of the flue gas. In the following paragraphs some
special terms used with reference to combustion calculations are discussed.
Theoretical oxygen is the oxygen required to burn all carbon in the fuel to carbon dioxide
and all hydrogen to water. Oxygen required for combustion is supplied through air. To ensure
complete combustion, usually more air is supplied than what is needed theoretically. If there
is no adequate supply of air, incomplete combustion results, and carbon monoxide and free
hydrogen will be present in the flue gases. Excess oxygen is the oxygen furnished through
air in excess of the theoretical requirement of oxygen for the combustion. It is usually
expressed as percent excess oxygen . Percent excess oxygen and percent excess air are the
same. If oxygen is already present in the fuel, the percent excess oxygen is based on the net
oxygen. Net oxygen is the total oxygen required for complete combustion minus the oxygen
present in the fuel. Though a large percent excess air is preferred from the point of view
of complete combustion , excess air supply is not without some problems. A large volume of
gas in the furnace reduces the temperature attained on combustion and increases the loss of
heat with the flue gas leaving the furnace.

10.1. 1 Orsat Analysis

The Orsat analysis lists the composition of the flue gas on a dry basis. The orsat apparatus
measures the amount of C02, CO and 02 in a given sample of flue gas. The principle of
measurement can be explained with the help of Figure 10.1.
 Material Balance with Chemical Reaction 299

4 Gas in

A^ r\
ft
M
ft Gas burette

Levelling
bottle

Gas absorption pipettes

Figure 10.1 Orsat apparatus.

The Orsat apparatus consists of a gas measuring burette in which a 100- ml water saturated
flue gas sample is initially taken . The gas from the burette can be passed through three
absorption pipettes in succession. The C 02 in the sample is absorbed by passing the gas
through the pipette containing KOH solution. After ensuring the complete absorption of C02,
the volume change of the gas is noted. The decrease in volume is the volume of C02 plus the
water vapour it contained. The amount of oxygen in the flue gas sample is next found out by
passing the gas through the second pipette which contains an oxygen-absorbing liquid such as
alkaline pyrogallate solution and by measuring the decrease in volume. Similarly, the CO content
is measured by absorbing the gas in cuprous chloride solution. The decrease in volume in each
case measures the volume of C02, 02 and CO respectively plus the water vapour associated
with each of these gases. The ratio of the amount of water vapour associated with each gas
to the amount of gas absorbed in each case is constant. This means that the decrease in volume
in each case is equal to the volume percent of the gas on a dry basis. For example, assume
that 100 mL of the gas sample contained 50 mL of C02, 10 mL of CO, 30 mL of 02 and 10
mL of H20 vapour. On absorbing C02, the decrease in volume would be 50 + 50 x ( 10/90)
= 55.56 mL which is the percent of C02 in the gas on a water-free basis. Similarly, the
concentrations of 02 and CO are respectively 33.33% and 11.11%. The percent of nitrogen is
found out by subtracting from 100 the sum of the percent concentrations of C02, CO and 02.
300 Stoichiometry and Process Calculations

The qualitative aspects of material balance in combustion process can be made clear with
the help of Figure 10.2.

Fuel Air Flue gas

C C C >
- -> CO2 CO
O O o * O2 > o2
S s * > so2 so3
H H H >
-

N2 N > N2 3 — N2

H,0 - H2O H,0

Ash
-> Ash
C, H, N, S, O
X3
o cr o
CO
Refuse
23 (From solid fuel )
Figure 10.2 Material balance in combustion .

In combustion process there are three streams: the fuel, the air supply and the flue gas.
Sometimes, as in the case of solid fuels, a refuse stream, which is constituted by the mineral
matter present in the fuel, and unbumed fuel constituents also will be present. The material
balances on the various elements can be written in order to establish the quantitative relationship
between different streams.
The masses of the fuel burned and the flue gases produced can be related by a carbon
balance. All the carbon in the flue gas (such as in C02, CO, soot, etc.) comes from the fuel,
since C02 in the air is negligible. The amount of refuse formed may be obtained by making
an inert material balance { ash balance ) around the furnace. The key component relating the
solid fuel and the furnace refuse is the ash. All the ash in the fuel leaves the furnace with the
refuse. Some of the carbon charged in the solid fuel remains unbumed and leaves with the
refuse. An ash balance and a refuse analysis would be necessary to determine the fraction of
carbon charged that is unbumed. The nitrogen in the fuel plus that in the air equals the nitrogen
in the flue gas. Thus the nitrogen balance can be used to find out the amount of air that was
supplied per unit mass of the flue gas. On combustion, the hydrogen in the fuel becomes water
and it leaves with the flue gas. The total water present in the flue gas is made up of water
produced by the combustion of hydrogen with oxygen plus the moisture present in the fuel and
air. The oxygen balance can thus be made to determine the amount of hydrogen in the fuel.
This gives
moles of oxygen used for burning H 2 = moles of 02 in the fuel and air - moles of
oxygen in the dry flue gas as C02, S02, CO, 02, etc.
Knowing that one mole of oxygen is equivalent to two moles of hydrogen, we can determine
the moles of hydrogen in the fuel that have combined with oxygen to form water. Since the
flue gas analysis is reported on a dry basis, it is necessary that the amount of water in the flue
 Material Balance with Chemical Reaction 301

gas be known to find the volume of wet flue gas. This is done by taking a water balance around
the furnace, i.e.
mass of water in fuel and air + mass of water formed by the
combustion of H 2 in the fuel
= mass of water in the wet flue gas
10.1.2 Proximate and Ultimate Analysis of Coal
The proximate analysis of coal is an empirical procedure for analysis of coal in order to list
the composition in terms of the following items, all expressed as percentages by weight of coal:

• Moisture: The loss of weight when coal is heated in an oven at 105°C.

• covered
Volatile combustible matter: The loss in weight when the coal sample is heated in a
crucible for about 7 minutes at 950°C minus the weight of the moisture.
• combustion
Ash: The weight of residue obtained when the sample of coal is subjected to complete
in a muffle furnace at 700°C-750°C.
• already
Fixed carbon: Calculated as 100 minus the sum of the moisture, volatile matter and ash
obtained, i.e.
FC = 100 - ( M + VCM + A ) (10.3)
where FC, M , VCM and A are the percentages of fixed carbon, moisture, volatile combustible
matter and ash respectively. Due to the environmental problems associated with the combustion
of sulphur, it is now required to report the percentage by weight of sulphur also in the
proximate analysis.
The ultimate analysis of coal gives the composition as the percentage by weight of the
various elements such as C, H, N, O, S, etc. and the ash. The ultimate analysis provides the
necessary data required for material balance in the combustion of coal. The analysis is carried
out by elaborate and standard chemical techniques. The carbon dioxide, water and sulphur
dioxide formed by burning coal in a sufficient supply of oxygen determine respectively the
amounts of carbon, hydrogen and sulphur in coal. Carbon dioxide and water are absorbed in
suitable solvents and sulphur dioxide in lead chromate. The nitrogen in the coal is determined
by the Kjeldahl method. The percentage of oxygen in the coal is found out by subtracting the
percentages of all other constituents from 100.
The hydrogen reported in the ultimate analysis includes the hydrogen in the volatile matter
and the hydrogen in the moisture present in coal. The carbon reported in the ultimate analysis
includes the fixed carbon and the carbon present in the volatile matter. The volatile matter
contains complex organic substances made up of C, H, O, N and S. The fixed carbon is the
combustible residue of tar and coke resulting from the pyrolysis reaction at 950°C. Oxygen and
total hydrogen may be reported in the ultimate analysis, or the oxygen may be reported as
equivalent “ combined water” in which case, the remaining hydrogen is the available hydrogen
or net hydrogen. The available hydrogen is the only hydrogen that requires oxygen from the
air for combustion.
302 Stoichiometry and Process Calculations

EXAMPLE 10.1 Propane is burned with excess air to ensure complete combustion. If 55 kg
of C02 and 15 kg of CO are obtained when propane is completely burned with 500 kg air,
determine the following:
(a ) The mass of propane burnt (in kilograms)
(b ) The percent excess air
( c ) The composition of flue gas
Solution Basis: 55 kg of C02 and 15 kg of CO obtained by burning propane with
500 kg of air
The combustion of propane in this example is schematically represented in Figure 10.3.

C02, 55 kg
Propane , Combustion of
F mol propane CO, 15 kg
Water
i L

Air, 500 kg
Figure 10.3 Combustion of propane ( Example 10.1).

The molecular weight of C02 is 44 and the molecular weight of CO is 28. Therefore,

Moles of C02 in the flue gas = —44 = 1.25 kmol

Moles of CO in the flue gas = —28 = 0.5357 kmol
— — = 17.24 kmol,
500
Air supplied =
29
(a ) Let F be the moles of propane burned. It can be calculated by a carbon balance:
moles of carbon in the inlet gas = moles of carbon in the exit gases
Since one mole of propane contains three moles of carbon, the carbon balance gives
3F = 1.25 + 0.5357 (A)
Therefore, the moles of propane burned F = 0.5952 kmol.
Mass of propane burned = 0.5952 x molecular weight of propane
= 0.5952 x 44.064 = 26.23 kg
( b ) One mole propane requires 5 moles of oxygen for complete combustion:
C 3 H8 + 502 -> 3C02 + 4H20 (B)
Theoretical oxygen requirement is
0.5952 x 5 = 2.976 kmol
 Material Balance with Chemical Reaction 303

Theoretical requirement of air is

—21 x 2.976 = 14.17 kmol

excess air , ^ air supplied - theoretical air _ _
Percent excess of air =
thoretical air
xlOO = —
theoretical air
x 100 1

17.24 - 14.17
xlOO = 21.67 %
14.17
( c ) The products of combustion contains C02, CO, 02, N 2, and H20 vapour produced on
combustion. The reactions that occur are as follows:
C 3 H8 + 502 -> 3C 02 + 4H20 (C )

02 ->
C3H8 +
^ 3CO + 4H20

When 0.5952 kmol propane is burnt, 0.5952 x 4 = 2.3808 kmol water is produced. The
(D)

moles of oxygen present in the combustion gases can be determined by an oxygen balance:
02 in the air supplied = 02 present in the flue gas as C02, CO and H20
+ unbumed oxygen
That is,

17.24 x
100
—
= 1.25 + 0.5357 x 0.5 + 2.3808 x 0.5 + unbumed 02
Therefore, the amount of free oxygen present in the flue gas is

17.24 x —
100
- (1.25 + 0.5357 x 0.5 + 2.3808 x 0.5) = 0.9122 kmol

[Alternatively the moles of oxygen in the flue gas can be obtained by considering the
reaction in steps. With every 3 mol C02 formed according to reaction C, 5 mol oxygen
is consumed, and with every 3 mol CO formed according to reaction D 3.5 mol
oxygen is consumed. Thus,

moles of oxygen consumed by reaction C = 1.25 x — = 2.0833 kmol

Therefore,

moles of oxygen consumed by reaction D = 0.5357 x —3.5 = 0.6250 kmol

total moles of oxygen consumed = 2.0823 + 0.6250 = 2.7083 kmol
moles of oxygen supplied = 17.24 x 0.21 = 3.6204 kmol
Moles of free oxygen present in the flue gas by an oxygen balance is equal to the moles
of oxygen supplied minus the moles of oxygen consumed . Therefore, moles of free
oxygen = 3.6204 - 2.7083 = 0.9121 kmol]
304 Stoichiometry and Process Calculations

The entire nitrogen in the air supplied will appear in the flue gas. Therefore, flue gas
contains 17.24 x 0.79 = 13.6196 kmol. The composition of the flue gas can now be
calculated as shown in the table below.
Constituent The number of moles Percent composition,
in the flue gas (mol%)

co2 1.25
1 25 -x 100 - 6.69%
18.6983
0 5357 -
CD 0.5357 xlOO 2.87%
18.6983
0- 9122
o2 0.9122 xlOO - 4.88%
18.6983

N2 13.6196 -
13 6196
18.6983
xlOO - 72.84%

2 - 3808
H2O 2.3808 x 100 - 12.72%
18.6983
Total 18.6983 100

EXAMPLE 10.2 Hydrogen-free coke containing 85 % (weight) carbon and the rest inert
materials is burned in a furnace. It is found that during combustion 5% of the coke charged
is lost unbumed. The flue gas analysis shows 14.84% C02, 1.65% CO, 5.16% 02 and 78.35%
N2. The flue gas leaves the furnace at 500 K and 100 kPa. Calculate the following:
(a) The percent excess air on the basis of complete combustion of coke
( b) The weight of air supplied per kg of coke charged
(c ) The volume of flue gas per kg of coke charged
(d) The composition of the refuse from the furnace
Solution Basis: 100 kmol flue gas
Flue gas, 100 kmol
C02 = 14.84 kmol
CO = 1.65 kmol
02 = 5.16 kmol
N 2 = 78.35 kmol

Coke, F kg Refuse,
85 % carbon > Furnace ^
Carbon = W = 0.05 F kg,
15 % inerts Inerts

Air, A kmol
Figure 10.4 Combustion of coke (Example 10.2).
 Material Balance with Chemical Reaction 305

Let F kg be the mass of coke charged and W kg be the mass of coke left unbumed per
100 kmol flue gas produced. W = 0.05 F .
The amount of coke charged to the burner to obtain 100 kmol flue gas can be obtained
by taking a carbon balance.
Carbon present in the flue gas = carbon in C02 + carbon in CO
= 14.84 + 1.65 = 16.49 kmol = 16.49 x 12 = 197.88 kg
Carbon in the coke charged = F x 0.85 kg
Carbon in the unbumed coke = W x 0.85 = 0.05F x 0.85
Carbon balance:
F x 0.85 = 0.05F x 0.85 + 197.88
Solving the above equation, we get
197.88
0.95 x 0.85
= 245.05 kg
( a ) Let A kmol air is supplied for combustion. Since the nitrogen in the flue gas is coming
from the air supplied, a nitrogen balance gives
A x 0.79 = 78.35
or A = 99.177 kmol
Thus,
Oxygen supplied = A x 0.21 = 99.177 x 0.21 = 20.827 kmol
Theoretical oxygen requirement is calculated as the moles of oxygen required for the
complete conversion of carbon in the coke charged to C02 . That is,

245.05 x 0.85
theoretical requirement of oxygen
12
= 17.358 kmol
excess oxygen
Percent excess of oxygen 1QQ
theoretical oxygen ^
20.827 - 17.358
x 100 = 19.99%
17.358
Therefore,
Percent excess air = percent excess oxygen = 19.99%

(b ) Air supplied = 99.177 kmol = 99.177 x 29 = 2876.133 kg

Coke charged = 245.05 kg
2876.133
Air supplied per kg of coke charged =
245.05
= 11.74 kg
306 Stoichiometry and Process Calculations

( c ) For 100 kmol flue gas, 245.05 kg of coke is charged. Therefore, the volume of flue
gas at 500 K and 100 kPa is

-
245.05^
i _ x 22.414
100 273.13
= 16.96 m3
( d ) The refuse from the furnace is made up of inerts in the coke charged and the unbumed
carbon. Therefore, the total weight of refuse is:
carbon in the refuse = F x 0.05 x 0.85 = 10.41 kg
inerts in the refuse = F x 0.15 = 36.76 kg
Therefore, the total weight of refuse is
36.76 + 10.41 = 47.17 kg
Composition of refuse is

carbon =
^ tx-
47.17
100 = 22.07 %

inerts =
^^
47.17
x 100 = 77.93%

EXAMPLE 10.3 A fuel oil containing 70% carbon by weight and the rest combustible
hydrogen and moisture is burned with excess air. The flue gas analyzed 9% C02, 2% CO, 3%
02 and 86% N2. Determine the following:
(a) The percentage of excess air
( b) The ratio of carbon to combustible hydrogen in the fuel on a weight basis
(c ) The ratio of carbon to total hydrogen in the fuel on a weight basis
(d) The percentages of combustible hydrogen and moisture in the fuel
( e) The mass of moisture present in the flue gas per kg of oil burned
Solution Basis: 100 kmol flue gas
Carbon content in the flue gas = carbon in C02 and CO = 11 kmol
Let F kg be the mass of fuel burned and A kmol be the amount of air supplied.
( a ) Nitrogen in the flue gas = 86 kmol
Since the fuel contains no nitrogen, the nitrogen present in the flue gas comes from
air. The nitrogen balance is
ozr
Ax 0.79 = 86 => A = = 108.86 kmol
0.79
Oxygen in the air supplied = 108.86 x 0.21 = 22.86 kmol
If CO in the flue gas were completely converted to C02, the moles of oxygen present
in the flue gas would be 3 - 1 = 2 kmol.
That is, excess oxygen is 2 kmol.
 Material Balance with Chemical Reaction 307

oxygen excess
Percent excess oxygen = xluO
theoretical oxygen

= 22.86 - 2 x 100 = 9.59%

( b ) The combustible hydrogen in the fuel is determined from the quantity of oxygen that
is consumed by the net hydrogen in the formation of water. Of the 22.86 moles of
oxygen supplied, the oxygen that is accounted in the flue gas as C02, CO or excess
oxygen is only 9 + 1 + 3 = 13 kmol. The difference has been utilized by the net
hydrogen in the formation of water. That is, the oxygen balance is
Oxygen in the air supplied = oxygen accounted in the flue
gas as C02, CO or excess oxygen
+ oxygen consumed by the net hydrogen
The amount of oxygen consumed by net hydrogen is
22.86 - 13 = 9.86 kmol
Therefore, the net hydrogen burned is
2 x 9.86 = 19.72 kmol = 39.76 kg
The mass of carbon burned is
9 + 2 = 11 kmol = 132 kg
The ratio of carbon to net hydrogen in the fuel is
132
39.76
= 3.32 :1
( c ) For 1 kg of net hydrogen in the fuel, carbon present is 3.32 kg. Let x kg be the mass
of moisture present in the fuel for every kilogram of net hydrogen present . It is given
that the weight percentage of carbon in the fuel is 70% . Therefore,
3 32
0.7 =
(1 + 3.32 + x)
which on solving gives x = 0.423 kg.
The mass of hydrogen present in 0.423 kg of moisture is
2 - 016
0.423 x = 0.047 kg
18.016
Therefore,
Total hydrogen present = 0.047 + 1 = 1.047 kg
The ratio of carbon to total hydrogen is
3.32
1.047
= 3.17 : 1
( d ) Carbon = 3.32 kg; combustible hydrogen = 1.0 kg and moisture = 0.423 kg. The
percentage composition by weight is
308 Stoichiometry and Process Calculations

1.00 1.00
net hydrogen = x l 00 = x 100 = 21.08%
(1 + 3.32 + 0.423) 4.743
0 423
moisture = ^^
4.743
x 100 = 8.92%

( e) Since the fuel contains 70% carbon, 21.08% net hydrogen and 8.92% moisture, the
products of combustion when 100 kg of fuel is burned will contain

8.92 + —2.016 x 21.08 = 197.3 kg

The mass of moisture in the flue gas per kg of fuel burned = 1.973 kg.

EXAMPLE 10.4 A producer gas contains 9.2% C02, 21.3% CO, 18% H 2, 2.5% CH4, and
the rest N2. It is burned with an excess supply of air. The flue gas analysed 9.05% C02, 1.34%
CO, 9.98% 02 and 79.63% N 2. Determine the following:
( a ) The volumetric ratio of air supplied to the fuel burned
( b ) The percent excess air supplied
( c ) The percent of nitrogen in the flue gas that came from the fuel.
Solution Basis: 100 moles of flue gas
Producer gas, F lcmol Flue gas, 100 kmol,
9.2% C02, 9.05% C02,
21.3% CO, Combustion 1.34% CO,
18% H 2, chamber 9.98% 02,
2.5% CH4, Ai 79.63% N2
N2 49%

Air, A kmol
Figure 10.5 Combustion of producer gas ( Example 10.4).

Let F moles of fuel be burned with A moles of air to obtain 100 moles of dry flue gas.
Carbon balance:
carbon in the fuel burned = carbon in the flue gas as C02 and CO
0.092F + 0.213F + 0.025F = 9.05 + 1.34 = 10.39 kmol
Therefore, the moles of fuel burned to produce 100 kmol flue gas, F = 31.4848 kmol.
Air supplied for the combustion may be obtained by a nitrogen balance. Nitrogen in the flue
gas is the sum of the nitrogen present in the fuel and that in the air. The mole percentage of
nitrogen in the producer gas = 100 - 21.3 - 9.2 - 2.5 - 18.0 = 49% .
Nitrogen balance:
nitrogen from the fuel + nitrogen in the air = nitrogen in the flue gas
31.4848 x 0.49 + A x 0.79 = 79.63
Solving this we get A = 81.2689 kmol.
 Material Balance with Chemical Reaction 309

81.2689
( a ) The molar ratio of air to fuel is = = 2.58 , which is the same as the volumetric
31.4848
ratio of air to fuel.
( b ) The percent excess of oxygen supplied can be calculated as
oxygen excess
percent excess = 1QQ
theoretical requirement ^
The flue gases contain 9.98 kmol oxygen. The amount of oxygen that would have been
present in the flue gas had the combustion were complete would be less than this by
the amount of oxygen required by CO present in the flue gas for its combustion to
C02. That is,
excess oxygen = 9.98 - 0.5 x 1.34 = 9.31 kmol
Theoretical requirement of oxygen = oxygen supplied - oxygen excess
= 81.2689 x 0.21 - 9.31 = 7.76 kmol
Percent excess of air = percent excess of oxygen
9.31
= 7.76 x 100 = 120%
( c ) 100 kmol of flue gas contains 79.63 kmol nitrogen. 100 kmol fuel results from the
49
combustion of 31.4848 kmol producer gas containing 31.4848 x = 15.43 kmol
nitrogen.
The percent of nitrogen in the flue gas that came from the fuel is
15 43
x 100 = 19.38%
79.63
Note: Consider the calculation of percent excess air in part (b). Instead of calculating the
theoretical requirement of oxygen as the difference between the oxygen supplied and oxygen
present in excess, the theoretical requirement of oxygen can be computed as the oxygen
required for complete combustion of the various constituents of the fuel based on the fuel
analysis. Ideally both calculations should give the same result . Here, let us calculate the oxygen
required by 31.4848 kmol producer gas. The producer gas contains 21.3% CO, 18% H 2 and
2.5% CH4.

CO H
2
022 — ) co2
CH 4 + 202 — C02 + 2H 2 O
^
H 2 + - O 2 ^ H 2O
2
Oxygen required by CO = 0.5 x 21.3 = 10.65 kmol
Oxygen required by methane = 2 x 2.5 = 5.0 kmol
Oxygen required by hydrogen = 0.5 x 18 = 9 kmol
310 Stoichiometry and Process Calculations

Theoretical requirement of oxygen is

(10.65 + 5.0 + 9.0)
x 31.4848 = 7.76 kmol
100
The value obtained is equal to the theoretical requirement already calculated in part (b ) on the
basis of the flue gas analysis. This will rarely be the case in many practical situations. Though
the composition of the products of combustion is a unique function of the composition of the
fuel and the air-fuel ratio employed, since the flue gas analysis and the fuel analysis are done
by two independent measurements, these data are rarely consistent. Any inconsistency in these
measurements may lead to difference in the values calculated for theoretical air requirement by
different methods. For example, try the following problem :
Producer gas containing 5.3% C02, 21.1% CO, 15.3% H 2, 1.0% CH4, and 57.3% N 2 is
burned in a furnace in an excess supply of air. The flue gas contains 14.1% C02, 2.3% 02
and 83.6% N 2. Find the percent excess air.
Calculate the percent excess air by the following three different formulae :
excess oxygen
Percent excess = xlOO
theoretical oxygen
excess oxygen
Percent excess = xlOO
oxygen supplied - excess oxygen
oxygen supplied - theoretical oxygen
Percent excess = xlOO
theoretical oxygen
and you will see that the percent excess air calculated by these different formulae are not the
same.

EXAMPLE 10.5 The following data were obtained in a test on coal fired steam generator. The
ultimate analysis of coal: C, 80.5%; H, 4.6%; O, 5.0%; N, 1.1%; ash, 8.8%. No carbon is lost in
the refuse. The Orsat analysis of flue gas: C02, 16.4%; 02, 2.3%; CO, 0.4%; N2, 80.9%. Calculate
( a ) The weight of dry gaseous products formed per 100 kg of coal fired
( b ) The percent excess air supplied for combustion
Solution Basis: 100 kmol flue gas
( a ) Let W be the mass of coal burned to produce 100 kmol dry flue gas. Taking a carbon
balance, we get
W x 0.805 = (16.4 + 0.4) x 12
This is solved to get W = 250.435 kg.
The mass of 100 kmol flue gas is calculated as below.
Component Moles (kmol) Mol. wt. Weight (kg)
co2 16.4 44 721.6
02 2.3 32 73.6
CO 0.4 28 11.2
N2 80.9 28.014 2266.3
Total 3072.7 kg
 Material Balance with Chemical Reaction 311

Therefore, the mass of dry flue gas produced by the combustion of 100 kg coal
3072 7
— x 100 = 1226.95 kg
= 250.435
( b ) Take a nitrogen balance:
nitrogen from coal + nitrogen from air = nitrogen in the flue gas
250.435 x 0.011 + 28.014* = 2266.3
where * is the moles of nitrogen in the air supplied . Solving the equation, we get
* = 80.80 kmol
The amount of oxygen in the air supplied is

80.80 X —79 = 21.48 kmol

The amount of oxygen required for complete combustion is
250.435 / 80.5
x
4.6 J_ _ _5_ = 19.2659 kmol
100 V
12 2.016 2 32
Percent excess air is
21.48 - 19.27
x 100 = 11.47%
19.27

EXAMPLE 10.6 A furnace is fired with a coal having the following analysis:
Ultimate analysis: C, 63%; H, 12%; O, 16% and ash, 9%.
Proximate analysis: fixed carbon, 39%; volatiles, 42%; moisture, 10% and ash, 9%.
1000 cubic metres of dry air at STP is supplied per 100 kg of coal fired. The dry refuse
from this furnace contains 10.8% fixed carbon, 9.0% volatiles, and 80.2% ash. Only 80% of
carbon that was burnt has gone to C02, the rest to CO. Find the following:
(a ) The composition of the volatile matter reported in the proximate analysis of coal
( b ) The mass and composition of the refuse
( c ) The Orsat analysis of the flue gas
( d ) The percent excess air supplied
( e) The mass of water vapour present per 100 moles of dry flue gas.
Solution Basis: 100 kg coal charged
( a ) 100 kg of coal contains 63 kg of carbon of which 39 kg is fixed carbon. Therefore,
the volatile matter contains 63 - 39 = 24 kg of carbon.

Coal contains 12 kg of hydrogen of which lOx = 1.12 kg of hydrogen is

18.016
present as moisture. Therefore, hydrogen in the volatile matter is 12 - 1.12 = 10.88
kg of hydrogen. Oxygen present in 10 kg of moisture is = 10 - 1.12 = 8.88 kg.
Therefore, oxygen present as volatile matter = 16 - 8.88 = 7.12 kg.
312 Stoichiometry and Process Calculations

The composition of volatile matter is:

Constituent Mass (kg) Weight %

Carbon 24.00 — X 100 = 57.14%

42
10 - 88
Hydrogen 10.88 x 100 = 25.91%
42
7 - 12
Oxygen 7.12 x 100 = 16.95%
42
Total 42.00

( b ) An ash balance on the furnace reveals that all the ash present in the coal appears in
the furnace refuse. Let W be the weight of refuse formed. 80.2% of the refuse is ash.
Then, the ash balance is:
9.00 = 0.802W
or
W = 11.22 kg
The weight of refuse is 11.22 kg of which ash is 9 kg , volatile matter is

11.22 x
100
= 1.01 kg , and fixed carbon is 11.22 x
100
= 1.21 kg . Since the volatile

57.14
matter is 57.14% carbon, the total carbon present in the refuse is 1.21 + 1.01 x
100
25.91
= 1.79 kg. Similarly, the total hydrogen present in the refuse is 1.01 x = 0.26 kg
100

and the total oxygen is 1.01 x — :— = 0.17 kg.

100
Thus the refuse analysis is

Constituent Mass (kg) Weight %

Carbon 1.79 15.95
Hydrogen 0.26 2.32
Oxygen 0.17 1.52
Ash 9.00 80.21
Total 11.22

( c ) The coal burned = 100 - mass of refuse = 100 - 11.22 = 88.78 kg.
The coal burned contains carbon, hydrogen and oxygen the amounts of which are
calculated as below:
Carbon = carbon in the feed - carbon in refuse
= 63 - 1.79 = 61.21 kg = 5.10 kmol
 Material Balance with Chemical Reaction 313

Hydrogen = hydrogen in feed - hydrogen in refuse

= 12 - 0.26 = 11.74 kg = 5.82 kmol
Oxygen = oxygen in feed - oxygen in refuse
= 16 - 0.17 = 15.83 kg = 0.495 kmol
Flue gas:
The flue gas contains C02, CO, H20, 02 and N2.
80% of the carbon burned forms C02 and 20% forms CO. Therefore,
C 02 formed = 0.8 x 5.10 = 4.08 kmol
CO formed = 0.2 x 5.10 = 1.02 kmol
Air supplied = 1000 cubic metres of dry air at STP
1000
22.414
= 44.615 kmol
This consists of 44.615 x 0.79 = 35.25 kmol N2 and 44.615 x 0.21 = 9.37 kmol oxygen.
Nitrogen in the flue gas = nitrogen in the air = 35.25 kmol
Hydrogen in the coal burned = 12 - 0.26 = 11.74 kg = 5.82 kmol.
Therefore, the flue gas contains 5.82 kmol water. Oxygen present in the flue gas can
be determined by an oxygen balance.
oxygen in the coal charged + oxygen in the air = oxygen in the refuse
+ oxygen present in the flue gas as C02, CO, and H20 + free 02
oxygen in the coal charged = 16 kg = 0.5 kmol
oxygen in the refuse = 0.17 kg = 0.005 kmol
oxygen in (C02 + CO + H20) = 4.08 + 0.5 x 1.02 + 0.5 x 5.82 = 7.50 kmol
Therefore, the oxygen balance yields
0.5 + 9.37 = 0.005 + 7.50 + free oxygen
Therefore, the amount of free oxygen is 2.36 kmol.
Flue gas analysis on a dry basis is given as follows:

Component Moles mol %

C02 4.08 9.55
CO 1.02 2.39
02 2.36 5.53
N2 35.25 82.53
Total 42.71

( d ) Oxygen supplied = 9.37 kmol

Oxygen required for complete combustion = oxygen required by carbon in the coal
+ oxygen required by hydrogen in the coal
- oxygen present in the coal
314 Stoichiometry and Process Calculations

Theoretical requirement of oxygen is

—12 + —2.016 x 0.5 - —32 = 7.73 kmol

Excess oxygen = oxygen supplied - theoretical requirement
9.37 -7.73 = 1.64 kmol
excess __ 1
Percent excess = xlOO
theoretical oxygen
1 64
= —7.73
— x 100 = 21.22%
Note: Excess oxygen is the free oxygen present in the flue gas if the fuel is completely
burned. Here it is equal to the free oxygen present in the flue gas less the oxygen
required by CO in the flue gas for converting it into C02 and the oxygen required by
the combustible matter in the refuse. The refuse contains 1.79 kg (0.149 kmol) of
carbon, 0.26 kg (0.129 kmol) of hydrogen and 0.17 kg (0.005 kmol) of oxygen.
Therefore, the material lost with the refuse requires 0.149 + 0.5 x 0.129 - 0.005 =
0.2085 for complete combustion. Therefore, the amount of excess oxygen is
2.36 - 0.5 x 1.02 - 0.2085 = 1.64 kmol

Percent excess = — — — — — - x 100 - 21.22%

• w/ / x• *

( e) Hydrogen in the coal burned = 12 - 0.26 = 11.74 kg = 5.82 kmol. Therefore, the flue
gas contains 5.82 kmol (104.85 kg) water. It means 104.85 kg of water vapour is
104.85
associated with 42.71 kmol dry flue gas. Thus, there is x 100 = 254.49 kg
42.71
of water vapour per 100 kmol dry flue gas.

10.2 OXIDATION OF SULPHUR COMPOUNDS AND RELATED

PROCESSES
Sulphur is one of the raw materials for the production of sulphuric acid. It is available as
elemental sulphur or as sulphide ores such as pyrites. Combustion of sulphur or sulphide ores
is carried out for producing sulphur dioxide. Some sulphur trioxide is also formed during
combustion. It is usually impossible to eliminate completely the formation of sulphur trioxide.
Usually, about 2-10 % of the sulphur burned is converted to trioxide.
02 -> S02
S +
2 S + 302 -> 2 S03
In the combustion gas analysis, the S03 content will not be given since it is removed from
the gas as H 2S04 before the analysis. However, its concentration in the gas can be determined
from the moles of oxygen supplied for combustion, which in turn is calculated from the
 Material Balance with Chemical Reaction 315

nitrogen content of the gas, and the oxygen that is accounted for in the S03-free gas. The
difference between the oxygen supplied and the oxygen accounted for in the product gas is the
oxygen that is consumed for the formation of S03.
When iron pyrites is burned in air the following reactions occur:
4FeS2 + 1102 -> 2Fe203 + 8S02
4FeS2 + 1502 — > 2 Fe203 + 8S03
Since the percent of S03 is not reported in the burner gas analysis, it has to be determined
by the quantity of oxygen unaccounted for in the analysis. The oxygen equivalent of nitrogen
in the burner gas gives the amount of oxygen supplied through air. Subtracting from this the
oxygen consumed for the formation of S02 and the excess oxygen present in the burner gas,
we get the oxygen that is unaccounted. The moles of S03 formed with this oxygen can be
calculated. It is probable that some of the S03 that is formed gets adsorbed in the solid refuse
known as cinder formed on combustion. Analysis of the cinder is necessary to determine the
fraction of the S03 formed that is adsorbed in it. The cinder is made up of Fe203 formed during
the reaction, the unbumed sulphides, and the incombustible materials known as gangue .
Assume that the burner gas analyzes 5% S02 and 10% oxygen, the rest being nitrogen.
The number of moles of oxygen supplied is obtained from the moles of nitrogen in the burner
gas. For a basis of 100 moles of the burner gas, the number of moles of oxygen supplied is
21
85 x —79
= 22.595 mol. The amount of oxygen consumed for the formation of 5 moles of S02

is, according to the chemical reaction given above, 5 x — = 6.875 mol. Therefore, the amount
8
of oxygen unaccounted for is 22.595 - 6.875 - 10 = 5.72 mol . Since according to the reaction
equation, 15 moles of 02 is required for the formation of 8 moles of S03, the moles of S03
g
formed is 5.72 x — = 3.05 mol. Not all this S03 may be present in the burner gas. A part may
15
get adsorbed on the cinder. The quantity adsorbed is to be measured by analysis of the cinder,
and by subtracting this quantity from the total S03 produced, the S03 in the burner gas can
be determined.
In the contact process for the manufacture of sulphuric acid, S02 is converted to S03 in
series of vessels known as converters.
1
so2 + ~
o2 — » so
3

For completing the conversion of S02 to S03, secondary air supply may be necessary in the
converters. The S03 leaving the converters is absorbed in concentrated sulphuric acid by
admitting the gas at the bottom of an absorption column packed with ceramic packings. 98.5
to 99% acid is used as absorption solvent, and it is fed at the top and flows counter-current
to the gas. Usually a 20% oleum product is obtained as the concentrated solution leaving the
absorption tower. (Oleum is S03 dissolved in H 2S04. One hundred kilograms of 20% oleum
contains 20 kg S03 dissolved in 80 kg of H2S04.)
316 Stoichiometry and Process Calculations

EXAMPLE 10.7 Find the Orsat analysis of the burner gas when pure sulphur is burned with
20% excess air. Of the sulphur burned, 5% is converted to S03 and the rest to S02.
Solution Basis: 1 kg-atom sulphur burned
s + o2 — > so 2
Theoretical requirement of oxygen = 1 kmol
Oxygen supplied = 1 . 2 kmol

Nitrogen in the air supplied = 1.2 x —79 = 4.514 kmol

Since only 95% is converted to S02, S02 produced is 0.95 kmol.
Therefore,
S03 produced = 0.05 kmol

Oxygen consumed = 0.95 + —3 x 0.05 = 1.025 kmol

Therefore,
Oxygen remaining = 1.2 - 1.025 = 0.175 kmol
The burner gas contains:

Component kmol Mole% Mole% on SO3 -free basis

0 95 0 95
S02 0.95 x 100 - 16.70 x 100 - 16.85
5.689 5.689 - 0.05
005
S03 0.05 x 100 - 0.88
5.689
0 175
0? 0.175 °' 175

5.689
x 100 - 3.08
5.689 - 0.05
X 100 - 3.10

4 514 4 514
N2 4.514 x 100 - 79.34 x 100 - 80.05
5.689 5.689 - 0.05
Total 5.689

The results in the last column gives the Orsat analysis of the burner gas.
EXAMPLE 10.8 In a sulphuric acid plant, pyrites containing 50% (weight) sulphur is burned
to give S02 which is subsequently converted to S03 in a converter. The analysis of the burner
gas shows 9.5% S02 and 7.0% oxygen. The cinder is analysed and it is found that it contains
2.5% sulphur as S03. Assuming that all the sulphur in the feed is burned, calculate the following:
(a) The weight of pyrites burned per 100 kmol S03-free burner gas
( b) The weight of cinder obtained per 100 kmol S03-free burner gas
(c ) The percent of the sulphur in the charge that is lost in the cinder
(d) The percent of sulphur charged that is there in the burner gas as S03
Solution Basis: 100 kmol S03-free burner gas
The amount of nitrogen present in the burner gas is
100 - (9.5 + 7.0) = 83.5 kmol
 Material Balance with Chemical Reaction 317

Since the nitrogen in the burner gas is that present in the air supplied for combustion, the
amount of oxygen supplied is

83.5 x —79 = 22.20 kmol

4FeS2 + 1102 2Fe203 + 8S02
4FeS2 + 1502 — > 2 Fe203 + 8S03
With every 8 kmol S02 in the burner gas, 2 kmol Fe203 is produced accounting for 3 mol of
oxygen. Therefore the total moles of oxygen accounted for = Moles of oxygen in the burner
gas + Moles of oxygen in the cinder as Fe203. This is equal to
3
9.5 + 7.0 + 9.5 x - = 20.06 kmol
o
The amount of oxygen unaccounted = 22.20 - 20.06 = 2.14 kmol .
2.14 kmol oxygen is consumed by sulphur in the pyrites for the formation of S03. As
15 mol oxygen is required for 8 mol S03, the total S03 formed is

2.14 x
15 —
= 1.14 kmol
( a) Total S burned = 9.5 + 1.14 = 10.64 kmol = 10.64 x 32.064 = 341.16 kg
This constitutes 50% of the pyrites burned. The total pyrites burned is
341.16
0.5
= 682.32 kg
( b ) 10.64 kmol sulphur is equivalent to — :— =
5.32 kmol FeS2. Since the molecular
2
weight of FeS2 is 119.975, the mass of FeS2 present in the ore is
5.32 x 119.975 = 638.27 kg
Weight of gangue = weight of pyrites burned - weight of FeS2 in the ore
= 682.32 638.27 = 44.05 kg
-

5.32 kmol FeS2 on combustion will produce

5.32 x —1 = 2.66 kmol Fe203

Therefore, the mass of Fe203 in the cinder is
2.66 x 159.694 = 424.79 kg
The cinder contains 2.5% sulphur as S03. That is, 100 kg of cinder contains
2.5
~
. = 0.078 kmol S or 0.078 kmol S033.
32.064
^
S03 present in 100 kg of cinder is
0.078 x 80.064 = 6.245 kg
The Fe203 and gangue together constitutes 100 - 6.245 = 93.755% of the total weight
of cinder.
318 Stoichiometry and Process Calculations

Let x be the weight of cinder. Then,

0.937 55x = 424.79 + 44.05 or x = 500.07 kg
Hence, the weight of cinder produced = 500.07 kg.
( c ) Since 100 kg of cinder contains 0.078 kmol sulphur, the total amount of sulphur lost
in the cinder is
0.078
500.07 x
IQQ
= 0.3901 kmol sulphur.
The total amount of sulphur burned is 10.64 kmol.
Percent of total S burned that is lost in the cinder is
0.3901
x 100 = 3.67 %
10.64
( d ) The mass of S03 present in the cinder is
6.245
500.07 x
100
= 31.23 kg
31.23 kg of S03 is equivalent to 0.3904 kmol S03. That is 0.3904 kmol S03 gets
adsorbed in the cinder. Since the total amount of S03 formed is 1.14 kmol, the amount
of S03 present in the burner gas is
1.140.3904 = 0.7496 kmol
-

Therefore, the percent of S charged that is present as S03 in the burner gas is
0.7496
x 100 = 7.05%
10.64

EXAMPLE 10.9 One hundred kilograms per hour of sulphur of 95% purity is burned in dry
air in a sulphur burner. The gas leaving the burner containing 15% S02, 5% 02 and 80% N2
enters a converter after mixing with secondary air. The gas leaving the converter has the
following analysis: S02, 4.5%; 02, 7.5% and N2, 88.0%. The converter gas is passed through
an absorber so that 95% of the S03 in the gas is absorbed in 98% H2S04 to produce 100%
sulphuric acid. Determine the following:
( a ) The volume of secondary air (in m3) supplied per hour at 100 kPa and 300 K
( b ) The mass of 98% H2S04 (in kilograms) supplied per hour
( c ) The mass of 100% acid (in kilograms) produced per hour
Solution Basis: 100 kmol S03-free converter gas
Figure 10.6 schematically represents the production of sulphuric acid in this example.
The amount of oxygen in the air supplied is

88.0 x —79 = 23.39 kmol

The amount of oxygen accounted in the converter gas is 12.0 kmol.
The amount of oxygen consumed for the formation of S03 is
23.39 - 12.0 = 11.39 kmol
 Material Balance with Chemical Reaction 319

Therefore, the amount of S03 formed is

11.39
1.5
= 7.59 kmol
The total amount of sulphur present in the gases leaving the converter is 7.59 + 4.5 = 12.09
kmol.
Or, 12.09 kmol sulphur on combustion produces 100 kmol S03-free converter gas.
Basis: 100 kmol S03-free burner gas
The amount of oxygen accounted for in the burner gas = 15.0 + 5.0 = 20.0 kmol. Since
the burner gas contains 80 kmol nitrogen, the amount of oxygen in the air supplied is

80 x —79 = 21.2658 kmol

98 % sulphuric
acid
-

Air Secondary air

02, 21%, 02, 21%,
N2, 79% N2, 79%
Absorber

100 kg of impure
sulphur, S = 95 %
Burner Converter
Converter gas
S 02, 4.5 %,
Burner gas
15% SO2
’
02, 7.5% and
5 % O2 N2, 88.0 %
80% N2
100% sulphuric acid
Figure 10.6 Production of sulphuric acid in Example 10.9.

Therefore, the amount of oxygen consumed forming S03 is

21.2658 20 = 1.2658 kmol
-

The amount of S03 present in the gases leaving the burner is

1.2658 x
1.5
—
= 0.8439 kmol
Therefore, the total sulphur burned to produce 100 kmol S03-free burner gas is
15.0 + 0.8439 = 15.8439 kmol
Basis: 100 kg impure sulphur charged
320 Stoichiometry and Process Calculations

The amount of sulphur burned is

95
95 kg = = 2.9628 kmol
Let x kmol S03-free burner gas be produced per 100 kg of sulphur charged. Since the total
moles of S present in the gas leaving the burner is 15 + 0.8439 = 15.8439 kmol, a sulphur
balance can be written for the burner, i.e.
15.8439
2.9628 = xx
100
Therefore, the moles of S03 free burner
- gas produced by the combustion of 2.9628 kmol
sulphur is
100
x= x 2.9628 = 18.70 kmol
15.8439
The composition of the burner gas can now be calculated:
S02 = 0.15 x 18.7 = 2.805 kmol
02 = 0.05 x 18.7 = 0.935 kmol
N2 = 0.80 x 18.7 = 14.960 kmol
Total = 18.70 kmol
0 8439
S03 = X 18.7 = 0.1578 kmol
100
A sulphur balance can be written for the combined system constituted by the burner and
converter. Let y be the moles of S03-free converter gas produced by the combustion of 2.9628
12:09
kmol sulphur. Then , 2.9628 = y x —100— .
Solving this, y , the moles of S03-free converter gas produced by the combustion of
2.9628 kmol sulphur is

— — x 2.9628 = 24.506 kmol

12.09
The converter gas contains:
S02 = 0.045 x 24.506 = 1.1028 kmol
02 = 0.075 x 24.506 = 1.838 kmol
N2 = 0.88 x 24.506 = 21.5653 kmol
Total = 24.506 kmol
Therefore ,

S03 — x 24.506 = 1.86 kmol

100
Now, refer to Figure 10.7, which schematically shows the material balance.
 Material Balance with Chemical Reaction 321

98 % sulphuric acid
1591.7 kg
-
Exit gas
502, 1.1028 kmol
02, 1.838 kmol
Air, 18.937 kmol Secondary air, N 2, 21.5653 kmol
02, 21% 8.36 kmol 503, 0.093 kmol
N2, 79 % 02, 21%
100 kg of N2, 79%
impure
sulphur, Absorber
S, 2.9628
kmol
Burner Converter
Burner gas Converter gas

S02, 2.805 kmol; 02, 0.935 kmol;

502, 1.1028 kmol
N„14.960 kmol; S03, 0.157 kmol
02, 1.838 kmol
N 2 , 21.5653 kmol
503, 1.86 kmol
100% sulphuric
acid, 1733.2 kg
Figure 10.7 Material balance in Example 10.9.

( a) The converter gas contains 21.5653 kmol nitrogen and the burner gas contains 14.960
kmol nitrogen. The difference must be the amount of nitrogen coming from the
secondary air supplied . Therefore, the amount of secondary air supplied is

(21.5653 - 14.960) x M = 8.36 kmol

At 100 kPa and 300 K, this corresponds to
oo.
8.36
101.3
x 22.414 x
x
300
100 273.15
= 208.5 m3 /h
( b ) Let x kg 98% sulphuric acid is supplied for absorption.
S03 absorbed = 0.95 x 1.86 x 80.064 = 141.47 kg
Then amount of 100% H 2S04 produced is
(x + 141.47) kg
Consider an S03 balance for the absorber.
S03 in the converter gas + S03 in the 98% sulphuric acid
= unabsorbed S03 in the exit gas + S03 in the 100% H2S04
or

1 M
141.47
/
_
+ 0.98xx
80.064
=
.
1 t1
( x + 141.47
/
)x
_
S03 absorbed + S03 in the 98% sulphuric acid = S03 in 100% H 2S04
80.064
98.08 98.08
322 Stoichiometry and Process Calculations

Solving this, we get x = 1591.7 kg.

98% H 2S04 required per hour = 1591.7 kg.
( c ) 100% sulphuric acid produced per hour is
x + 141.47 = 1733.2 kg

10.3 CARBON DIOXIDE FROM LIMESTONE

The processes analyzed in this section are based on limestone as the raw material and are
important in the lime and cement industries. Lime, sold as quicklime consists of 90% calcium
oxide and 0-5% magnesia. Lime is produced by the calcination of limestone in lime kilns (rotary
kilns are preferred for large production rates) where the carbonates of calcium and magnesium
are converted to the respective oxides, and carbon dioxide is obtained as a by-product. The
reactions occurring are the following:
CaC03 + C + 02 -> CaO + 2C02
MgC03 + C + 02 -> MgO + 2C02
As the suitability of lime for any particular use depends on its composition, it is frequently
necessary to regulate the rate of supply and composition of the charge to the calciner. The
material balance calculations are necessary for achieving this as well as for estimating the
amount of C02 obtained as the by-product. Carbon dioxide is used in food industries as a
refrigerant and in carbonated beverages. Also, it is an important fire-extinguisher and a raw
material for many products.
The amount of lime produced per unit weight of fuel charged is known as the fuel ratio,
which can be readily evaluated from the analysis of kiln gas provided the analysis of fuel and
limestone are known. If the fuel ratio is specified, the composition of the product can be
estimated by the material balance. The following examples illustrate the calculations generally
encountered in the calcination of limestone.

EXAMPLE 10.10 Limestone mixed with coke is being burnt in a kiln. An average analysis
of the limestone is CaC03 = 84.5%, MgC03 = 11.5% and the rest inerts. The coke contains
76.0% carbon, 21% ash and 3% moisture. The calcination of CaC03 is only 95% complete and
that of MgC03 is 90%. The carbon in the coke is completely burnt to C02. The kiln is fed
with one kg of coke per 5 kg of limestone. Calculate the weight percent of CaO in the product
leaving the kiln. Assume that the moisture in the feed is completely vaporized.
Solution Basis: A charge consisting of 5 kg of limestone and 1 kg of coke
The limestone charged as feed consists of the following constituents:
4.225
CaC03 = 5 x 0.845 = 4.225 kg = Qg
= 0.0422 kmol

0.575
MgC03 = 5 x 0.115 = 0.575 kg = —84.312
— = 6.82 x 10 “
3
kmol

Inerts = 5 x 0.04 = 0.2 kg

 Material Balance with Chemical Reaction 323

The coke charged contains the following constituents:

0.76
Carbon = 0.76 kg = = 0.0633 kmol
^
0.03
Water = 0.03 kg = = 1.665 x 10 3 kmol
18.016
Ash = 0.21 kg
The reactions occurring are as follows:
CaC03 + C +
02 -> CaO + 2 C02
MgC03 + C + 02 -> MgO + 2C02
The product contains CaO, MgO, unconverted CaC03 and MgC03, inerts and ash
CaO = 0.95 x 0.0422 = 0.0401 kmol = 0.0401 x 56.08 = 2.2482 kg
3
MgO = 0.90 x 6.82 x 10 "

= 6.138 x 10 3 kmol = 6.138 x 10 3 x 40.312 = 0.2474 kg

~ ~

CaC03 = 0.05 x 4.225 = 0.2113 kg

MgC03 = 0.10 x 0.575 = 0.0575 kg
Inerts = 0.2 kg
Ash = 0.21 kg
The total weight of product is
2.2482 + 0.2474 + 0.2113 + 0.0575 + 0.2 + 0.21 = 3.1744 kg
The weight percent of CaO in the product leaving the kiln is
2.2482
x 100 = 70.82%
3.1744
EXAMPLE 10.11 Pure C02 may be prepared by treating limestone with aqueous H2S04. The
limestone used contained CaC03 and MgC03, the remainder being inert insoluble materials. The
acid used contained 12% H 2S04 by weight. The residue from the process had the following
composition— CaS04: 9.00%, MgS04: 5.00%, H2S04: 1.2%, inerts: 0.50%, C02: 0.2% and
H20: 84.10%. During the process, the mass was warmed, and C02 and H20 vapour were
removed. Calculate the following:
( a) The analysis of limestone used
( b) The percentage excess of acid used
(c) The mass of water vaporized and removed per 100 kg of limestone
(d) The mass of C02 obtained per 100 kg of limestone
Solution Basis: 100 kg of residue
Molecular weight of CaS04 = 136.144 and molecular weight of MgS04 = 120.376
The amount of CaS04 present in the residue is
9.00
9.00 kg = = 0.0661 kmol
136.144
324 Stoichiometry and Process Calculations

The amount of MgS04 present in the residue is

5.00
5.00 kg = 120.376 = 0.0415 kmol
(a) CaC03 + H2S04 -> CaS04 + H20 + C02
MgC03 + H 2S04 — > MgS04 + H20 + C02
The mass of CaC03 burned to produce 0.0661 kmol CaS04 is
0.0661 kmol = 0.0661 x 100.08 = 6.6153 kg
The mass of MgC03 burned to produce 0.0415 kmol MgS04 is
0.0415 kmol = 0.0415 x 84.312 = 3.4989 kg
Therefore, the limestone used has the following analysis:

Constituent Mass (kg) Weight %

6 6153
CaC03 6.6153 x 100 = 62.32
10.6142
3 4989
MgC03 3.4989 x 100 = 32.96
10.6142
Inerts 0.50 ( 100 - 62.32 - 32.96) = 4.72
Total 10.6142

( b ) The amount of H 2S04 required by CaC03 and MgC03 for complete reaction is
(0.0661 + 0.0415) = 0.1076 kmol = 10.5534 kg
The mass of excess H 2S04 present in the refuse is 1.2 kg.

Percent excess acid supplied = — —1.2—

X\J • w/
x 100 = 11.37 %

(c) Total sulphuric acid supplied = 10.5534 + 1.2 = 11.7534 kg

Since the acid used is 12% sulphuric acid, the mass of water entering the process is

— 0.12 x 0.88 = 86.1916 kg

The amount of water produced in the reaction is
0.1076 x 18.016 = 1.9385 kg
Total water present = 86.1916 + 1.9385 = 88.1301 kg
Since 100 kg of residue contains 84.10 kg of water, the mass of water vaporized is
88.1301 - 84.10 = 4.0301 kg
This is the amount of water vaporized per 10.6142 kg of limestone.
The amount of water vaporized per 100 kg of limestone is
4.0301
x 100 = 37.97 kg
10.6142
 Material Balance with Chemical Reaction 325

( d ) The amount of C02 produced per 100 kg of residue is

0.1076 kmol = 0.1076 x 44 = 4.7344 kg
The amount of C02 released per 100 kg of residue is
4.7344 _ 0.20 = 4.5344 kg
Therefore, the amount of C02 released per 100 kg of limestone is
4 5344
— — — x 100 = 42.72 kg
10.6142

10.4 REACTIONS INVOLVING PHOSPHORUS AND PHOSPHORUS

COMPOUNDS
Phosphorus exists in nature as phosphate rock. Phosphate rock is mixed with coke and is
reduced to elemental phosphorus in an electric furnace. The liquid yellow phosphorus ( P4)
formed can be converted to red phosphorus by heating.
2Ca3( P04)2 + 10C + 6Si02 -> P4 (yellow grade) + 6CaSi03 + 10CO
523-723 j
P4 (yellow grade) — £ > p4 (red grade)
In India almost all the phosphate rock processing is done for the production of phosphoric acid,
which in turn is converted to calcium and ammonium phosphate for using as fertilizers.
Ca3( P04)2 + 3H2S04 + 6H20 -> 2H3P04 + 3(CaS04 2H20)
Pyrophosphoric acid ( H 4P207) can be produced by heating the orthophosphoric acid ( H3P04)
to 523 K. Hydrochloric acid leaching may also be used for the production of phosphoric acid.
Ca 3(P04)2 + 6 HC1 -> 2 H3P04 + 3CaCl2
Other phosphorus compounds of industrial importance are the different grades of phosphates
of calcium, ammonium and sodium. Based on the method of production from phosphate rock,
there are two grades for calcium phosphate; they are superphosphate and triple superphosphate,
both used as fertilizers.
[Ca 3( P04)2]3 CaF2 + 7 H 2S04(aq) —»> 103CaH 04 - CaS04
4( P )2 7 (superphosphate) + 2 HF
[Ca 3( P04)2]3 CaF2 + 14H 3P04 — CaH PO4( 4 )2 (triple superphosphate) + 2 HF
The basic reaction in the manufacture of ammonium phosphate is the neutralization of
phosphoric acid with ammonia.
NH 3 + H 3P04— » NH H P04 (monoammonium phosphate)
4 2

NH3 + NH H P04 — > ( NH ) HP04 (diammonium phosphate)

4 2 4 2

Sodium phosphates are manufactured from pure phosphoric acid. The orthophosphates
include monosodium phosphate (NaH 2P04), disodium phosphate ( Na 2HP04) and trisodium
phosphate (Na3P04). These salts are used in water treatment, baking powder, fire proofing,
detergent and cleaners.
326 Stoichiometry and Process Calculations

The calculations in processes involving phosphorus and phosphorus compounds are illustrated
with the help of Examples 10.12 and 10.13.
EXAMPLE 10.12 Trisodium phosphate (TSP) is an important water softening compound.
The production of TSP is carried out in a two-step process.
Na2C03 (s ) + H3PO4 (aq) -> Na2HP04 (aq) + H20 (1) + C02 (g)
Na2HP04 (aq) + NaOH (s ) Na3P04 (aq) + H20 (1)
In the first step, a dilute phosphoric acid containing 1.25% H 3P04 is neutralized by reacting
with a stoichiometric quantity of powdered dry soda ash to form a solution of disodium
phosphate. In the second step, the neutralization is completed by the addition of sufficient solid
caustic soda to produce a solution of TSP. The hydrated salt of trisodium phosphate
( Na 3P0412H20) is produced from the solution by evaporation and subsequent crystallization.
For a basis of 1000 kg of dilute phosphoric acid, calculate
(a ) The maximum weight of TSP that can be produced assuming 100% yield in both the
reactions
( b ) The volume of C02 at 310 K and 100 kPa saturated with water vapour given that the
vapour pressure of water at 310 K is 6.27 kPa
Solution Basis: 1000 kg of dilute phosphoric acid treated.
Molecular weight of phosphoric acid = 97.998.
The amount of H3P04 present in the dilute acid is
1 25 12 5
1000 x —
100
— = 0.1276 kmol
= 12.5 kg = 97.998
( a ) Since one mole of phosphoric acid gives one mole of trisodium phosphate, moles of
trisodium phosphate produced = 0.1276 kmol.
Molecular weight of TSP (Na 3P04T 2H20) = 380.166
Maximum weight of TSP obtained = 0.1276 x 380.166 = 48.51 kg
(b ) Moles of C02 produced = 0.1276 kmol.
Since the C02 produced is saturated with water vapour and the vapour pressure of
water at 310 K is 6.27 kPa, moles of water vapour present with 0.1276 kmol C02 is
f\ 97 3
0.1276 x = 8.5357 xl 0
“

kmol
(100 - 6.27 )
Total moles of wet C02 produced = 0.1276 + 0.0085 = 0.1361 kmol

Volume of CO, = 0.1361 x

^^
100
x
310
273.15
x 22.414 = 3.51 m 3

EXAMPLE 10.13 Sodium phosphate is produced by the reaction of soda ash with phosphoric
acid:
H 3P04 + Na 2C03 -> Na 2HP04 + C02 + H20
Na2HP04 + NaOH -> Na 3P04 + H20
 Material Balance with Chemical Reaction 327

The first reaction is carried out by treating an aqueous solution of soda ash with commercial
phosphoric acid containing 85% acid. The disodium phosphate solution is then treated with
50% caustic lye to produce a 20% solution of trisodium phosphate in water. To produce 1000
kg of trisodium phosphate solution, calculate
( a ) The quantity and composition of aqueous soda ash solution
( b ) The weight ratio in which the soda ash solution and commercial phosphoric acid are
to be mixed
Solution Basis: 1000 kg 20% solution of trisodium phosphate in water
Na 3P04 produced = 1000 x 0.2 = 200 kg
200
= 163.974 = 1.2197 kmol
( a ) The amount of soda ash required for the reaction is
1.2197 kmol = 1.2197 x 106 = 129.29 kg
The amount of phosphoric acid reacted is
1.2197 kmol = 1.2197 x 97.998 = 119.53 kg
The amount of NaOH reacted is
1.2197 kmol = 1.2197 x 40.008 = 48.80 kg
Phosphoric acid is available as 85% solution in water, NaOH is present as 50% solution
in water and soda ash is supplied as an aqueous solution. Let x kg water be present
in the soda ash solution. Then we can write the water balance for the process:
water present in the soda ash solution + water present in the aqueous NaOH solution
+ water present in the phosphoric acid solution + water produced
= water present in the trisodium phosphate.
48.80 119 53
x+ x 0.5 + — X 0.15 + 1.2197 x 2 x 18.016 = 800
0.5 0.85
Solving the above equation, we get x = 686.16 kg.
Amount of aqueous soda ash solution = 129.29 + 686.16 = 815.45 kg
129-29
Concentration of soda ash solution = x 100 = 15.86%
815.45
( b ) Since the phosphoric acid reacted is 119.53 kg, the weight of commercial acid mixed
119 53
is = 140.62 kg . The weight of soda ash solution mixed is 815.45 kg.
0
^
weight of soda ash solution _ 815.45 _ 5.8
weight of commercial phosphoric acid 140.62 1
328 Stoichiometry and Process Calculations

10.5 RECOVERY OF METALS AND NON-METALS FROM ORES

Chemical engineering techniques find wide applications in metallurgical industies manufacturing
iron and steel, aluminium, copper, lead and zinc, etc. Iron and steel industry is the most
prominent among the metallurgical industires. Hematite (Fe203), magnetite ( Fe304), pyrites
( FeS2), and siderite ( FeC03) are the common ores of iron. Hematite is the principal ore used
for the producton of iron and steel.
The first step in the manufacture of steel is the production of pig iron in a blast furnace.
The charge consisting of the ore, coke and the limestone flux is introduced into the blast
furnace. Hot air blast is introduced at the bottom of the furnace. Air reacts with coke producing
CO and heat, and iron oxide gets reduced to molten pig iron which is collected at the bottom
of the furnace. Though many different reactions occur in various regions of the furnace, the
essential process occurring in the furnace can be represented by the following chemical
reaction:
Fe203 + 3C -> 2Fe + 3CO
At the highest temperature in the furnace, a part of the silica present is reduced to the metallic
state and is dissolved in the molten iron while the remaining silica and alumina in the charge
reacts with the metallic bases present in the flux and a fusible slag consisting of complex
silicates and aluminates of calcium , magnesium and iron are formed. Thus, the products of a
blast furnace operation are the pig iron, slag and blast furnace gas, the latter being a mixture
of nitrogen, CO, and water vapour with small amounts of hydrogen and methane. The slag
consists of the lime, magnesia, and alumina and alkalies originally present in the charge together
with some silica and manganese oxides.
Example 10.14 illustrates a simple material balance calculation for a blast furnace operation
in which the amount of flux required for producing a given quantity of pig iron is calculated
knowing the composition of the ore, the flux and the coke. The methdos of calculations are
applicable to similar reactions in the recovery of other metals.

EXAMPLE 10.14 For producing 1000 kg of pig iron of composition 95% Fe, 4 % C and
1 % Si, iron ore containing 85.0% Fe203 and the rest Si02 is reduced in a blast furnace using
1000 kg of coke containing 90% C and 10% Si02. The flux used contains 90% CaC03, 5%
MgC03 and 5% Si02. If it is desired that the slag contains 40% ( CaO + MgO), how much
flux is required for producing 1000 kg of pig iron ? Assume that no iron is present in the
slag.
Solution Basis: 1000 kg of pig iron produced in the blast furnace
Figure 10.8 schematically shows the production of pig iron.
Let x be the weight of iron ore charged, y be the amount of flux added and z be the weight
of slag produced, all expressed in kilograms.
Assuming that no iron is present in the slag, the iron balance gives
111.694
xx 0.85 x = 950
159.694
Solving this, we get the weight of iron ore charged, x = 1597.95 kg.
 Material Balance with Chemical Reaction 329

Coke, 1000 kg
90 % carbon,
10 % Si 02
Pig iron , 1000 kg
95 % Fe, 4% C, 1% Si
r

Iron ore
85 % Fe203, Blast furnace
15 % Si02
ii
Slag t
60 % Si 02
40 % ( CaO + MgO)
Flux 90% CaC03,
5 % MgC03,
5 % Si02
Figure 10.8 Production of pig iron in Example 10.14.

Silicon balance:
15 28.086 10 28.086 5 28.086
1597.95 x x + 1000 x x + yx x
100 60.086 100 60.086 100 60.086
^ + zx
60 28.086
= 10 x (A)
100 60.086
(CaO + MgO) balance:
/
90 56.08 5 40.305 40_
jx x + x = zx
V
100 100.08 100 84.305 100
which can be simplified as z = 1.3205 y (B )
Substituting ( B) into (A ) and simplifying, we get y = 428.9 kg.
Thus, the amount of flux required to produce 1000 kg of pig iron = 428.9 kg.

10.6 NITROGEN, AMMONIA AND NITRIC ACID

In this section we discuss through example problems the material balance calculations in
processes such as the synthesis of ammonia, air oxidation of ammonia to form nitric oxide,
the manufacture of urea from ammonia and carbon dioxide, the manufacture of nitric acid by
the oxidation of ammonia and by the reaction of nitrates with sulphuric acid, etc.
Being the major constituent of air, nitrogen is the most abundant raw material which is
commercially utilized for the production of ammonia. Ammonia serves as the source for
nitrogen fertilizers in the form of liquid and aqueous ammonia solutions, ammonium salts and
urea. It also serves as the source of nitric acid and many nitrogen compounds.
Ammonia is produced by the high-pressure catalytic reaction of nitrogen and hydrogen.
Synthesis gas which is a mixture of nitrogen and hydrogen in the stoichiometric ratio (1:3)
compressed to about 100-1000 bar is converted to ammonia in the presence of promoted iron
catalyst at 773-823 K.
330 Stoichiometry and Process Calculations

N2 + 3H 2 2NH3
The old process for the manufacture of HN03 is by the reaction of sulphuric acid with
sodium nitrate.
2 NaN03 + H2S04 -> 2 HN03 + Na2S04
The prominant process for the manufacture of nitric acid nowadays is the air oxidation of
ammonia. Compressed air mixed with anhydrous ammonia is sent through the converter packed
with a Pt-Rh alloy catalyst where the oxidation of ammonia to NO occurs at about 1073 K.
The product gases containing about 10-12% NO is mixed with air in the oxidizer-absorber
system to convert NO to N 02 at about 313-323 K. N02 is absorbed in water producing
HN 03 of 57-60% strength. The major reactions occurring in the air oxidation of ammonia
process for HN03 manufacture are as follows:

NH,3 + -022 -> N0 + - H 220

4 2
2NO + 02 2N02
3N02 + H20 -> 2 HN03 + NO
2N02 -> N204
Among the nitrogen fertilizers, the most important one is urea. In the ammonium carbamate
decomposition process for the manufacture of urea, ammonia and carbon dioxide are compressed
to 100-200 bar and reacted at 445-465 K. Urea is formed from the ammonium carbamate
solution by dehydration.
C02 + 2NH3 -> NH4 COO NH 2
NH 4 COO NH 2 -> NH2 CO NH2 + H20

EXAMPLE 10.15 Nitric oxide is produced by the air oxidation of ammonia :

4NH3 + 502 -> 4NO + 6H20
The following side-reaction also occurs:
4NH3 + 302 ^ 2N2 + 6H20
The product gases are scrubbed to remove all water and 80% of NO produced. The gases
leaving the scrubber have the following analysis: 02 = 5.6%, N2 = 92.0%, NO = 2.4%.
Determine the following:
( a ) The percent excess air used
( b ) The fraction of the ammonia fed that is taking part in the side reaction
Solution Basis: 100 mol gas leaving the scrubber
The composition of the gas:
NO = 2.40 mol
N 2 = 92.00 mol
02 = 5.60 mol
 Material Balance with Chemical Reaction 331

The amount of NO present in the gas is 2.4 mol which is 20% of the total NO produced.
2.4
Therefore, the amount of NO produced by the reaction is —0.2 = 12 mol.
Let x mol nitrogen is produced by the reaction. Then, the amount of nitrogen present in
the air supplied is
92 - x mol (A)
Since 4 moles of NO formed in the reaction accounts for 5 moles of oxygen and 2 moles of
nitrogen accounts for 3 moles of oxygen, the total oxygen used up in the reaction is
5 3
12 x — + xx — = 15 + 1.5x mol
4 2
Since 5.6 mol oxygen is present in the products, the total oxygen supplied is
15 + 1.5x + 5.6 = 20.6 + 1.5x
The amount of nitrogen associated with the oxygen supplied is

(20.6 + 1.5x) x — = 77.495 + 5.643x (B)

Comparing Eqs. ( A ) and ( B), we have

77.495 + 5.643x = 92 - x
On solving this equation, we get
x = 2.1835
Or the amount of nitrogen produced by the reaction = 2.1835 mol.
( a ) 12 mol NO in the products requires reaction of 12 mol ammonia and formation of
2.1835 mol nitrogen requires reaction with 2 x 2.1835 = 4.367 mol ammonia, the total
ammonia reacted is
12 + 4.367 = 16.367 mol
The theoretical requirement of oxygen is the oxygen required by ammonia for its
complete conversion to NO according to the first reaction is

16.367 x - = 20.4588 mol

4
Oxygen supplied = 20.6 + 1.5x = 23.8753 mol
23.8753 - 20.4588
Percent excess oxygen = x 100 = 16.7 %
20.4588
(b) Ammonia fed = 16.367 mol
The amount of ammonia converted to N2
2 x 2.1835 = 4.367 mol
Therefore, the fraction of ammonia that is taking part in the side reaction is
332 Stoichiometry and Process Calculations

4.367
16.367
= 0.267
{ Note: Solve this problem taking 1 mole NH3 admitted as a basis. Let x be the number
of moles of ammonia that take part in the side reaction.)
EXAMPLE 10.16 In the manufacture of nitric acid, pure dry sodium nitrate is treated with
95% (weight) sulphuric acid.
2 NaN03 + H2S04 -> 2 HN03 + Na2S04
Acid is supplied in excess to ensure that the resulting nitre cake is liquid containing 35%
sulphuric acid by weight. The cake contains 1.5% water by weight. In addition 2% of the nitric
acid formed will remain with the cake. For a basis of 100 kg of sodium nitrate treated, calculate
the following:
( a ) The weight and composition of the nitre cake
(b ) The weight of sulphuric acid to be used
( c ) The weight of nitric acid product obtained
( d ) The water vapour that is distilled from the nitre cake
Solution Basis: 100 kg of sodium nitrate reacted

Moles of NaN03 reacted = —85— - 1.1765 kmol

Mass of H 2S04 consumed = — -— x 98.08 = 57.6956 kg
Mass of HN03 produced = 1.1765 kmol = 1.1765 x 63.008 = 74.1289 kg

Mass of Na2S04 produced = — -— x 142.064 = 83.569 kg

( a ) Nitric acid remaining with the cake = 0.02 x 74.1289 = 1.4826 kg
Nitre cake contains 83.569 kg of Na 2S04, 1.4826 kg of nitric acid which together will
constitute 100 - 35.0 - 1.5 = 63.5% of the total weight of cake. Therefore, the total
weight of cake is
(83.569 + 1.4826)
0.635
= 133.94 kg
The composition of the cake:
Na2S04 = 83.569 kg (62.39%)
H 2S04 = 46.879 kg (35.00%)
HN03 = 1.483 kg ( 1.11%)
Water = 2.009 kg ( 1.50%)
Total = 133. 94 kg
( b ) The mass of H 2S04 consumed = 57.6956 kg
The mass of H 2S04 present in the cake = 46.879 kg
The total H 2S04 required = 104.5746 kg
 Material Balance with Chemical Reaction 333

The weight of 95% sulphuric acid is

104.5746
0.95
= 110.08 kg
( c ) Since 2% of the nitric acid formed is lost with the cake, the mass of nitric acid product
is
0.98 x 74.1289 = 72.65 kg
( d ) The amount of water associated with sulphuric acid supplied = 110.08 x 0.05 = 5.504
kg. Out of this, 2.009 kg of water remains with the cake. Therefore, the water vapour
that is distilled off from the cake is
5.504 - 2.009 = 3.495 kg
Figure 10.9 schematically represents the material balance of this example.

95 % sulphuric acid, 110.08 kg

H2S04, 104.575 kg
H20. 5.505 kg

Water vapour,
3.495 kg
j

Sodium
Nitric acid
nitrate ,
100 kg manufacture

i r
Nitre cake , 133.94 kg
Na 2S04, 83.569 kg (62.39 % )
j
H 2S04, 46.879 kg ( 35 % )
Nitric acid,
H 20, 2.009 kg ( 1.5 % )
72.65 kg
HN03, 1.483 kg ( 1.11 % )
Figure 10.9 Material balance in nitric acid production of Example 10.16.

10.7 CHLORINE, HYDROCHLORIC ACID AND CHLORINATION

Electrolysis of brine results in the production of two industrially important chemicals: chlroine
and caustic soda ( NaOH).
2NaCl + 2 H20 -> 2NaOH + Cl2 + H2
Diaphragm electrolytic cell produces 10-12% NaOH solution whereas mercury electrolytic cell
gives concentrated NaOH of strength 70%.
In the Deacon process for the manufacture of chlorine by the air oxidation of hydrochloric
acid, a dry mixture of hydrochloric acid and air is passed over a heated Fe203 catalyst. Acid
is oxidized in the presence of air, which is supplied in excess of that theoretically required:
4HC1 + 02 -> 2 H20 + 2C12
Chlorine is industrially very important chemical. Its uses include production of chlorinated
solvents, insecticides ( DDT, BHC ) , plastics ( PVC ) , refrigerants ( methyl chloride ) ,
334 Stoichiometry and Process Calculations

hydrochloric acid , etc. It is also used in pulp and paper bleaching, textile bleaching and water
treatment .
Some of the important chlorination reactions are as follows:
( a ) Oxychlorination of ethylene to ethylene dichloride:
2C 2H4 + 4HC1 + 02 -> 2C 2H4C12 + 2 H20
( b ) Chlorination of glacial acetic acid to mono and dichloroethylene:
CH3COOH + Cl2 CH2ClCOOH + HC1
CH 2ClCOOH + Cl2 -4 CHCl2COOH + HC1
( c ) Catalytic vapour phase chlorination of carbon disulphide to carbon tetrachloride:
CS2 + 3C12 -4 CC14 + S2C12
( d ) Manufacture of methyl chloride by the chlorination of methane in the presence of a
copper catalyst at 723 K:
CH4 + Cl2 CH3CI + HC1
The material balance calculation involved in the electrolytic process for the manufacutre of
chlorine is illustrated in Example 10.17 and problems on the other important processes are given
in the exercise at the end of the chapter.

EXAMPLE 10.17 Purified brine at the rate of 50 kg/h is sent to an electrolytic cell for
producing chlorine:
2NaCl + 2 H20 2NaOH + Cl2 + H2
Only 50% of NaCl in the charge is electrolyzed. The gases leaving the cell carry with them
water vapour in the ratio 0.03 mol/mol gas formed. The solution leaving the cell contains 10%
NaOH which is concentrated to 50% NaOH in evaporators. The NaCl present in the solution
fed to the evaporator is crystallized and removed so that the concentrate leaving the evaporators
contain only 1.5% NaCl. Calculate the following:
(a) The rate of production of 50% NaOH in kg/h
( b) The rate of production of chlorine and hydrogen gas
( c) The rate at which NaCl is crystallized in kg/h
(d) The rate of evaporation of water in kg/h
Solution Basis: 50 kg/h of brine charged
Let the brine contain x kg of NaCl and the rest water. Therefore, the mass of water present
= 50 - x kg.

The amount of NaCl reacted is

0.5x
0.5x kg = kmol
58.45
2NaCl + 2 H20 -4 2NaOH + Cl2 + H2
 Material Balance with Chemical Reaction 335

The mass of water reacted is

0.5*
x 18.016 = 0.1541JC kg
58.45

Gases
Cl 2, H2,
H ^ O 0.03 mol /mol of gas Water vapour

10 % NaOH 50% NaOH solution,

Brine, 50 kg /h NaCl 1.5%
Electrolytic solution Evaporator cum
-> crystallizer >
cell

NaCl Crystals
Figure 10.10 Electrolysis of brine in Example 10.17.

Gases produced:

Chlorine = x -= 4.2772 x 10 3 x kmol

“

58.45 2
= 0.3033* kg

Hydrogen = 1= 4.2772 x 10 3 x kmol

X
“

58.45 2
= 8.6228 x 10-3x kg
Mass of water vapour present in the gas
0.03 x 2( 4.2772 x lO 3 )* = 2.5663 x lO^x kmol = 4.6235 x 10 3x kg
’ "

Solution leaving the cell:

NaCl = 0.5* kg
0 5*
NaOH = —58.45
— x 40.008 = 0.3422* kg
Water = water in the brine charge - water reacted - water present in the gas
= 50 - x - 0.1541* - 4.6235 x 10 3* "

= 50 - 1.1587* kg
Total weight of solution = 0.5* + 0.3422* + 50 - 1.1587*
= 50 - 0.3165* kg
Since NaOH in the solution leaving the cell constitutes 10% of the total weight of solution ,
we have the following relationship:
0.3422* = 0.10(50 - 0.3165*)
The above equation gives, * = 13.3743 kg .
336 Stoichiometry and Process Calculations

( a ) The solution leaving the cell is taken to the evaporator. This solution contains
NaOH = 0.3422* = 4.5767 kg
NaCl = 0.5* = 6.6872 kg
Water = 50 - 0.3165* = 34.5032 kg
The solution leaving the evaporator contains 50% NaOH, and NaOH balance on the
evaporator gives
4.5767 = 0.5 y
where y is the amount of solution leaving the evaporator in kg/h . Solving , we get
y = 9.1534 kg.
Therefore, the amount of 50% NaOH solution produced = 9.1534 kg/ h
( b) Chlorine produced = 0.3033* = 4.0564 kg
Hydrogen produced = 8.6228 x 10 3* kg = 0.1153 kg
~

( c ) NaCl in the solution leaving the evaporator is only 1.5%, the amount of NaCl present
in the solution is
0.015 x 9.1534 kg = 0.1373 kg
Since the amount of NaCl entering the evaporator is 6.6872 kg, the amount of NaCl
crystallized is
0.1373 = 6.5499 kg/h
6.6872 -

( d ) The weight of water in the concentrated solution leaving the evaporator is

total weight of solution - weight of NaOH - weight of NaCl
= 9.1534 - 4.5767 - 0.1373 = 4.4394 kg
The amount of water entering the evaporator is 34.5032 kg .
Gases, 4.2335 kg
Cl 2, 4.0564 kg
H 2, 0.1153 kg Water vapour,
H 20, 0.0618 kg 30.0637 kg
i ik

Brine, 50 kg/h 10% NaOH

NaCl, 13.3743 kg, solution 50 % NaOH solution,
H20, 36.6257 kg 45.7671 kg 9.1534 kg
Electrolytic Evaporator cum
" crystallizer
cell NaCl, 6.6872 kg NaOH, 4.5767 kg
NaOH, 4.5767 kg NaCl, 0.1373 kg
H20, 34.5032 kg H,0, 4.4394 kg
t
NaCl crystals,
6.5499 kg
Figure 10.11 Material balance in Example 10.17.
 Material Balance with Chemical Reaction 337

Therefore, a water balance on the evaporator gives:

34.5032 = 4.4394 + water evaporated and removed in the evaporator
Therefore, the weight of water evaporated is
34.5032 4.4394 = 30.0637 kg
-

Figure 10.11 shows the material balance in Example 10.17.

10.8 HYDROGENATION, HYDRATION AND OXIDATION

In addition to the applications discussed so far, the material balance will be required to find
answers to such questions as:
• How much hydrogen is required for the hydrogenation of an unsaturated edible oil?
• What are the quantity and composition of the product gases that leave the reaction
chamber where the vapour-phase oxidation of methanol to formaldehyde takes place in
presence of air?
• At what rate are hydrocarbon fuels produced when coal is hydrogenated in a supply of
air and steam? What should be the supply of air and steam for the reaction of a given
quantity of coal?
• Given the analysis of the gas leaving the reaction chamber where ethylene is subjected
to oxidation, what is the percent conversion of ethylene and what is the percent yield of
ethylene oxide?
The material balance problems of the above type are encountered in processes employing the
hydrogenation, hydration and oxidation reactions. Hydrogenation reactions involve the addition
of hydrogen to a compound. Generally hydrogenation is used to improve existing products, to
convert complex raw materials into valuable chemicals, and to transform solid fuels into liquid
fuels. The commercial applications of hydrogenation include hydrogenation of oils, high-pressure
hydrogenation of carbon monoxide to synthetic methanol and higher alcohols, hydrogenation of
fatty acids to alcohols for the production of detergents, etc. The unit process of hydrolysis is
a double decomposition reaction between a compound and water. The saponification of fats,
the inversion of sugars, the conversion of starch, the saccharification of cellulose, the breakdown
of protein are examples of hydrolysis. Oxidation is one of the most powerful tools used in the
synthesis of chemical compounds.
The material balance calculation generally encountered in the various processes outlined in
this section is illustrated for the process of oxidation of methanol to formaldehyde using air in
the following example. Other processes can be seen in exercise problems 10.101 through
10.110.
EXAMPLE 10.18 Formaldehyde is made by the oxidation of methanol with air. The analysis
of the exit gas from the reactor shows 64.49% N2, 13.88% 02, 5.31% H20, 11.02% CH3OH,
4.08% HCHO and 1.22% HCOOH. Calculate the following:
( a ) The percent conversion of formaldehyde
( b ) The ratio of air to methanol in the feed
338 Stoichiometry and Process Calculations

Solution Basis: 100 mol reactor exit gas

The following reactions take place in the reactor.
CH3OH + 02 HCOOH + H20

CH 3OH +

^ 02 -> HCHO + H 20
( a) Let x moles of methanol reacted to produce 100 mol gas. A carbon balance on the
reactor gives
x = 11.02 + 4.08 + 1.22 = 16.32 mol
The amount of methanol reacted = 16.32 mol.
The amount of methanol converted to formaldehyde = 4.08 mol .

Percent conversion of formaldehyde = x 100 = 25 %

16.32
( b ) Air supplied can be determined by a nitrogen balance.
The amount of air supplied is

64.49 x — = 81.63 mol

79
The ratio of air to methanol in the feed is
81.63
16.32
= 5.00

10.9 PROCESSES IN BIOLOGICAL, ENVIRONMENTAL AND ENERGY SYSTEMS

The principles of process calculations that we have applied to conventional processes can be
readily extended to solve material and energy balance problems dealing with biotechnology,
energy conservation, environmental pollution abatement, safety and health hazards. Though a
detailed discussion is beyond the scope of this book, some illustrative problems with a brief
discussion of related terms not covered so far are given here.
Stoichiometry of bioprocesses provides information on substrate conversion into product
and cell mass production from substrate. The term substrate refers to medium such as glucose
on which the biomass ( bacteria, fungi, etc.) are expected to grow either on the surface or in
solution. The following simple equation can be used to represent the process:
—
Cells + medium + 02 > more cells + extracellular product + C02 + H 20 ( 10.4 )
As nitrogen sources, compounds such as ammonia, ammonium, urea, nitrate, secondary
treatment wastes are used for biomass growth. Products may contain cellular as well as
extracellular products. Cellular products are the biomasses that are produced in the reaction(s).
Growth takes place throughout the biomass, not restricted to the surface. A product may occur
jointly with biomass growth that probably will have to be separated from the biomass. Various
metabolites such as acetates, citrates, glycerol, and so on as well as C02 and H20 constitute
the extracellular products.
 Material Balance with Chemical Reaction 339

The following equivalent reaction can also be written to represent the general chemical
equation for bioprocesses:

CwH ^ OyNz + a02 + bHgOAN, -> cCUaOpNs + dC02 + eH 20 + / C;H,OfNm ( i 0.5 )

(Substrate ) ( Nitrogen source ) ( Dry biomass) (Extracellular product )

where a, b, a, /3, S, x, y, z depend on the type of cell involved a, b, c, d, e and / are

,

stoichiometric coefficients. In anaerobic processes, second term on the left side is not present.
A cell contains elements other than C, H, O and N, but the minor components such as P, S ,
K, Ca , Mg, Cl and Fe require so little 02 that they are often treated as ash, a non-reacting
compound. The cells are generally represented by the molecular formula CH O N . In the
^ ^
absence of sufficient information on the cell composition, an approximate cell composition of ^
CHL8O0.5Na 2 is accepted. The stoichiometric equation is generally normalized to 1 mole of
carbon source compound. The values of stoichiometric coefficients are required to predict the
yield of product and biomass, the oxygen demand for the process, etc.

10.9.1 Yield and Yield Coefficients

Stoichiometric or theoretical yield is defined as the total mass or moles of product formed per
unit mass or moles of reactant used to form that particular product . Observed or apparent yield
is the mass or moles of product present per unit total mass or moles of reactant consumed.
Yield coefficients are denoted by Y and several such coefficients are used. Thus,
YX / s = mass or moles of biomass produced per unit mass or moles of substrate consumed
YP/ S = mass or moles of product formed per unit mass or moles of substrate consumed
Yp/ x = mass or moles of product formed per unit mass or moles of biomass
Yx/0 = mass or moles of biomass formed per unit mass or moles of oxygen consumed
YCo /s = mass or moles of C 02 formed per unit mass or moles of substrate consumed
2

10.9.2 Elemental Balance

Elemental balance helps in determining the stoichiometric coefficients. For illustration, consider
a process represented by the following equation:
CwH ^ OyNz + a02 + bHgOhNi -> cCUa0 02 + eU 20 + / C,.H*OfNm
(Substrate ) ( Nitrogen source ) ^ 6 + dC
( Dry biomass) (Extracellular product )

C balance w = c + d + fi (10.6)
H balance x + bg = ca + 2e + fk ( 10.7)
0 balance y + 2 a + bh = cP + 2d + e + fl ( 10.8 )
N balance z + bi = c8 + fm ( 10.9)

As the elemental balance generally fails to provide sufficient data, additional informations
such as respiratory coefficient, degree of reduction, etc., are required to determine stoichiometric
coefficients. The values of c and / ( f = 0 when no extracellular products are formed) are
sometimes obtained by measurements.
340 Stoichiometry and Process Calculations

_ moles of biomass produced

moles of substrate consumed
moles of extracellular product
/= moles of substrate consumed

10.9.3 Respiratory Quotient

Respiratory coefficient ( RQ) is defined as the number of moles of C02 formed from one mole
of 02 consumed.

RQ = - ( 10.10 )
a
Respiratory coefficient provides information on the metabolic state of the cell . A high RQ means
that much C02 is produced, and hence, the metabolism operates at high efficiency. Equations
(10.6) through (10.10) are solved for five unknowns a, b, c, d and e .

10.9.4 Degree of Reduction

Degree of reduction ( y ) is defined as the number of equivalents of available electrons per gram
atom of carbon. Available electrons are those that would be transferred to oxygen upon
oxidation of a compound to C02, H20, NH3. Degree of reduction provides another independent
equation to find the stoichiometric coefficients. Degree of reduction ( y) for C = 4, H = 1,
N = -3, O = -2, P = 5, S = 6.
For example, the degree of reduction of ethanol is evaluated as follows:
C 2H5OH: [2(4) + 6(1) + l (-2)]/2 = 12/2 = 6
In the absence of extracellular products formed during the reaction , we can write
wys - Aa = cyB (10.11)
where yB and ys are the degree of reduction of substrate and biomass, respectively.

a= ~ ( wYs ~
CYB ) (10.12)

Equation (10.12) can also be written as

4a , cyB _l
(10.13 )
wys wys
4a
wys = number of electrons transferred to 02
cyB
wys = number of electrons transferred to biomass
 Material Balance with Chemical Reaction 341

Maximum value of stoichiometric coefficient c (all electrons are used for biomass synthesis)
is

r WYs
'- max =
'

CYB
When a product is also formed ,

wYs
max
IYP
where yP is the degree of reduction of the product.

10.9.5 Oxygen Requirement

A number of empirical measures of oxygen usage in biosystems are employed to measure
oxygen demand. The most important parameters used in biological processes and environmental
systems are the chemical oxygen demand (COD), total oxygen demand (TOD), biochemical
oxygen demand (BOD) and theoretical oxygen demand (ThOD). The definitions are given below.
Chemical oxygen demand (COD): Since there are many organic compounds that are difficult
or impossible to decompose biologically, the parameter COD has been defined indicating the
amount of oxygen required for oxidizing all organics completely. A chemical oxidant is added
to the sample, the consumption of which is then determined . The internationally dominant
method today is the ‘dichromate’ method, which is characterized by the acidification of the
sample with sulphuric acid and the addition of silver nitrate. The COD measures all organic
carbon with the exception of certain aromatics which are not completely oxidized in the
reaction . Substances such as sulphides, sulphites and ferrous iron are also oxidized and reported
as COD. Nitrogen in ammonia is not oxidized.
Total oxygen demand (TOD): It is the quantity of oxygen required to completely oxidize all
the organic and inorganic compounds present in the sample and is based on the same principle
as COD. To define TOD, the sample is thermally oxidized in an oven and the emerging oxygen
is measured directly in the carrier gas. The amount of oxygen is reported as milligrams of
oxygen per litre containing the sample, or as grams of oxygen per gram of sample .
Biochemical oxygen demand (BOD): The quantity of oxygen required by microorganisms
to oxidize the organic compounds in the sample is determined by a BOD test. The test is carried
out for five days at 20°C. The quantity of oxygen used is determined by the difference in the
dissolved oxygen in the sample in the beginning of the test and at the end of the test . BOD
is expressed as grams oxygen per gram sample. It is used mainly for evaluating water and
waste water quality.
Theoretical oxygen demand (ThOD): It is the quantity of oxygen required according to a
balanced chemical reaction equation to oxidize the reactants to C02, H20, and the highest
oxidation state of other products, ignoring any extracellular product from a sample ( f = 0). The
highest state of nitrogen compounds is nitrates.
342 Stoichiometry and Process Calculations

EXAMPLE 10.19 Production of single cell proteins from hexadecane is given by the following
equation. If respiratory quotient (RQ) is 0.4, determine the stoichiometric coefficients.

—
C16 H 34 + a 02 + & NH 3 » cCH1 66 Oa 27 Na 2 ( Biomass) + dC 02 + eH 20
>

Solution
By definition, RQ = d / a = 0.40 (A)
C balance: 16 = c + d (B )
H balance: 34 + 3 b = 1.66c + 2 e (C )
O balance: 2a = 0.27c + 2d + e (D)
N balance: b = 0.2c (E)

On solving,
a = 11.73, b = 2.26, c = 11.31, d = 4.69, e = 11.03

EXAMPLE 10.20 Ammonia is used as the nitrogen source for the production of biomass
Klebsiella aerogenes ( CH 1 73Oo.43N0 24) from substrate glycerol aerobically. 0.5 g biomass is
< >

produced for each gram of glycerol consumed. The biomass contains 6% ash. No extracellular
products are formed. Determine the oxygen requirement for this process.
Solution Molecular weight (MW ) of glycerol = 92.064
Molecular weight ( MW ) of biomass Klebsiella aerogenes CHj 73O0 43 N 0 24 = 23.99
Molecular weight ( MW ) with ash = 23.99/0.94 = 25.52
Degree of reduction for substrate glycerol (C 3H803),
3 x 4 + 8 xl + 3 x (-2)
_
7s = — .
= 4.67
Degree of reduction for biomass CPf j3O0.43N0.24,
4 x 1 + 1 x 1.73 - 2 x 0.43 - 3 x 0.24
7B = I 4.15

Number of C atoms in glycerol = 3

Yield of biomass Yxs = 0.5 g/g of substrate
The general equation is
CwRxOyNz + a02 + bHgOhNi -> cCRaOpN 5 + dC 02 + eH 20
(Substrate) ( Nitrogen source ) (Dry biomass)

Yx/ S = mass of biomass produced per unit mass of substrate consumed

v
_ Mass of cells _ cx MW of cells _ n.c
* x/s U J
Mass of substrate MW of substrate
MW of substrate 92064
Coefficient c = Yx / s x MW of cells
0.5
A C
x
25.52
1.80
 Material Balance with Chemical Reaction 343

Oxygen requirement is
wxys -cxyB 3 x 4.67 - 1.80 x 4.15
a= = 1.63 mol 02 per mol substrate
4 4
On mass basis, oxygen demand = 1.63 x 32/92.064 = 0.567 g oxygen/g substrate.

EXAMPLE 10.21 Anaerobic digestion of volatile acids by methane bacteria is represented by

the equation given below:
CH 3COOH + & NH 3 — > cCH 1 4O0 4 N0 2 ( Biomass ) + c?C02 + cH 20 + fCH 4
The composition of methane bacteria is CH! 4O0 . 4N02. For each gram acetic acid consumed, 0.60 g
C02 is evolved. How does the yield of methane under these conditions compare with the
maximum possible yield?
Solution In anaerobic digestion, no oxygen participates in the reaction.
Molecular weight of biomass (methane bacteria) CH! 4Oo.4N 0 2 = 22.6
Degree of reduction of biomass, yB = 4 xl + l x l .4 + (-2) x 0.4 + (-3) x 0.2 = 4
4 x 2 + 1 x 4 + ( 2) x 2
Degree of reduction of substrate, CH3COOH, Ys = “
=4
Degree of reduction of CH4, y p = 4xl + lx4 = 8
0.60 gram C0 2 is produced from one gram acetic acid.

That is,
0.60/44 _ mo\ QQ 2 / mo\ acetic acid
1/60.032
So, d = 0.82.
From elemental balance, the stoichiometric coefficients are determined . The general equation

,
C
^ Hx , ,
(Substrate )
*,
0 N + fl02 + & H 0 N
( Nitrogen source )
-> cCHaOpNs + d C 02 + cH 20 + / C;HjtO / Nm
(Dry biomass) (Extracellular product )

Here, the extracellular product is CH4.

N balance: b = 0.2c (A)
C balance: 2 = c + d +/ (B )
O balance: 2 = 0.4c + 2 d + e (C )
H balance: 4 3 b = 1.4c + 2c + 4/
+ (D)
On solving, we get / = 0.82.
So, product yield = 0.82 mol/mol substrate
wy _ 2x4 ,
fYp 1x 8
Comparing the values of / and /max, / = 0.82 /max .
344 Stoichiometry and Process Calculations

EXAMPLE 10.22 A bioreactor was charged with 5000 kg/ h of an aqueous solution of
fermented grain containing 15% by weight glucose (C6H1206). Yeast digests the glucose to
form ethanol and acrylic acid (C2 H3COOH).
C6 H1206 ^ 2C2 H50H + 2C02

If 150 kg C02
°
C6 Hi 2 * 2C H COOH + 2H20
6

is produced and 110 kg

2 3

glucose remains in the broth, determine

unreacted
the percent composition by weight of the products in the broth.
Solution Basis: 5000 kg/h 15% glucose solution
Glucose charged = 5000 x 0.15/180.096 = 4.164 kmol
C02 produced = 150/44 = 3.41 kmol
Glucose reacted to produce C02 and ethanol = 3.41/2 = 1.705 kmol
Ethanol produced = 1.705 x 2 x 46.048 = 157.02 kg
Unreacted glucose = 110/180.096 = 0.61 kmol
Glucose reacted to produce acrylic acid = 4.164 - 1.705 - 0.61 = 1.849 kmol
Acrylic acid produced = 1.849 x 2 x 72.032 = 266.37 kg
Water remaining = 5000 x 0.85 + 1.849 x 2 x 18.016 = 4316.61 kg
The product composition is as follows:

Component Mass, kg Weight %

Ethanol 157.02 (157.02/4850) x 100 = 3.24
Acrylic acid 266.37 (266.37/4850) x 100 = 5.49
Glucose 110.00 (110.00/4850) x 100 = 2.27
Water 4316.61 ( 4316.61/4850) x 100 = 89.00
4850.00

EXAMPLE 10.23 In an experimental investigation on renewable energy resources, rice husks

were subjected to pyrolysis. After pyrolysis, the gas analyzed 6.4% C02, 0.1% 02, 39% CO,
51.8% H 2, 0.6% CH 4 and 2.1% N2. It entered a combustion chamber at 300 K and a pressure
of 120 kPa and was burned with 50% excess dry air at 295 K and 101.3 kPa. 10% of the CO
remained unconverted . For each cubic metre of gas entering the combustion chamber, determine:
(a ) Air supplied in cubic metres
(b) Composition of product gas
(c ) Cubic metres of product gas at STP
Solution Basis: 100 kmol of pyrolysis gas entered the combustion chamber.
6.4 kmol C02, 0.1 kmol 02, 39 kmol CO, 51.8 kmol H2, 0.6 kmol CH 4, 2.1 kmol N2
Reactions requiring 02 are:
CO + l /202 -> C02
H2 + l /202 -> H20
CH4 + 202 -> C02 + 2H20
 Material Balance with Chemical Reaction 345

39 51.8
( a ) Oxygen required =
3
1
3
- 2 x 0.6
1 — 0.1 = 46.5 kmol

Oxygen supplied = 50% excess = 46.5 x 1.5 = 69.75 kmol

69.75
Air supplied =
0.21
= 332.14 kmol
Volume of air entered at 295 K and 101.3 kPa,
nRT 332.14 X 8.314 X 295
V = P 101.3
= 804 L? m 3
Volume of pyrolysis gas entered at 120 kPa and 300 K =
nRT 100 x 8.314 x 300
P 120
= 2Q78 5 m 3
8041 /7 , 3
Air supplied per cubic metre of entering gas = - 3.87 m
207 o.5

( b ) The composition of product gas is as follows:

Component kmol Mol %

co2 6.4 + 35.1 + 0.6 = 42.1 10.8
CO 3.9 1.0
N2 2.1 + 262.4 = 264.5 68.1
02 69.75 + 0.1 - ((35.1/2) + (51.8/2) + 1.2) = 25.2 6.5
H2O 51.8 + 1.2 = 53 13.6
Total 388.7 100

( c ) Total moles of product gases = 388.7 kmol

Volume of the product gas at STP, V = 388.7 x 22.414 = 8712.3 m 3
EXAMPLE 10.24 Fuel cell can be considered as the energy supplier for the future. A fuel cell
is an open system into which fuel and air are fed and produces electricity and waste products.
In a fuel cell using methane as fuel, C 02 and water are the products along with electricity.
Special membranes and catalysts are used to promote oxidation of methane with air. If air and
methane are fed to the fuel cell in the molar ratio 10: 1, determine the composition of the
products.
Solution Basis: Methane and air admitted in the ratio 1:10.
CH4 + 202 -> C 02 + 2 H20
Moles of oxygen = 10 x 0.21 = 2 . 1
Moles of nitrogen = 7.9
346 Stoichiometry and Process Calculations

Component Moles Mole %

CHt 0 0
02 2.1 -2 = 0.1 0.91
N2 7.9 71.82
co2 1.0 9.09
H2O 2.0 18.18
Total 11.0 100.0

EXAMPLE 10.25 Air oxidation and chlorination are two processes employed in waste water
treatment for odour removal. But, chlorination using HOC1 solution is preferred as it not only
destroys H 2S and other odourous compounds but also retards the growth of bacteria. 0.1 cubic
metres of waste water contains 63 ppm H2S. If a 5 % solution of HOC1 in water is used,
determine the quantity required. The reaction is
HOC1 + H2S -> S + HC1 + H20

Solution Basis: 0.1 m 3 solution contains 63 ppm H2S.

3
63 ppm = 63 mge/L = 63 xl 0 g =

1 mol H 2S requires 1 mol HOC1.

“

^^—
34.081
x l O3 = 1.849 mol/m 3

HOC1 required = 1.849 x 0.1 = 0.1849 mol

HOC1 supplied = 2 x 0.1849 mol = 0.3698 mol
Weight of HOC1 = 0.3698 x 52.461 = 19.4 g
Weight of 5% solution = 19.4/0.05 = 388 g ( = 0.388 kg )

EXAMPLE 10.26 Activated sludge process is one of the processes for sewage treatment.
After treatment, the sludge produced must be dewatered and disposed . Sludge incineration is
one of the options for sludge disposal. In a typical treatment plant, the dried sludge with the
composition C = 40%, S = 32%, H2 = 4% and 02 = 24% is mixed with fuel oil and burned in
a furnace with air. The effluent gases leaving the furnace analyzed S02 = 1.52%, C02 = 10.14%,
02 = 4.65%, N 2 = 81.67% and CO = 2.02%. Determine:
(a ) The weight percent of carbon and hydrogen in the fuel oil
(b) Ratio of weights of sludge to fuel oil fed to the furnace
Solution Basis: 100 kmol product gas
N 2 comes from air only. N2 = 81.67 kmol
02 supplied = 81.67 x 21/79 = 21.71 kmol
C in product gas = 10.14 + 2.02 = 12.16 kmol
S in product gas = 1.52 kmol
All S comes from sludge. Weight of S = 1.52 x 32.065 = 48.74 kg
48.74 kg = 32% of sludge.
 Material Balance with Chemical Reaction 347

Sludge burned = 48.74/0.32 = 152.31 kg

C = 40% = 152.31 x 0.4 = 60.92 kg
H 2 = 4% = 0.04 x 152.31 = 6.092 kg
02 = 24% = 0.24 x 152.31 = 36.55 kg
Total oxygen present = 36.55/32 + 21.27 = 22.41 kmol
Oxygen present in flue gas = 1.52 + 10.14 + 4.65 + 2.02/2 = 17.32 kmol
So, oxygen used by hydrogen = 22.41 - 17.32 = 5.04 kmol
H 2 from sludge = 6.092/2.016 = 3.022 kmol
H 2 from fuel oil = 5.09 - 3.022 = 2.068 kmol = 4.169 kg
Carbon in the product gas = 12.16 kmol = 145.92 kg
Carbon from sludge = 60.92 kg
So, carbon from fuel oil = 145.92 - 60.92 = 85 kg
(a ) Weight percent of carbon and hydrogen in fuel oil
Fuel oil, C = 85 kg = 95.33%
H = 4.169 kg = 4.67 %
(b) Weight of dry sludge = 152.31 kg
Weight of oil = 89.169 kg
Weight ratio of sludge to oil = 152.31/89.169 = 1.71

EXERCISES

Combustion of solid, liquid and gaseous fuels

10.1 A synthesis gas analyzing 6.0% C 02, 0.5% 02, 40.0% CO, 50% H2 and the rest N2
is burned with 50% excess air. What is the composition of the flue gas?
10.2 A gas mixture consisting of 80% ethane and 20% oxygen is burned in an engine with
200% excess air. 80% of the ethane goes to C02, 10% to CO and 10% remains
unbumed. Calculate the composition of the exhaust gases on
( a ) a wet basis
( b ) a dry basis
10.3 Pure propane is burned with as much quantities of air as is required to limit the carbon
dioxide content in the flue gas to 8%. How much excess air is to be supplied?
10.4 One kilomole methane is completely burnt to form C02 and water vapour using 10%
excess air than that required for complete combustion. The resulting gas mixture is
treated to remove all the water content.
( a ) What will be the volume of dry gas leaving the burner at 110.3 kPa and 275 K?
( b ) How many kilograms of water are removed from the products of combustion?
348 Stoichiometry and Process Calculations

10.5 Pure methane is completely burned with air. The gas leaving the burner which contains
no oxygen is passed through a cooler where some of the water is removed by
condensation. The mole fraction of nitrogen in the gas leaving the cooler was 0.8335.
Calculate the following:
(a ) The analysis of the gas leaving the cooler
( b ) Water condensed in kg per kmol of methane burned
( c ) The partial pressure of water in the gas leaving the cooler at 325 K and 1.5 bar
10.6 A mixture of ethane (C2H6) and ethene (C2H4) occupies 40 L at 1 atm and 400 K. The
mixture reacts completely with 130 g of 02 to produce C02 and H20. Assuming ideal
gas behaviour, calculate the mole fractions of C2H4 and C2H6 in the mixture.
10.7 Pure methane is completely burned with air. The outlet gases from the burner which
contains no oxygen , are passed through a cooler, where some of the water is removed
by condensation. The gases leaving the cooler have a nitrogen mole fraction of 0.75.
Calculate the following:
(a ) The analysis of the gases leaving the cooler
( b ) The mass of water condensed per one kilogram of methane burned
( c ) The average molecular weight of the gases leaving the cooler
10.8 Calculate the flue gas analysis on the dry basis for the following furnace operation. The
fuel contains 85% carbon and the rest hydrogen on a weight basis. 40% excess air is
used. It is found that all H 2 is converted to H20 and 95% carbon to carbon dioxide
and the rest to carbon monoxide.
10.9 Producer gas has the following composition by volume: carbon monoxide = 25.0%,
carbon dioxide = 4.0%, oxygen = 3.0% and nitrogen = 68.0%.
(a ) Determine the volume of the gas at 1 bar and 290 K per kg of carbon.
( b ) 100 m 3 of the gas at 1 bar and 290 K is to be burned with 20% excess air than
that is theoretically required for complete combustion. What volume of air is
required at 1 bar and 290 K?
( c ) For the conditions in part (b), what would be the composition of the gas after
complete combustion?
10.10 A producer gas contains 28% CO, 3.5% C02, 0.5% 02 and 68% N 2. 100 kg of this
gas is burned with 20% excess air. If the combustion is only 90% complete, determine
the following:
(a ) The composition of the flue gas
( b ) The weight of the gaseous products
10.11 A gas mixture analyzing 6% pentane, 10% butane, 15% propane, 10% ethane, 55%
methane and 4% nitrogen by volume is burned at a rate of 100 m3 per hour at 350
kPa and 300 K with 12% excess air. Air is supplied at 100 kPa and 300 K. It is found
that the flue gas which leaves at 105 kPa and 800 K contains C02 and CO in the mole
ratio 18:1. Determine the following:
(a ) The rate of air supply (m 3 per hour)
( b ) The Orsat analysis of flue gas
( c ) The flue gas produced (m3 per hour)
 Material Balance with Chemical Reaction 349

10.12 A fuel oil analyzing 85% (weight) C and 15% (weight) H is oxidized with 50% excess
air. For the oxidation of 100 kg of oil, calculate the following:
(a ) The air requirement in kilograms
( b ) The composition of the flue gas
( c ) The average molecular weight of the flue gas
10.13 A fuel gas on a dry basis contains 80% methane, 6% ethane, 4% propane, 2% oxygen
and 8% nitrogen. The fuel saturated with water vapour at 300 K and 101.3 kPa and
measuring 100 m 3 is burned with 50% excess air supplied at 305 K and 101.3 kPa with
a relative saturation of 60%. The vapour pressure of water is given by the Antoine
equation:
3799.887
In P s = 16.26205 -
T - 46.854
where P is in kPa and temperature is in K. Calculate the following:
(a ) The analysis of the gas leaving the combustion chamber
( b ) The volume of the gas (in m 3) leaving the furnace at 550 K and 101.3 kPa
assuming complete combustion
( c ) The dew point of the flue gas.
10.14 A liquid fuel analyzing 88% (weight) C and 12% (weight) H2 when burned with excess
air gives a flue gas of the following composition on a dry basis: C02 = 13.5%, 02 =
3.5% and N2 = 83.0%. Calculate the following:
(a ) The percent excess air used
( b ) The volume of dry flue gases at STP per 100 kg of the fuel burned
10.15 The Orsat analysis of the flue gas produced by the combustion of a hydrocarbon fuel
shows 10.2% C02, 1.0%CO, 8.4% 02 and 80.4% N2. What is the atomic ratio of H
to C in the fuel?
10.16 The Orsat analysis of the flue gas resulting from the combustion of a pure hydrocarbon
fuel oil is found to be: C02 = 14.6%, CO = 2.0%, 02 = 2.8%, N 2 = 80.6%. Calculate
the composition of the fuel in weight percent.
10.17 A hydrocarbon fuel is burned with dry air. The combustion gases leave the furnace at
750 K and 100 kPa. The flue gas analysis shows C02 = 12.0%, CO =1.0%, 02 = 4.0%
and N2 = 83%. What is the dew point of the stack gas? The vapour pressure of water
is given by the Antoine equation:
3799.887
In P s = 16.26205 -
T - 46.854
where P is in kPa and temperature is in K .
10.18 Pure propane is burnt in an excess of air to give the following analysis of combustion
products in volume percent: C02 = 5.0, CO = 3.5, H20 = 11.4, 02 = 7.0, N2 = 73.1.
Calculate the percent of excess air used.
350 Stoichiometry and Process Calculations

10.19 The Orsat analysis of flue gas produced by the combustion of pure methane in excess
of dry air is 8.17% C02, 0.96% CO, 5.04% 02 and 85.83% N2. Calculate the percent
excess air used for combustion.
10.20 The Orsat analysis of a flue gas produced by the combustion of a pure hydrocarbon
fuel with an excess of dry air is found to be 8.5% C02, 1.0% CO, 5.0% 02 and 85.5%
N2. Calculate
(a ) the percent excess air used for combustion and
( b ) the weight ratio of C:H in the fuel.
10.21 A gas containing only CH 4 and N 2 is burned with air yielding a flue gas that has an
Orsat analysis of C02 = 8.7%, CO = 1.0%, 02 = 2.0% and N2 = 88.3%. Calculate
the following:
(a ) The percent composition of the fuel
( b ) The percent excess air used
10.22 The exhaust gases from a diesel engine using a high grade fuel oil show 9.76% C02,
8.18% 02, and the rest N2. Calculate the following:
(a ) The H /C weight ratio in the fuel
( b ) The amount of dry air supplied per kilogram of fuel burnt
( c ) The total amount of exhaust gases in kilograms per kilogram of fuel burnt.
10.23 A solid fuel has the following analysis: H = 5.0%, S = 4.0%, C = 65%, O = 10% and
inerts = 16%.
The fuel is burned with 20% excess air. If only 80% of the carbon burned gets
converted to C02, 15% is converted to CO and 5% is left behind as soot, determine
the composition of the combustion gases.
10.24 The flue gas produced by the combustion of pure carbon with excess air contains N2
and 02 in the ratio 7.18:1 by mole and C02 and CO in the ratio 2: 1, what is the percent
excess air used? No other compounds are present in the flue gas.
10.25 Coal containing 80% carbon and 6% ash by weight when burned leaves a cinder which
contains 90% ash and 10% carbon. If 100 kg of coal is charged, calculate the
following:
(a ) The weight of cinder produced
( b ) The per cent fuel value wasted
10.26 The combustible matter in a certain sample of coal is found to be 80% C and 20%
H by weight. 50 kg of coal is burned with 1000 kg of air. The Orsat analysis of the
combustion gas showed C02 to CO in the ratio 3:2. Determine (a) the percent excess
air and (b) the total moles of flue gas produced.
10.27 When coal containing 74% C , 14.9% H and 11.1% ash is burned, it gives a flue gas
containing 12.5% C02, 1.0% CO, 1.5% 02 and 85% N2 on a dry basis. Determine the
following:
(a ) The mass of coal fired in kilograms per kilomole of dry flue gas
( b ) The percent excess air used
( c ) The amount of air supplied in kilograms per kg of coal burned
 Material Balance with Chemical Reaction 351

10.28 A gaseous fuel made up of methane and ethane is burned with enriched air containing
50% oxygen and 50% nitrogen. The flue gas analysis on a dry basis is 25% C02, 15%
02 and 60% N2. Determine the following:
(a ) The mole percent of methane in the fuel
( b ) The moles of air used per mole of fuel
10.29 A fuel gas consisting entirely of methane and ethane is burned with air to yield a flue
gas whose Orsat analysis is 8.68% C02, 6.44% 02 and 84.88% N2. Calculate the
following:
(a ) The analysis of the fuel in mole percent
( b ) The percent excess air
10.30 A furnace is fired with natural gas consisting of 95% methane and 5% nitrogen. The
flue gas analysis shows 9.1% C02, 0.2% CO, 4.6% 02, 86.1% N2. Calculate the
percentage excess air supplied.
10.31 A pure hydrocarbon gas is burned with air and the Orsat analysis of the flue gas gave
the following results: initial volume = 100 mL, volume after caustic absorption = 92.6
mL, volume after pyrogallol absorption = 87.1 mL , volume after cuprous chloride
absorption = 83.4 mL. On the basis of this analysis, determine the following:
(a ) The percent excess air
( b ) The atomic ratio of carbon to hydrogen in the fuel
( c ) The volume of dry flue gas (in m 3) at STP formed per kg fuel burned
10.32 A relatively pure saturated hydrocarbon gas is burnt with air in a small furnace. The
Orsat analysis of the sample of flue gas gives the following data :
Initial volume of the sample = 100 mL, volume after caustic absorption = 93.21 mL,
volume after pyrogallol absorption = 85.74 mL, volume after cuprous chloride absorption
= 83.48 mL. Determine the following:
(a ) The percent excess air
( b ) The atomic ratio H/C in the fuel and the molecular formula of the fuel
( c ) The volume (in cubic metres) at STP of flue gas produced by the combustion of
one kg of fuel
10.33 A furnace is supplied with a gaseous mixture of ethanol, acetic acid and nitrogen
containing 15% nitrogen by volume at 400 K and 90 kPa. It is burned in excess of
air and the flue gas contains 12.5% C02, 1.7% CO, 3.2% 02 and 82.6% N2. The flue
gas leaves the furnace at 550 K and 100 kPa. Calculate the following:
(a ) The percent excess air
( b ) The percentage ethanol in the fuel by volume
( c ) The moles of air per mole of fuel used
( d ) The volume of flue gas in cubic metres per 100 m 3 of fuel burned.
10.34 A producer gas analyzing 2.0% C02, 30.0% CO, 2.0% 02, 8.00% H 2 and 58.0% N2
is burned with 20% excess air. Due to an air leak the flue gas gets diluted and the Orsat
analysis (with water as the confining fluid) of the diluted flue gas is found to be
10.71% C02, 3.57% CO, 7.99% 02 and 77.73% N2. Calculate the following:
352 Stoichiometry and Process Calculations

(a ) The moles of air leaked into the flue gas per 100 kg fuel burned
( b ) The analysis of the dry flue gas before dilution
10.35 The flue gas leaving two boilers, one using natural gas analyzing 96% methane and 4%
C02 and the other using hydrocarbon oil containing C and H in the mole ratio 1 :0.9
has the following analysis: C02 = 10.0%, 02 = 4.5% and N2 = 85.5%. What percent
of the total carbon burned comes from the natural gas?
10.36 One hundred kg per hour of a pure hydrocarbon gas CwH 2„+2 at 295 K is burnt in a
furnace. The flue gas produced analyzed 9.57% C02, 6.38% 02 and the rest nitrogen.
The flue gas leaves the furnace at 700 K and 100 kPa. Calculate the following:
(a ) The atomic ratio H/C, and from this the formula of the fuel
( b ) The volumetric ratio of flue gas to fuel gas
( c ) The amount of flue gas produced in cubic metres per minute
10.37 A fuel gas is made up of 20% propane and 80% CwH 2 n +2 , where n is a whole number.
It is burned with an oxygen-enriched air stream containing 50% oxygen and 50%
nitrogen. The flue gas analyzed 29.72% C02, 3.49% CO, 7.17% 02 and 59.62% N 2.
Determine the following:
(a ) The percent excess air used
( b ) The empirical formula of CwH2„+2
( c ) The rate of air supplied in m3/h at 400 K and 350 kPa if the fuel is burned at a
rate of 1000 cubic metres per hour at 300 K and 110 kPa
( d ) The moisture carried by the flue gas in kg/h.
10.38 The Orsat analysis of the flue gas from an oil-fired furnace is C02: 8%, CO: 3.0%,
02: 4%, and N2: 85%. An analysis indicates that the oil contains 78% by weight carbon,
the remainder being combustible hydrogen and moisture. Air enters at 300 K and 1.013
bar. Assume air to be dry. Calculate the following:
(a ) The percentage excess air used
( b ) The carbon-hydrogen weight ratio of fuel oil
( c ) The volume of air used per kg of oil fired
( d ) The mass of moisture (kilograms) in the flue gas per kg of oil fired
10.39 A furnace is burning fuel oil having the following analysis on a weight basis: 85.0% C,
14.0% H and 1.0% S. Dry air is used for combustion and is supplied in 20% excess.
10 percent of the carbon bums to CO and S is converted completely to S02. It has
come to light that there is an air leak at some point in the base of the stack. The air
is at 300 K and 100 kPa with 70% relative saturation. The Orsat analysis of the stack
gases above this point indicates concentration of C02 and S02 together as 8%. What
percent of the stack gas is air leaked into it? The vapour pressure of water at 300 K
is 3.56 kPa.
10.40 Coal having the following analysis on a dry basis and containing 3.9% moisture on a
dry basis is burned with excess air.
C = 83.05%, H = 4.45%, O = 3.36%, N = 1.08%, S = 0.70% and ash = 7.36%.
Air used contains 0.0048 kg of water vapour per kg of dry air. The Orsat analysis of
 Material Balance with Chemical Reaction 353

the combustion gases gave the following result: C02 + S02 = 15.4%, CO = 0.0,
02 = 4.0% and N 2 = 80.6%. The refuse analyzed 14.0% unbumed ash-free coal and
the rest ash. Check the consistency of the given data and calculate the percent excess
air used.
10.41 Coal having the following analysis on a dry basis and containing 3.9% moisture is
burned with excess air.
C = 65.4%, H = 5.3%, O = 18.5%, N = 1.1%, S = 0.60% and ash = 9.1%.
The Orsat analysis of the combustion gases gave the following result: C02 + S02 =
13.0%, CO = 0.76, 02 = 6.17%, H 2 = 0.87% and N 2 = 79.2 %. Determine the
following:
(a ) The mass of coal fired per 100 kmol of dry flue gas analysed.
( b ) The ratio of the moles of total combustion gases to the moles of dry air supplied
( c ) The total moles of water vapour in the stack gas per 100 kg of coal if the air is
dry
( d ) The percent excess air
10.42 A furnace is fired with a coal analyzing 70% carbon , 5% hydrogen , 12% combined
moisture, 5% free moisture and 8% ash. The relative saturation of air with water
vapour is 60% at 295 K and 101.3 kPa. The combustion of coal is complete and the
refuse contains no combustible matter. The flue gas leaves at 875 K and 100 kPa and
has the following analysis on a dry basis: C02 = 9%, CO = 2%, 02 = 7% and N2 =
82%. The vapour pressure of water at 295 K is 2.64 kPa. Calculate the following:
(a ) The percent excess air
( b ) The volume of flue gas (m 3) formed per kg of coal
( c ) The volume of air (m 3) supplied per kg of coal.
10.43 Hydrogen-free coke containing 85% (weight) carbon and the rest inert materials is
burned in a furnace. It is found that during combustion, 5% of the coke charged is
lost unbumed. The flue gas analysis shows 15.0% C02, 2.0% CO, 4.5% 02 and 78.5%
N2. The flue gas leaves the furnace at 500 K and 100 kPa. Calculate the following:
(a ) The percent excess air assuming complete combustion of coke.
( b ) The weight of air supplied per kg of coke charged
( c ) The volume of flue gas per kg of coke charged
( d ) The composition of the refuse from the furnace
10.44 100 kg/h of coal containing 75.0% C, 4.4% H, 8.5% O, 1.2% S, 1.4% N and 9.5%
ash is burnt with 20% excess air which contains 0.01 kg of water per kg of dry air.
During combustion, 90% of the carbon is burnt to C02 and the rest to CO; and all
sulphur is oxidized to S02. The refuse produced is dry and contains only ash. Calculate
the following:
(a ) Wet air supplied in kg/h
( b ) Wet furnace gas in kmol/h
( c ) Analysis of wet furnace gas
354 Stoichiometry and Process Calculations

10.45 One hundred kilograms of coal having the analysis 70% C, 5% H, 1.0% N, 9.0% O,
2% moisture, and 13.0% ash is contacted with 75 kg of steam in a producer gas plant.
Dry air is also supplied to the unit. The producer gas analyzed 13.11 % C02, 16.38%
CO, 4.37% CH4, 18.08% H 2 and 48.06% N2.The producer gas mixed with undecomposed
steam leaves the gas producer. Tar formed in the unit is found to be 10% of the weight
of coal charged and contained 10% (weight) hydrogen and the rest carbon. Refuse
contains 8% C, and the rest ash. Calculate the following:
(a ) The amount of dry air supplied, in kilomoles
( b ) The percentage of steam fed to the gas producer that is undecomposed
( c ) The volume of wet producer gas (in m 3) obtained at STP
10.46 Producer gas is obtained by burning coke in a restricted supply of air so that more CO
is produced than C02. A producer gas having the CO:C02 mole ratio of 5:1 is to be
prepared from the coke containing 75% carbon and 25% ash. The solid residue after
combustion contains 5% unbumed carbon. Calculate the following:
(a ) The moles of gas produced per 1000 kg of coke burnt
( b ) The moles of air supplied per 1000 kg of coke burnt
( c ) The percentage of carbon lost in the ash
10.47 The ultimate analysis of coal is 78% carbon, 6% hydrogen, 7% oxygen , 3% sulphur,
2% nitrogen and 4% ash. The proximate analysis is 65% FC, 4% moisture, 27% VM
and 4% ash. Calculate the masses of the combined water and net hydrogen in the coal.
10.48 During a test on a coal-fired steam generator, the following data were obtained :
Ultimate analysis of coal: carbon 80.5%, hydrogen 4.6%, oxygen 5.0%, nitrogen
1.1 %, sulphur 1.5% and ash 7.3%. Data on the refuse from ash pit: ash content 96%
and carbon 4%. Orsat analysis of flue gas: C02 16.4%, 02 2.3%, CO 0.4% and N2
80.9%. Calculate the following:
(a ) The weight of dry gaseous products formed per 100 kg of coal fired
( b ) The percent excess air supplied for the combustion
10.49 Coal containing 72% carbon, 15% ash and the remainder being net hydrogen and
moisture is completely burnt in dry air. The Orsat analysis of the flue gas is 9% C02,
4% CO, 8% 02 and the rest N2. Calculate the following:
(a ) The net hydrogen content in the fuel
( b ) The percent excess air used
( c ) The volume of wet flue gas per kg of coal at STP
10.50 Coal with the following ultimate analysis is burned in boiler: carbon 66%, hydrogen
4%, nitrogen 1%, combined water 6%, free water 4% and ash 19%. The refuse drawn
from the ash pit contains 12.6% carbon and the rest ash. The flue gas analysis gives
C02 11.51 %, 02 7.64%, CO 0.09% and N2 80.76%. The humidity of dry air is 0.012
kg/kg dry air. For 100 kg of coal fired, determine the following:
(a ) The percent excess air supplied
( b ) The mass of wet air supplied
( c ) The weight of moisture in gaseous products
( d ) The volume of total flue gases at STP
 Material Balance with Chemical Reaction 355

10.51 A furnace is fired with coal having the following proximate analysis: 2.9% moisture,
33.8% volatile matter, 53.1% fixed carbon and the rest ash. Only incomplete data are
available for the ultimate analysis of coal. These are 1.1% sulphur and 73.8% carbon.
The dry refuse from the furnace analyzed as 3.1% volatile matter, 18.0% fixed carbon,
and 78.9% ash. The Orsat analysis of the flue gas is C02 = 12.1%, CO = 0.2%,
02 = 7.2% and N2 = 80.5%. Air enters the furnace at 293 K with 60% humidity at
101.3 kPa. For 100 kg of coal charged, determine the following:
(a ) The total carbon content in the refuse
( b ) The weight of dry flue gases
( c ) The volume of wet air admitted
( d ) The available hydrogen in the coal
(e ) The complete ultimate analysis of coal
10.52 A furnace is fired with coal of the following analysis: carbon 60%, hydrogen 14%,
oxygen 16%, ash 10% and negligible nitrogen and sulphur. The proximate analysis is
40% FC, 41% VM, 9% moisture and 10% ash. The refuse has the following analysis:
40% FC , 60% ash. It is dry. 1200 m3 of air at 100 kPa, 295 K with a partial pressure
of water of 1350 Pa is supplied per 100 kg of coal. The total pressure of the wet flue
gas is 100 kPa. The ratio of mol C02 to mol CO in the flue gas is 4:1. Determine the
following:
(a ) The percent excess air
( b ) Orsat analysis of flue gas
( c ) Partial pressure of water vapour in the hot wet flue gas
Oxidation of sulphur compounds and related processes
10.53 The analysis of a gas entering the secondary converter in a contact sulphuric acid plant
is 5% S02, 15% 02 and 80% N2. The gas leaving the converter contains 1.06% S02
on an S03-free basis. Calculate the percentage of S02 converted.
10.54 Pure sulphur is burned with excess air to give sulphur trioxide. Due to incomplete
oxidation some sulphur dioxide is also formed. The analysis of the burner gases
showed 8.2% S03, 0.91% S02, 8.65% 02 and 82.24% N2. Determine the following:
(a ) The percent excess air supplied
( b ) The volume of burner gases at 1.2 bar and 600 K per kg of sulphur burned
( c ) The volume of air supplied at 1.013 bar and 288 K per kg of sulphur burned.
10.55 The gases leaving a sulphur burner has the following analysis: 9.8% S02, 8.5% 02 and
81.7% N 2. The gas is sent to a converter where S02 is converted to S03. The gas
leaving the converter is found to contain 0.5% S02, 4.44% 02 and the rest nitrogen.
What percent of the S02 entering the converter is oxidized to S03?
10.56 In the manufacture of sulphuric acid from elemental sulphur, the sulphur is fed to the
burner where it is burned with 100% excess air to produce sulphur dioxide. The
conversion of sulphur to sulphur dioxide is only 90%. The hot combustion gases from
the burner are taken to a converter where S02 is converted to S03. This conversion
is 95% complete. Calculate the following:
356 Stoichiometry and Process Calculations

(a ) The amount of air supplied to the burner per 100 kg of sulphur burned
( b ) The composition of the burner gas
( c ) The composition of the converter gas
10.57 Iron pyrites (FeS2) is burnt with air 100% in excess of that required to oxidize all iron
to Fe203 and all sulphur to sulphur dioxide. Calculate the composition of the exit gases,
if 80% of sulphur is oxidized to sulphur dioxide and the rest to sulphur trioxide. All
iron is oxidized to Fe203.
10.58 The analysis of a gas entering the secondary converter of a contact sulphuric acid plant
is 4% S02, 13% 02 and 83% N 2. In the converter, S02 is oxidized to S03. The gases
leaving the converter contains 0.45% S02 on an S03-free basis. Calculate the percent
conversion of S02.
10.59 The Orsat analysis of a gas leaving a pyrites burner shows 10% S02 and 5% 02 and
the rest N2. What percent of the sulphur burned is oxidized to S03?
10.60 In the combustion of iron pyrites containing 85% FeS2 and 15% gangue, some FeS2
is lost in the cinder unbumed. If the cinder carries 1.5% sulphur as FeS2, how many
kilograms of FeS2 are lost in the cinder per 100 kg of pyrites charged?
10.61 In the combustion of iron pyrites containing 85% FeS2 and 15% gangue, a portion of
the S03 formed during the combustion gets adsorbed in the cinder. If the cinder carries
1.5% sulphur as S03, what mass of S03 is adsorbed by the cinder per 100 kg of
pyrites charged?
10.62 The combustion of iron pyrites containing 90% FeS2 and 10% gangue is found to
produce a burner gas having the Orsat analysis of 10% S02 and 5% 02 and the rest
nitrogen . Determine the volume of gas (in m 3) leaving the burner at 101.3 kPa and
300 K per 100 kg of pyrites charged.
10.63 A mixture of pyrites and zinc sulphide ore is burned in a burner. The mixture contains
75% pyrites and 25% zinc sulphide ore. The pyrites yield 90% FeS2 and the rest
gangue. The zinc sulphide ore contains 70% ZnS and the rest inerts. A sample of cinder
yields 4.0% S. 70% of the sulphur in the cinder is in the form of S03 absorbed in it,
and the rest is unoxidized FeS2. Based on 100 kg of mixed charge, calculate the
following:
(a ) The amount of cinder formed and its analysis
( b ) The percentage of the sulphur left in the cinder based on the total sulphur charged
10.64 In the manufacture of sulphuric acid by the chamber process, iron pyrites having the
composition 75% FeS2 and 25% gangue is burned at 773 K using air. The reaction is
4FeS2 + 1102 — > 2 Fe203 + 8S02
The gases leaving the burner contains 9.3% S02, 8.95% 02 and 81.75% N2. For 100 kg
of pyrites charged, calculate the following:
(a ) The volume of air (in m 3) supplied at 300 K and 100 kPa
( b ) The percent excess air used
( c ) The volume of gas (in m3) leaving the burner at 773 K and 100 kPa
 Material Balance with Chemical Reaction 357

10.65 In a contact sulphuric acid plant, pyrites is burned in dry air to produce a gas analyzing
10% S02 and 7% 02. The cinder carries 2% by weight sulphur as S03. The burner
gas at a rate of 2000 m 3/h at 365 K and 100 kPa is fed to an absorber to absorb the
entire S03 present in it. 70% H2S04 is used for the absorption at a rate of 25 kg/h
and produces 90% H 2S04. Determine the percentage of FeS2 in the pyrites charged.
10.66 One hundred kilograms of pyrites containing 32% S is mixed with 10 kg of pure
sulphur and is burned in excess air. A part of sulphur is converted to S03 and the
remaining part to S02. But the sulphur trioxide in the combustion gases will not be
detected in the Orsat analysis. The Orsat showed 13.5% S02, 3.0% 02 and 83.5% N2.
Assuming that the entire S03 in the combustion gases comes from the oxidation of
pure sulphur, what is the fraction of the sulphur charged that is converted to S03?
10.67 Impure FeS2 is burned to give a burner gas containing 8.0% S02, 10.2% 02 and 81.8%
N 2.

FeS2 H
4
02 — ^ —2 Fe 203 + 2S03
FeS2 H
4
02 — ^ —2 Fe 203 + 2S02
Fe203 + 3S03 — » Fe (S04)
2 3

The pyrites contains 48% (weight) sulphur and the cinder contains 2% ( weight)
sulphur as Fe2(S04)3 and no FeS2. For a basis of 100 kg of pyrites burned, calculate
the following:
(a ) The weight of cinder
( b ) The moles of burner gas constituents
( c ) The percentage excess air based on conversion to S03
( d ) The percentage conversion of S to S03.
10.68 A mixture of pure sulphur and pyrites analyzing 85% FeS2 and 15% gangue is burnt
in a standard pyrites burner. The burner gas contains 10% S02, 7% 02, and 83% N2
on a S03-free basis and contains 1 mole of S03 per 100 moles of S03-free burner gas.
The cinder contains 2% S as S03. Calculate the percentage of FeS2 in the charge.
10.69 In the contact process for the manufacture of H 2S04, S03 is obtained by burning iron
pyrites ( FeS2) in air. The air supplied is 40% in excess of that required for the complete
conversion of all S to S03. However, in the burner, only 40% of the sulphur is
converted to sulphur trioxide and the remainder is converted to S02. Iron is oxidized
to Fe203. Of the pyrites charged, 15% is lost by falling through a grate. The burner
gas is taken to a converter, where 95% of S02 present is converted to S03. For a basis
of 100 kg pyrites charged, calculate the following:
(a ) The weight of air supplied, kg
( b ) The burner gas analysis, wt%
( c ) The total weight of S03 produced in kilograms
( d ) The converter gas analysis, vol%
(e) The weight of cinder in kilograms
358 Stoichiometry and Process Calculations

10.70 In the contact process for the manufacture of sulphuric acid, iron pyrites (FeS2) is
burned with air so that iron is oxidized as Fe203 which leaves with the cinder and S
is oxidized to its oxides. It is found that in the burner 40% of sulphur is converted to
S03 and the rest to S02. The latter is further oxidized to S03 in the catalytic converter.
This conversion may be assumed to be 96% complete. About 10% of the pyrites
charged is lost unbumed and leaves with the cinder. The air supplied to the burner is
40% in excess of that required for the conversion of all S to S03.
(a ) How many kilograms of air are supplied per kg of pyrites charged?
( b ) What is the percent composition on a weight basis of the gases leaving the burner?
( c ) What mass of S03 is obtained per 100 kg of pyrites charge?
( d ) What is the degree of conversion of S in the charge to S03?
10.71 Dry pyrites containing 48% sulphur is burned in a sulphuric acid plant. The cinder
carries 2% sulphur as S03. The burner gas analysis shows 8.25% S02, 7.85% 02 and
the rest N2. The burner gas is passed through a converter where S02 is oxidized to
S03. The converter gas is admitted into an absorber to absorb the S03 in 70% H2S04.
The gas leaving the absorber is free of S03 and contains 1.09% S02, 4.73% 02 and
94.18% N2, and the acid produced is 100% H2S04. No secondary air supply is used
in the converter. For 100 kg of pyrites charged, determine the following:
(a ) Moles of S02 in the burner gas
( b ) Mole percent of S03 in the converter gas
( c ) The amount of 100% acid produced in the absorber
10.72 Sulphuric acid can be produced as a by-product in the manufacture of zinc from
sulphide ores. The ore analyzes 65% ZnS and 35% inert impurities by weight. The ore
is burned in a furnace and the resulting S02 is converted to S03 in a catalytic reactor.
The S03 is then absorbed by water to give sulphuric acid, the final product being 2%
water and 98% H 2S04 by weight. A total of 99% of sulphur in the ore is recovered
in the acid. The chemical reactions are:
ZnS + —
1.502 > ZnO + S02
S02 + 0.5 O 2 — > S03
S03 + H20 H 2S04
Compute
(a ) The quantity of the product sulphuric acid produced in a zinc plant that processes
2 x 105 kg/day of ore
( b ) The quantity of water required per day
10.73 In a sulphuric acid plant, 100 kg/h of dry pyrites containing 90% FeS2 and 10% inert
material is burned with dry air in the burner. Only 85% of FeS2 is oxidized . In the
burner, 90% of the sulphur burnt is oxidized to S02 and the balance to S03. Dry air
supplied is 50% in excess of that required for the complete conversion of S to S03.
Burner gas is fed to a converter where 95% of the S02 is converted to S03 using the
oxygen present in the burner gas. All the S03 produced is absorbed in 70% H 2S04 fed
 Material Balance with Chemical Reaction 359

at a rate of 100 kg/ h in an absorption tower. No S03 is adsorbed on the cinder.

Determine the following:
(a ) The percentage of sulphur in cinder
( b ) The amount of sulphuric acid produced in kg/h
( c ) The concentration of the acid product
( d ) The amount of gas leaving the absorber in kg/h
(e ) The composition of the gas leaving the absorber

Carbon dioxide from limestone

10.74 A limestone analyses 92.9% CaC03, 5.4% MgC03 and 1.7% insolubles.
(a ) How many kilograms of CaO can be made from 1000 kg of this limestone?
( b ) How many kilograms of C02 can be recovered per kg of limestone?
( c ) How many kilograms limestone are needed to make 1000 kg of lime?
10.75 Carbon dioxide is produced by treating limestone with sulphuric acid. The analysis of
the residue leaving the process showed 9.0% CaS04, 5.5% MgS04, 1.0% H 2S04,
0.5% inerts and 0.1% C02 and 83.9% water. The limestone charged contains calcium
carbonate, magnesium carbonate and inert insoluble matter. The C02 and water vapour
produced are removed. Determine the following:
(a ) The percent composition of the limestone used
( b ) The percent excess acid used
( c ) The quantity of C02 recovered per 100 kg of limestone charged
10.76 The calcinations of limestone can be represented by the following reactions:
CaC03 ^ CaO + C02
MgC 03 MgO + C02
In a certain operation 100 kg of limestone containing only calcium and magnesium
carbonates and no inert materials is calcined producing 30 m 3 of C02 at 348.32 K and
atmospheric pressure. What is the composition of the limestone in weight percent?
10.77 Carbon dioxide is produced by treating limestone ore with 15.0% sulphuric acid.
1000 kg of ore consisting of CaC03, MgC03 and inert materials is mixed with an
excess of acid:
CaC03 + H 2S04 ^ CaS04 + C02 + H20
MgC03 + H 2S04
^ MgS04 + C02 + H20
The liquid product containing 6.37% MgS04, 1.25% H2S04 and the rest water is
treated with pure CaC03 to neutralize the free acid. The solid residue consisting of
CaS04 and inerts is separated from the liquid by filtration . If the filter-cake analyzed
1 kg of inert per 20 kg of CaS04, determine the following:
(a ) The composition of the limestone used
( b ) The moles of C02 produced
( c ) The weight of CaC03 required to neutralize the excess acid
( d ) The percent excess of acid used
360 Stoichiometry and Process Calculations

10.78 A lime furnace bums 100 kg of coal containing 80% C, 5% H, 2% N, 1.0% S and
12% ash and limestone containing 82.0% CaC03, 7.0% MgC03 and 11.0% inert
material with excess air. The average stack gas analysis is 14.42% C02, 6.03% 02,
and 79.55% N2. C02 percentage includes S02 also. Calculate the following:
(a ) The percent excess air used for combustion
( b ) The fuel ratio on a weight basis
( c ) The amount of limestone supplied, in kilograms
( d ) The amount of total lime produced, in kilograms

Reactions involving phosphorus and phosphorus compounds

10.79 In the manufacture of phosphorus, calcium phosphate is mixed with sand and charcoal,
and heated in an electric furnace. The silica used is 15% in excess of that theoretically
required to convert all the phosphorus to silicate. Charcoal used is 50% in excess of
that required to combine with oxygen in the phosphorus pentoxide to form carbon
monoxide. It is observed that the conversion to silicate is 85% complete and reduction
of the oxide to phosphorus is only 70% complete. Determine the following:
(a ) The ratio in which phosphate, sand and charcoal are mixed before they are sent
to the furnace
( b ) The quantity of phosphorus produced per 100 kg of the above mixture
10.80 The off-gases from the phosphate reduction furnace analyzes 8.0% P4, 85.0% CO, and
7.0% N2 on a mole basis. This gas is burned with air under such conditions that the
phosphorus is selectively oxidized. The oxides of phosphorus (P406 and P4O 10) present
in the flue gas are precipitated by cooling and separated. After separation, the gases
analyzed 0.8% C02, 23.0% CO, 68.0% N2 and 8.2% 02. Calculate the following:
(a ) The percent of CO entering the burner that is converted to C02
( b ) The percent of P4 that is oxidized to P4O10.
10.81 Phosphorus is produced by reacting calcium phosphate with silica and carbon in an
electric furnace:
Ca 3(P04)2 + 3Si02 3CaSi03 + P205
2P205 + 5C ^ 4P + 5C02
Calcium silicate forms a liquid slag, whereas phosphorus passes off as vapour along
with C02 and is condensed. Phosphate rock containing 80% Ca 3(P04)2 and the rest
inert impurities is charged with 25% excess silica and 50% excess carbon. The first
reaction is 80% complete, whereas the second is 90% complete. Calculate the following
on a basis of per 1000 kg of the rock charged to the furnace:
(a ) The weight of phosphorus produced
( b ) The weight of calcium silicate produced
( c ) The percent recovery of phosphorus
 Material Balance with Chemical Reaction 361

Recovery of metals and non-metals from ores

10.82 One hundred kilograms of flurospar containing 75% by weight CaF2 and 25% inert
materials is treated with concentrated sulphuric acid to produce hydrofluoric acid (HF).
CaF2 + H 2S04 -> CaS04 + 2HF
Pure sulphuric acid is used in 30 percent excess of that theoretically required . 95% of
the hydrofluoric acid produced in the reaction chamber leaves as gas while the remaining
5% leaves with the solid residue which consists of CaS04 produced in the reaction,
the unreacted sulphuric acid and the inert materials.
(a) Determine the amount of solid residue formed.
(b) Express the concentration in weight percent.
10.83 Copper is extracted from its ore having the following analysis: CuS = 10%, FeS2
= 30%, inerts = 60%. The ore is first crushed and subjected to flotation during which
70% of the inert materials are eliminated. The resulting concentrate has the following
analysis: CuS = 16%, FeS2 = 48%, inerts = 36%. This is then roasted where the
following reactions occur:

2CuS H
2
02 — ^ Cu 20 + 2S02
2FeS2 + —2 02 — > Fe203 + 4S02
The Cu20 is then reduced to metallic copper. If 1000 kg of copper ore is originally
charged, how many kilograms of the metal can be obtained if there is 3% loss during
the reduction of the oxide to the metal.
10.84 For producing 1000 kg of pig iron of composition 94% Fe, 5% C and 1 % Si, iron ore
containing 89.6% Fe203 and the rest Si02 is reduced in a blast furnace using 1000 kg
of coke containing 90% C and 10% Si02. The flux used contains 94% CaC03,
3% MgC03 and 3% Si02. If it is desired that the slag contains 40% (CaO + MgO),
how much flux is required for producing 1000 kg of pig iron? Assume that no iron
is present in the slag.
10.85 Powdered bauxite is reacted with dilute sulphuric acid to produce aluminium sulphate.
In a typical operation, 1000 kg of bauxite containing 50% A1203 is treated with 1700
kg of 75% sulphuric acid. The reacted mass is filtered to remove solid residue. The
filtrate is concentrated to crystallize 2000 kg of A12(S04)3 9H20. Calculate the following:
*

(a ) The percent excess reactant used

( b ) The degree of completion of the reaction
( c ) The weight and composition of solid residue produced.
362 Stoichiometry and Process Calculations

Nitrogen, ammonia and nitric acid

10.86 Synthesis gas consists of nitrogen and hydrogen in the ratio 1 :3. It is prepared by
mixing air with pure hydrogen. Oxygen is removed as water formed in the reaction
between hydrogen and oxygen. For treating 100 moles of air containing 21% oxygen,
78% nitrogen and 1 % argon, determine (a) moles of hydrogen added (b) weight of
water condensed in kg.
10.87 A plant produces 600 tons/day of ammonia. Nitrogen and hydrogen in the mole ratio
1 :4 is sent to the converter. The gases leaving the converter contains these gases in
the ratio 1 :4.25. Calculate the volume of gases measured at 773 K and 100 kPa that
is admitted to the reactor per day.
10.88 In the fixation of nitrogen by the arc process, air is passed through an electric arc.
Some of the nitrogen is oxidized to NO which on cooling is oxidized to N02. Of the
N02 formed, 66% will get associated to N204 at 300 K. The gases are then passed
into absorption towers where HN03 is formed by the following reaction:
H20 + 3N02 NO + 2HN03
The NO liberated in this reaction will be reoxidized in part and form more nitric acid.
In the operation of such a plant, it is found possible to produce gases from the arc
furnace in which the nitric oxide is 2% by volume while hot. The gases are cooled to
300 K at a pressure of 1.013 bar before being sent to the absorber. Calculate the
following:
(a ) The complete analysis by volume of the hot gases leaving the furnace assuming
that the air entering the furnace was of average composition
( b ) The partial pressures of N02 and N204 in the gases entering the absorption tower
( c ) The weight of HN03 formed by 1000 m 3 of gas entering the absorption system
if the conversion to HN03 of the combined N2 in the furnace gases is 85%
complete
10.89 HN03 is produced by treating NaN03 with 95% H2S04. The resulting nitre cake
contains 34% H 2S04 and 1.5% H20. 2% of the HN03 formed remains in the cake. The
reaction is complete. Calculate the following:
(a ) The weight of nitre cake per 100 kg of NaN03
( b ) The composition of nitre cake
( c ) The weight of aqueous H2S04 used
( d ) The weight of HN03 and H20 distilled from the nitre cake for 100 kg of NaN03
10.90 Urea is produced synthetically by reacting ammonia and carbon dioxide to form
ammonium carbamate which is then decomposed to urea and water:
2NH3 + C02 NH 2COONH 4
NH 2COONH 4 NH 2CONH 2 + H 2O
The conversion of ammonia is only 60%. If 1000 kg of urea is to be produced,
determine the following:
(a ) The volume of ammonia fed at STP
( b ) The amount of water produced
 Material Balance with Chemical Reaction 363

10.91 In the nitric acid manufacture 100 m 3/h of ammonia at 300 K and 101.3 kPa is mixed
with air and passed over a catalyst in a converter and the following reaction takes
place:
4NH3 + 502 -> 6H20 + 4NO
The gases are then passed into an oxidizing tower where the oxidation is completed
according to the following reaction:
2NO + 02 -> 2N02
The gases from the oxidizing tower are passed into a cooling tower where N02 is
absorbed in 150 kg/ h of water and forms nitric acid as per reaction:
3N02 + H20 -> 2 HN03 + NO
The overall reaction in the process is given by
NH3 + 202 -> HN03 + H20
Oxygen present in the air supplied is 20% in excess of that required for complete
oxidation of the ammonia to nitric acid and water. Assume that ( 1 ) the degree of
completion of the reaction in the converter is 85% and no other decompositions take
place, (2) 90% of the nitric oxide entering the oxidizing tower is oxidized to nitrogen
peroxide, and (3) the cooling tower exit gas contains no water vapour and all N02 is
absorbed in water. Calculate the following :
(a ) The amount of air to be used at 300 K, 101.3 kPa in m3/h
(b) The moles of gases leaving the converter and its composition
(c ) The moles of gases leaving the oxidiser and its composition
(d ) The amount in kg/ h and concentration by weight percent of nitric acid produced
Chlorine, hydrochloric acid and chlorination reactions
10.92 Hydrochloric acid is oxidized to chlorine by air in the presence of a catalyst. Air is
supplied 30% in excess of the theoretical requirement and the oxidation of the acid is
60% complete. Calculate the following:
(a ) The ratio of acid to air on a weight basis
( b ) The composition of the gases leaving the reactor on a weight basis
10.93 Chlorine is produced by the oxidation of hydrogen chloride gas with air
4HC1 + 02 -> 2 C12 + 2H20
The reaction is carried out at 1.2 x 105 N/m2 and 400 K. 50 percent excess air is used
and the reaction is only 80 percent complete. Calculate
(a ) The volume of air admitted per 100 m3 of HC1 if both air and HC1 enter the reactor
at 1.0 bar and 290 K
( b ) The volume of gases leaving the reactor per 100 m 3 of HC1 entering
( c ) The weight of chlorine produced per 100 m 3 of HC1 entering
( d ) The percent composition by volume of the exit gas on a dry basis
364 Stoichiometry and Process Calculations

10.94 In the Deacon process for the manufacture of chlorine, a dry mixture of hydrochloric
acid and air is passed over a heated catalyst. Acid is oxidized in the presence of air,
which is supplied 20% in excess of that theoretically required:
4HC1 + 02 -> 2H20 + 2C12
Calculate the following for the oxidation of 1 kg of acid:
(a ) The amount of air supplied, in kilograms
( b ) If 60% conversion is achieved, the composition of the product gases expressed
in weight percent
( c ) The dew point of the exit gas stream which is at a pressure of 100 kPa and
temperature of 450 K
The vapour pressure of water is given by the Antoine equation:
3799.887
In Ps = 16.26205 -
T - 46.854
where pressure is in kPa and temperature is in K.
10.95 Carbon tetrachloride is made by chlorination of carbon disulphide in the following two
steps:
CS2 + 3C12 CC14 + S2C12
CS2 + 2S2C12 ^ CC14 + 6S
The reactants are admitted in stoichiometric ratio. Determine the mass of carbon
tetrachloride and sulphur produced from 1000 kg of sulphide if
(a ) The conversion in both the reactions are 100%
( b ) The yield is 85% in the first reaction and 90% in the second reaction .
10.96 Catalytic vapour-phase chlorination of CS2 gives carbon tetrachloride:
CS2 + 3C12 CC14 + S2C12
The products leaving the converter analyzed 26.0% CC14, 26.0% S2 C12, 17.5% CS2 and
30.5% Cl 2. Determine the following:
(a ) The excess reactant and the percent excess
( b ) The percent conversion
( c ) The quantity of CC14 obtained (in kilograms) per 100 kg of chlorine admitted
10.97 Ethylene dichloride is manufactured by the oxychlorination of ethylene:
2C 2 H4 + 4HC1 + 02 -> 2C2 H4C12 + 2H20
Though ethylene and air are supplied respectively 5% and 10% in excess over those
required for the complete conversion of hydrogen chloride, the conversion attained is
found to be only 90%. For 500 kmol of HC1 supplied, calculate the following:
(a ) The moles of the reactant and products
(b) The mass of the reactants and products
(c ) The composition of the reactant stream in weight percent
(d ) The composition of the product stream in weight percent.
 Material Balance with Chemical Reaction 365

10.98 Monochloroacetic acid (MCA) is produced at a rate of 5000 kg/h by chlorination of

glacial acetic acid with gaseous chlorine.
CH3COOH + Cl2 CH2ClCOOH + HC1
Chlorine is supplied at a rate of 4500 kg/h. It is found that 300 kg/h of dichloroacetic
acid (DCA ) also is formed according to
CH 2ClCOOH + Cl2 -> CHCl 2COOH + HC1
Acetic acid is supplied in excess to minimize DCA production. Determine the conversion
and yield of MCA.
10.99 Hydrochloric acid is made by the action of NaCl with H 2S04. The following reactions
occur in series:
NaCl + H 2S04 -> NaHS04 + HC1
NaHS04 + NaCl Na2S04 + HC1
One thousand kilograms of pure NaCl is treated with aqueous sulphuric acid solution
of strength 75% H 2S04. The solid cake obtained analyzed 91.5% Na 2S04, 4.8%
NaHS04, 2.0% NaCl, 1.3% H20 and 0.4% HC1. Determine the following:
(a ) The degree of completion of the first reaction
( b ) The degree of completion of the conversion to Na 2S04
( c ) The quantity of acid added
( d ) The quantity of cake obtained
(e ) The weight of gases if the gases driven off are HC1 and water vapour
9.100 For purification of silicon from the metallurgical grade to the semiconductor grade,
100 kg of the metal is reacted with hydrogen chloride gas at 573 K. From several
polychlorinated silanes that are formed in the reaction, trichlorosilane (HSiCl3), which
is a liquid at room temperature, is separated by fractional distillation. Determine the
quantity of pure trichlorosilane separated in the distillation unit if the gases leaving
analyzed 21.0% H 2SiCl 2, 14.0% SiCl4 and 65% H 2.

Hydrogenation, hydration and oxidation

10.101 Coal is hydrogenated in a fluidized bed reactor in the presence of air and steam at
675 K in order to produce gaseous hydrocarbon fuels. 2000 kg per hour of coal
containing 10% inert material by weight is charged into the reactor from the top, and
air and steam admitted from the bottom at a rate of 25 000 kg/h and 3500 kg/h
respectively. Assuming the complete conversion of coal, determine the flow rate of exit
gases in kg/ h.
10.102 An organic ester of formula C 19H3602 is to be hydrogenated at a rate of 100 kg/h to
yield C 19 H3802. The hydrogen required for the plant, which runs continuously, is
available as 50 L cylinders in which the gas is contained at 70 bar and 300 K. How
many cylinders should the company order per week ?
366 Stoichiometry and Process Calculations

10.103 Formaldehyde is made by the oxidation of methanol with air. The analysis of the exit
gas from the reactor shows 63.1 % N2 , 13.4% 02, 5.9% H20, 12.3% CH3OH, 4.1%
HCHO and 1.2% HCOOH. Calculate the following:
(a ) The conversion per pass
( b ) The ratio of air to methanol in the feed
10.104 In a propylene plant, 100 kg/h of pure propane is fed to a catalytic reactor where it
is converted to a gas containing 25% propylene, 45% propane, and 30% hydrogen by
volume. This reactor gas is separated in a separator unit into three streams: ( 1 ) light
gas containing 1.2% propane, 0.8% propylene and all hydrogen formed in the reactor,
(2 ) desired product containing 99% propylene and 1% propane, and (3) bottom product
containing 2% propylene and 98% propane. All the bottom product is returned back
to the reactor. Calculate the following :
(a ) The amount of product obtained in kg/h
( b ) The amount of propane recycled, kg/h
( c ) The amount of propane in light gas, kg/h
10.105 Formaldehyde is produced by the gas phase oxidation of methanol with air over a
catalyst

1
CH3OH + - 02 -> HCHO + H20
100 m3 of methanol vapour at 1.013 x 105 N/m2 and 550 K is to be treated. If 10%
excess air is supplied and the reaction is only 80% complete, calculate the following:
(a ) The composition of the product gas
( b ) The volume of product gases at 1.5 x 105 N /m2 and 800 K
10.106 Ethylene oxide is produced by burning ethylene gas with air in the presence of a
catalyst. In the reaction, a substantial portion of ethylene is converted to ethylene oxide,
a small fraction is completely oxidized to C02, and water and some gases remain
unconverted. The ethylene oxide in the product gas is recovered by absorption. The
Orsat analysis of the gases leaving the absorber is: 8.77% C02, 4.38% 02 and 4.38%
ethylene. Calculate the percent of the ethylene fed to the reactor that is converted to
the oxide.
10.107 Ethylene glycol (CH 2OH)2 is produced by air oxidation of ethylene to ethylene oxide
and subsequent absorption of the oxide in water.
1
C 2 H4 + ~
02 — ^ C2H40

C2 H 40 + H20 -> ( CH 2 OH)2

A portion of the ethylene is oxidized to C02:
C 2 H4 + 302 -> 2C02 + 2H20
100 kmol of a gas mixture containing 10% ethylene and 90% air is fed to the oxidizer.
The gases leaving the reactor are absorbed in water fed at the rate of 10 moles per
 Material Balance with Chemical Reaction 367

100 moles of the original gas mixture. The off-gases leaving the absorber gave the
following analysis on a dry basis: C 2 H4 2.31%, C02 6.94% and the rest oxygen and
nitrogen. The gases leave the absorber at 101.325 kPa saturated with water vapour at
306 K. (The vapour pressure of water at 306 K is 5 kPa.) Determine the following:
(a ) The moles of ethylene glycol produced
( b ) The percent conversion of ethylene to glycol
( c ) The moles of dry gases leaving the absorber
( d ) The weight percent of ethylene glycol in the glycol water solution
10.108 Acetylene is produced industrially by reacting calcium carbide and water:
CaC2 + H20 -> CaO + C 2H2
Calcium carbide containing 8% inert impurities is reacted with water so that the
reaction goes to completion. For producing 1000 kg of acetylene, calculate the following:
(a ) The weight of impure carbide needed
( b ) The weight of solid residue after the reaction
( c ) The weight ratio of acetylene to water vapour if the acetylene produced is saturated
with water vapour at 306 K and 101.3 kPa. The vapour pressure of water at
306 K is 5 kPa.
10.109 Ethanol is produced by the hydration of ethylene :
C2H4 + H20 -> C2H5OH
Some of the product is converted to ethyl ether by the side reaction
2C2 H5OH -> (C 2H5)20 + H20
The feed to the reactor contains 25% C2 H4, 65% H20, and the balance inert materials
on a mole basis. An ethylene conversion of 10% and ethanol yield of 90% is achieved.
Compute the composition of the reactor output stream.
10.110 A pilot plant reactor was charged with 50 kg of naphthalene and 200 kg (98% by
weight) of sulphuric acid. The reaction was carried out for 3 hours at 430 K. The
reaction goes to completion:
C 10H 8 + H 2S04 C 10H7(SO3H) + H20
C10H8 + 2H 2S04 C 10H6(SO3H)2 + 2 H20
The product distribution by weight was found to be 18% monosulphonate and 82%
disulphonate of naphthalene. Calculate
(a ) The quantities of monosulphonate and disulphonate products
( b ) The complete analysis of the product
11 Bypass, Recycle and
Purge Operations

Chemical processing would have been a smooth affair, if the desired changes could be brought
about by taking the input streams in a single pass through the series of equipment that constitute
the process unit. But, this is not the case in many situations where the single pass operations
usually fail to provide the desired change . Chemical reactions generally never go to completion
when sent through the system in a single pass. It becomes necessary to return back the
unconverted streams and admit them to the process units again along with the feed admitted
afresh. Returning the streams back ensures higher conversion and higher yield of the products.
Reuse of materials in such recycle loops leads to reduction in cost and improvement in
efficiency of the process. It is also true that in some cases, it may not be necessary to admit
the entire input streams to certain stages of the process. Such streams that are allowed to skip
one or more stages and go directly to another downstream stage are called bypass streams. The
desired change can be brought about by admitting the remaining part of the input streams to
the process unit that was skipped by the major part of the input stream . The processed stream
is then mixed with the bypass stream downstream from the unit in such proportions as
demanded by the process. Purging operations are performed when there is accumulation of
undesired materials within the recycle loop. By bleeding off a small fraction of the streams, the
undesired impurity can be maintained within acceptable limits. In this chapter, we will discuss
— —
these three special streams recycle, bypass and purge and explore the material balance
calculations involving them in detail.

11.1 BYPASS
Bypass is employed mainly for effecting relatively small changes in a process stream . This is
achieved by introducing large changes in a small portion of the original stream and diverting
the other portion without passing it through the unit accomplishing this change. The portion
so diverted is known as bypass stream . The stream that is passed through the process unit is
later mixed with the bypassed stream to get the final desired change in the combined stream .
368
 Bypass , Recycle and Purge Operations 369

For example, consider the air-conditioning practised in process industries to produce air of
desired humidity. Air can be humidified or dehumidified by passing it through a spray chamber
where water is sprayed into the air stream. An accurate control of the final humidity is possible
by splitting the air stream into two parallel streams and subjecting one stream to the humidification
or dehumidification operation described and bypassing the other stream around the humidifier
or dehumidifier. The desired final mixture is obtained by combining the bypass stream with the
conditioned air (refer to Figure 11.1).
B, bypass stream

E, final
A , Gross feed product
Process unit
C D

Figure 11.1 Bypass operation.

A portion of the gross feed stream ( A ) is diverted before entering the process unit and
constitutes the bypass stream ( B). The remaining portion ( C) is passed through the unit and
subjected to the necessary operation or process. The streams A , B and C have the same
composition as well as other properties. The product stream leaving the processing unit ( D )
combines with the bypass stream and forms the final product ( E ) of the desired properties.
Bypass is desired when we need a product with properties in-between the untreated
process stream and the process outlet product. For example, in a juice concentration process,
the dehydration process runs most effectively by removing more water than is actually desired.
A small portion is subjected to dehydration, which is later mixed with the major portion of the
unprocessed feed in a bypass loop.

EXAMPLE 11.1 Air at 320 K saturated with water vapour is dehumidified by cooling to
285 K and by condensation of water vapour. Air leaving the dehumidifier saturated at 285 K
is mixed with a part of the original air which has bypassed the dehumidifier. The resulting air
stream is reheated to 320 K. It is desired that the final air contains water vapour not more than
0.03 kg per kg of dry air. Calculate:
(a) The dry air bypassed (kg) per each kg of dry air sent through the dehumidifier
( b ) The water vapour condensed in the dehumidifier (kg) per 100 m3 of air sent through it
( c ) The volume of final air obtained per 100 m 3 of air passed through the dehumidifier.
The total pressure is atmospheric and the vapour pressures of water are 1.4 kPa at 285 K
and 10.6 kPa at 320 K.
Solution Basis: 1 kg of dry air passed is through the dehumidifier.
Let x kg of dry air be present in the air bypassed.

Saturation humidity of air at 320 K = ~~

rrr x = 0.0725 kg of water/kg of dry air
Tzr
—
101.3 10.6 29

1.4 18
Saturation humidity at 285 K =
101.3 - 1.4 29
= 0.0087 kg of water/kg of dry air
370 Stoichiometry and Process Calculations

A C D E F
Dehumdifier Heater
M
A , B , C : Saturated air at 320 K, D: Saturated air at 285 K
E : Air containing 0.03 kg of water vapour/kg of dry air
F : Air heated to 320 K, containing 0.03 kg of water vapour/kg of dry air

Figure 11.2 Bypass operation in Example 11.1 .

Humidity of air leaving the dehumidifier = 0.0087 kg of water/kg of dry air

Humidity of air bypassed = 0.0725 kg of water/kg of dry air
These two air streams are combined to give the air with a humidity 0.03 kg of water
vapour per kg of dry air at point M . Take a moisture balance at point M . We get
1 x 0.0087 + x x 0.0725 = (1 + x) x 0.03
On solving, we get x = 0.5012.
(a ) 0.5012 kg of dry air is bypassed per kg of dry air sent through the dehumidifier.
( b ) For each kilogram of dry air passed through the dehumidifier, water condensed = 0.0725
- 0.0087 = 0.0638 kg .

1 kg of dry air = 1 + 0.0725 = 1.0725 kg of wet air = —1 + —0:—0725

— = 0.0385 kmol of wet air
0.0385 kmol of air = 0.0385 x 22.414 = 0.8632 m 3 at STP
1 01325 320
0.8632 m 3 at STP = 0.8632 x x = 1.0115 m 3 at 101.3 kPa and 320 K
1.013 273.15
3
For 1.0115 m of air sent through the dehumidifier, 0.0638 kg of water vapour is condensed.
0.0638
For 100 m3 of air, amount of water vapour condensed x 100 = 6.3075 kg .
1.0115
(c) 0.5012 kg of dry air is bypassed per 1 kg dry air passed through the dehumidifier.
Hence, for each kilogram of dry air, the final air obtained is 1.5012 kg of dry air. Since 1 kg
of dry air along with the accompanying water vapour has a volume of 1.0115 m3, the kilogram
of dry air in the final air is
1.5012
x 100 = 148.41 kg
1.0115
148.41
Moles of dry air produced =
29
= 5.1177 kmol
 Bypass, Recycle and Purge Operations 371

,
Moisture content in the final air - 0.03
k8 fw te
°
kg of dry air
= 0.03 x "
18
= 0.0483
kmo1 of water
of
kmol air
dry

It means that 1.0483 kmol of wet air is present per each kilomole of dry air. Therefore,

total moles of final wet air = 5.1177 x * = 5.3651 kmol . At 320 K and 101.3 kPa, this
has a volume of 5.3651 x 22.414 x
101.3
x
273.15
= 140.91 m 3
The volume of final air per 100 m, 3 of air passed through the dehumidifier = 140.91 m 3.

11.2 RECYCLE
A system with recycle is one in which a stream leaving a processing unit is partly returned to
the same unit for reprocessing or reusing. The recycling of the fluid stream in chemical
processing is a common practice to increase yields, to increase the purity, to enrich a product,
to conserve heat, or to improve operations. Recycling may also be used to recover an expensive
catalyst, reuse a lubricant or refrigerant, maintain feed concentration below certain levels by
diluting the process streams either to control flow or to control the rate of reaction . A common
example is the drying operation where a portion of the hot air leaving the dryer is recycled to
conserve heat or to reduce the rate of drying by controlling humidity of the air entering the
dryer. In a fractionating column, a part of the distillate is returned to the column as reflux to
enrich the product.
The recycling operation is shown in Figure 11.3. The product stream D is split into two
streams and one is recycled (B). The other stream is removed as the net product (E) from the
operation. The physical properties and chemical constitution of streams D, E and B may be
same or different depending on the operations that the stream D has undergone before it is
separated into streams E and B . However, in majority of cases, the process effluent (D),
process product (E) and the recycle (B) have identical compositions. The recycled stream
combines with the fresh feed (^4 ) and enters the unit as gross feed (C). The ratio of the quantity
of a substance in the recycled stream to the quantity of the same substance in the fresh feed
is known as recycle ratio.
B , Recycle stream

A, Fress feed C D E, Net product

Process unit

Figure 11.3 Recycle operation.

In processes involving chemical reactions, recycle is generally employed to increase the

yield. Many organic reactions do not give 100% yield of the desired product. In cases where
372 Stoichiometry and Process Calculations

the yield is low, the unconverted reactants are separated from the product and sent back to the
reactor as recycle stream and joined with a stream of reactants that enter the reactor. In
ammonia synthesis, the gas mixture leaving the converter after recovery of ammonia is recycled
through the converter. Recycle process involving chemical reactions can be schematically
represented as shown in Figure 11.4.
Recycle stream
(unreacted mass)

Fresh feed Net product

Reaction vessel

Product separator

Figure 11.4 Recycle in processes with chemical reaction .

Recycle process necessitates the specification of two types of conversions— the overall
conversion and the single pass conversion . The overall conversion is the fraction of the reactant
in the fresh feed that is reacted considering the overall process.
moles of reactant _ moles of reactant in the product
. in the fresh feed from the overall process
^
Overall conversion =
moles of reactant in the fresh feed
moles of reactant in stream A - moles of reactant in stream E
moles of reactant in stream A
The single pass conversion is the fraction of the reactants that actually enter the reactor
in a single pass that is converted.

_ ,
Single pass conversion
.
=
moles of reactant fed
into the reactor
_
moles of reactant
leaving the reactor
moles of reactant fed into the reactor
_ moles of reactant in stream C - moles of reactant in stream D
moles of reactant in stream C
Two types of material balances may be written— (1) the overall material balance in which
the net feed material is equated to the net products, and (2) the once-through material balance,
in which the gross feed is equated with the gross products. Material balances can be written
for several different systems shown by the dashed envelopes 1, 2, and 3 in Figure 11.5.
Envelope 1 contains the entire process including the recycle stream, but the material balance
over this gives no insight into the recycle stream. However, the balances written over envelopes
—
2 and 3 contain recycle streams. Consider a chemical reaction A + B > C being carried out
in a unit shown below, where the single pass conversion of A is 25%. Assume that the reactants
are present in stoichiometric proportions in the fresh feed. What is the amount recycled per
100 moles of fresh feed?
 Bypass , Recycle and Purge Operations 373

i?, Recycle stream Envelope 1

Envelope 3
Envelope 2

E , Net product
A 9 Fresh feed Processing unit

Figure 11.5 Material balance in recycle operation.

Taking an -balance or A + B balance for the overall unit (envelope 1 ) does not give us any
^
information on the recycle. Consider envelope 2 that encompasses the reactor and the separator
in which the recycle is separated from the reaction products, and take a material balance for
A + B assuming that R moles are recycled per 100 moles of fresh feed. For steady-state material
balance for processes with chemical reaction , the general material balance can be written as
material in = material out + material consumed due to chemical reaction
Since the moles entering the reactor is 100 + R, we get
100 + R = (100 + /?) 0.25 + R
which gives R = 300 moles.

EXAMPLE 11.2 Final purification stage in the preparation of a pharmaceutical product A

from natural sources requires centrifuging and continuous filtration as depicted in Figure 11.6.
Determine the flow rate of the recycle stream in kg/h.

Recycle, 0.5 kg of A!kg of water

Centrifuge Filter
Feed, 100 kg/h 65% A , 35% Product, 93%
(20% A in water) water A, 7% water
Water
Figure 11.6 Recycle operation in Example 11.2.

Solution Basis: 100 kg/ h fresh feed

Let R kg/h be the recycle stream, P kg/h be the product stream and W kg/ h be the amount
of water separated and removed in the centrifuge.
374 Stoichiometry and Process Calculations

Considering the envelope which contains the centrifuge and the filter, the total material and
component- balance yield
^
100 = P + W (A)
20 = 0.93 P (B)
Solving these equations, we get P = 21.51 kg/h and W = 78.49 kg/h.
Now, consider material balance about the filter. Let x be the flow rate of the streams
entering the filter. Then, total material balance gives
x= P+R (C )
Component-
^ balance

0.65* = —1.5 R + 0.93 P ( D)

Substitute P = 21.51 in Eqs. (C) and (D) and solve the equations simultaneously. The result
is R = 19.
The amount of recycle stream = 19 kg/h.

EXAMPLE 11.3 A wet solid containing 70% water is mixed with recycled dry solid to reduce
the water content to 50% before being admitted into the granulator. The solid leaving the
granulator is fed to a drier where it is brought into contact with dry air initially containing 0.25%
water by weight. In the drier, the air picks up moisture and leaves with a moisture content of
5%. The solids leaving the drier contain 20% water. A portion of this solid is recycled.

50% water,
50% solid Moist air, 5% water Air, 0.25% water

/ t
Granulator Dryer
Wet solid , 1000 kg /h, 20% water,
70% water, 30% solid 80% solid

Figure 11.7 Recycle operation in Example 11.3.

For 1000 kg/h of wet solid sent to the granulator as fresh feed, determine:
(a) The amount of solid recycled
(b) The circulation rate of air in the drier on a dry basis.
Solution Basis: 1000 kg/ h of fresh solid feed containing 70% water. Let R be the amount
of recycle stream, S be the amount of combined stream entering the granulator, P be the
amount of dry solid product withdrawn from the dryer, Gx be the amount of air admitted to
the dryer and G 2 be quantity of air leaving the dryer. Consider the balance for moisture-free
solid over the outer envelope which covers the granulator as well as the dryer.
1000 x 0.3 = P x 0.8
which gives P = 375. Now, take material balance at point A where the recycle stream joins the
fresh feed.
 Bypass , Recycle and Purge Operations 375

R kg/h
20% water,
80% solid

Wet solid,
1000 kg/h, 5 kg/g
70% water, o 50% water,
50% solid
30% solid A

Figure 11.8 Material balance around point A.

Total material balance,

1000 + R = S
Water balance,
1000 x 0.70 + R x 0.20 = 5 x 0.5
Solution of the above equations give R = 666.67 and S = 1666.67.
Refer to Figure 11.9 which shows the quantity and composition of material entering and
leaving the dryer. The solids entering the dryer, S = 1666.67 kg, solids leaving = P + R =
1041.67 kg.
G2 kg/h moist air. (7 kg/h,
5% water ( y2 = 0.05) 0.25% water ( y { = .0025)

t Dryer
5 1666.67 kg/h 1041.67 kg/h
20% water,
80% solid
Figure 11.9 Material balance around the dryer in Example 11.3.

Since all the dry air entering the dryer is present in the air stream leaving the dryer, the
material balance for the dry air is simply
Gi ( l - y\ ) = G2( l - y2 )
Here, yj = 0.0025 and y2 = 0.05 so that Eq. (9.58) becomes
0.9975
G2 = G1, 0.95
= 1.05 G1, (A)

Finally, we can take a water balance around the drier, which is

S x 0.5 + Gjyj = G2 y2 + ( P + R ) x 0.20 (B)

Using Eq. ( A ) and substituting known values into Eq. ( B), we get

1666.67 x 0.5 + 0.0025Gj = 1.05Gj x 0.05 + 1041 x 0.20

376 Stoichiometry and Process Calculations

Therefore, Gx = 12502.7 kg.

(a) The amount of solid recycled = R = 666.67 kg/h
(b) Circulation rate of dry air = G { ( 1 - yx ) = 12502.7 x 0.9975 = 12500 kg/h

—
EXAMPLE 11.4 The reaction A > 2B + C takes place in a catalytic reactor (see Figure 11.10).
The reactor effluent is sent to a separator. The overall conversion of A is 95%. The product
stream from the separator consists of B, C and 0.5% of A entering the separator, while the
recycle stream consists of the remainder of the unreacted A and 1 % of B entering the separator.
Calculate the
(a ) Single pass conversion of A in the reactor
( b ) Molar ratio of recycle to feed.

Product stream A, B and C

Feed , pure A Reactor Sen? rator

A -> 2 B + C

Recycle stream: A and B

Figure 11.10 Recycle operation in Example 11.4 .

Solution Basis: 100 mol A in the fresh feed.

Since the overall conversion is 95%, the product stream leaving the separator contains
5 mol A 9 95 x 2 = 190 mol B and 95 mol C. Since the amount of A in the product stream
is only 0.5 % of A entering the separator, the amount of A entering the separator is

5 x —0.5 = 1000 mol. 99% of the B entering the separator should leave with the product

stream. Then, the amount of B entering the separator is 190 x

99
= 191.92 mol. Since no
C is present in the recycle stream, C entering the separator is 95 mol, same as the C leaving
in the product stream.
(a ) Now, the stream leaving the reactor consists of A = 1000 mol, B = 191.92 mol and
C = 95 mol. The recycle stream consists of A = 1000 - 5 = 995 mol and B = 191.92
- 190 = 1.92 mol .

The combined feed entering the reactor contains A = 100 + 995 = 1095 mol and
B = 1.92 mol. Since A entering the reactor is 1095 mol and A leaving the reactor is
(1095 - 1000) _
1000 mol, single pass conversion of A = ——
1095
x 100
1A
- 5.08%

(b ) Moles recycled = 995.00 + 1.92 = 996.92 mol. Moles of fresh feed = 100. Therefore,
996.92
ratio of recycle to fresh feed =
100
= 9.97.
 Bypass , Recycle and Purge Operations 377

EXAMPLE 11.5 Refined sugar is converted to glucose and fructose according to

C 1 2 H 2 2 O1 1 + H20 — > C H1206 + C H1206

6 6
Sucrose rf -Glucose rf -Fructose
The conversion of sucrose in one pass through the reactor is found to be 71.7%. A part
of the product leaving the reactor is recycled in such quantities that after mixing the recycle
stream with the fresh feed, the combined concentration of glucose and fructose in the stream
entering the reactor is 4%. For 100 kg sucrose solution containing 25% sucrose and 75% water
charged to the reactor as fresh feed, calculate:
(a ) The recycle flow
( b ) The combined concentration of fructose and glucose in the recycle stream.
Solution Basis: 100 kg sucrose solution admitted as fresh feed
Refer to Figure 11.11. Let R kg of reactor exit be recycled and joins with the fresh feed
at point 1 before entering the reactor. Let x be the weight fraction of sucrose and y be the
weight fraction of inversion sugar (glucose and fructose) in the recycle stream. It is given that
the weight fraction of glucose and fructose in the combined stream is 0.04. Let z be the weight
fraction of sucrose in the combined stream entering the reactor.

Recycle stream, R kg, weight fraction

sucrose = x, glucose + fructose = y

Fresh feed, *
_ Reaction Product
100 kg sucrose Point 1 vessel

Combined feed, 100 + R kg,

weight fraction sucrose = z,
glucose + fructose = 0.04

Figure 11.11 Recycle in processes in Example 11.5.

We can write a sucrose balance at point 1 as

25 + R x = (100 + /?) z (A)
Similarly, glucose + fructose balance yields
R y = (100 + R ) 0.04 (B)
A sucrose balance around the reactor can be written as follows:
Sucrose entering the reactor = sucrose consumed in the reaction + sucrose leaving the
reactor
(100 + R ) z = 0.717 (100 + R ) z + (100 + R ) x (C )
378 Stoichiometry and Process Calculations

Note that the total material intering the reactor is equal to the total material leaving the
reactor, both being equal to (100 + R ) kg. Equation (C) can be simplified as
x = 0.283 z (D )
In Eqs. (C) and (D), the amount of sucrose converted to fructose and glucose = 0.717
( 100 + R ) z kg . Then , the glucose and fructose formed in the reactor is
360.192
0.717(100 + R ) z x kg . A glucose + fructose balance around the reactor is written by

equating the sum of the amount in the stream entering the reactor and the amount formed by
the reaction to the amount in the stream leaving the reactor.

360 192
(100 + R ) 0.04 + 0.717 (100 + R ) z *
342.176
= (100 + R ) y (E)

This equation can be simplified to

y = 0.04 + 0.7548z ( F)
Equations (A), (B), (D) and (F) are solved simultaneously and the following values are obtained.
x = 0.06, y = 0.20, z = 0.212, R = 25
(a) Recycle flow, R = 25 kg
( b) Combined concentration (weight fraction) of glucose and fructose in the recycle stream,
y = 0.20. Or glucose and fructose constitute 20% by weight of the recycle stream .

11.3 BLOWDOWN AND PURGE

A major limitation sometimes encountered in recycling operation is the gradual accumulation of
inert materials or impurities in the recycled stock . The impurities may accumulate to such a
level that the process automatically comes to a stop. This difficulty can be overcome by
bleeding off a fraction of the recycled stock as shown in Figure 11.12.

P , Purge stream
Recycle stream xp weight fraction inerts

Net product
F , Fresh feed * Process unit
,
x weight fraction inerts

Figure 11.12 Purging operation .

Similarly, in processes involving chemical reaction employing recycle, if a small amount of

a non-reactive material is present in the feed, it may be necessary to remove the non-reactive
material in a purge stream to prevent its building up above the maximum tolerable value. In the
 Bypass , Recycle and Purge Operations 379

synthesis of ammonia from atmospheric nitrogen and hydrogen, the percentage conversion of
a 1:3 mixture is 25% in a single pass through the reactor. The ammonia formed is removed
by cooling and condensation under high pressure and the unconverted nitrogen and hydrogen
are re-circulated to the reactor. The methane present in the feed stream through the methanation
reaction of hydrocarbon feed stock and argon coming from the atmospheric nitrogen enter the
converter with the synthesis gas and accumulate in the gas stream entering the converter. The
build-up of methane and argon beyond the permissible upper limit can be prevented by purging
off a fraction of the recycled stream (refer to Figure 11.13). In the manufacture of methanol
from synthesis gas also, purging is necessary to prevent accumulation of methane.

Feed, N? + H 2 , Ar N2, H2, NH3, Ar

Reactor
Separator Product
N 2 + 3H 2 = 2NH 3
NH3

Purge stream
Recycle stream N2, H2, Ar
Figure 11.13 Purging operation in process with chemical reaction.

In the electrolytic refining of copper employing the recycle of electrolyte, the accumulation
of impurities is prevented by bleeding off a portion of the electrolyte and replacing the same
with fresh electrolyte. In the steam boiler using feed water containing dissolved solids, the
solids would accumulate in the boiler, as steam is removed. A certain amount of boiler contents
are periodically removed as “ blowdown” which, in principle , is analogous to purging operation.
If the impurities or inert material is removed only through the purge stream , then the
amount of inerts entering with the fresh feed should be equal to the amount of inerts in the
purge. Let P be the amount of purge, and xp be the composition of the inert in it. Then,
PxP = Fxj
where F is the quantity of fresh feed and xj is its inert concentration. Thus, the quantity purged
off can be evaluated as

feed rate x mole fraction of inerts in the feed

Purge =
^
mole fraction of inerts in the recycle

EXAMPLE 11.6 One half of the high-pressure steam after being utilized for power generation
is sent to the plant as process steam. The other half is returned to the boiler as condensate
carrying 50 ppm solids.
To keep the solid level in the boiler below 1600 ppm solids, a part of the boiler water is
blown down continuously. The fresh boiler feed water is found to contain 500 ppm solids. If
steam produced is free of solids, calculate the weight ratio of feed water to the blowdown
water.
Solution Refer to Figure 11.14. Let F be the feed water rate, B be the rate of blowdown,
S be the high-pressure steam produced and P be the rate at which the process steam leaves
380 Stoichiometry and Process Calculations

the power generation unit. P is also the rate at which condensate is returned to the boiler. The
total material balance over the overall unit is
F= B+ P (A)

High-pressure steam

Boiler Power
Feed water Condensate generation Process
steam
Blowdown

Figure 11.14 Blowdown operation in Example 11.6.

Take a solid balance around the boiler.

500 _50 _ 1600

Fp x —10
6
- + Px — - = B x
io 6
- 6
10
which can be simplified as
5F + 0.5P = 16B (B)
Eliminating P from Eq. ( B) using Eq. (A), we get
5F + 0.5(F - 5) = 165 => 5.5F = 16.55

.. -
which means
F
— =
16.5
=3
.
B 5.5
Ratio of feed water to blowdown = 3.

—
EXAMPLE 11.7 For the reaction A > 5, the process flow diagram is shown in Figure 11.15.
The fresh feed of A contains 0.5% of inerts by volume. 60% conversion of A per pass is
obtained. The concentration of inerts going into the reactor at ( 1) must be held at 2% by
volume. All streams are ideal gases and the process is at steady state.
(a ) How many moles need to be recycled per mole of total feed to the reactor at (1)?
( b ) How many moles need to be purged?
( c ) What is the overall conversion of A1

Fresh feed , A , I (1 ) (2 ) B
Reactor Separator

(3 )
P , Purge , ^4 , /
Recycle, A, I

Figure 11.15 Purging operation in Example 11.7 .

 Bypass , Recycle and Purge Operations 381

Solution Basis: 1 mol combined feed entering the reactor at point ( 1 ).

Let F be the moles of fresh feed introduced (see Figure 11.15). Composition of the streams
at points (1), (2) and (3) can be found out first. At point ( 1), the inert content is 2%. Therefore,
A at point (1) is 0.98 mol, inerts = 0.02 mol. Since single pass conversion is 60%, stream at
point (2 ) contains A = 0.40 x 0.98 = 0.392 mol, B = 0.60 x 0.98 = 0.588 mol, inerts = 0.02
mol. Since B is completely removed from the separator, stream at point (3) contains 0.392 mol
A and 0.02 mol inerts. Let R be the moles of the gas recycled and P be the moles purged.
Then ,
R + P = 0.392 + 0.02 = 0.412 (A)

Also, the composition of R and P are the same as stream (3). Inert content in the recycle

stream is = ^ ^
x 100 = 4.85 % . The purge stream also has the same inert content.

Taking a component - A balance over the combined system , we get

A in the fresh feed = A leaving with the purge stream + A consumed in the reaction
Number of moles of A consumed in the reaction is the same as the number of moles of
product B leaving the separator, which is equal to 0.558 mol. Therefore,

F x 0.995 = Px 0.9515 + 0.588 => P = 1.0457F - 0.618 (B)

An inert balance at the point where fresh feed is mixed with the recycle ,

F x 0.005 + R x 0.0485 = 1 x 0.02 (C )

Equations (A), ( B ) and (C ) can be solved to get the following:

F = 0.6552 mol, P = 0.0671 mol, R = 0.3448 mol
(a) Moles of recycle stream = 0.3448 mol
(b) Moles of purge stream = 0.0671 mol
(c ) Moles of A converted = 0.588 mol
Moles of A entering in the fresh feed = 0.995 x 0.6552 = 0.6519 mol
0.588
Overall conversion of A = x 100 = 90.2%
0.6519

EXAMPLE 11.8 Carbon monoxide and hydrogen react to give methanol

CO + 2H 2 -> CH 3OH
The conversion of CO entering the reactor is only 20%. A feed stream consisting of 33%
CO, 66.5% H 2, and 0.5% CH4 is mixed with a recycle stream and fed to a reactor. Methanol
leaving the reactor is separated and the unconverted gases are recycled. To prevent the
accumulation of CH 4 and keep its concentration in the recycle stream at 3%, a portion of the
recycled stream is blown off. For 100 moles of fresh feed, determine :
382 Stoichiometry and Process Calculations

(a ) The moles of recycle stream

(b) The moles of purge stream
(c ) The composition of the purge stream
(d ) The moles of methanol produced.
Solution Basis: 100 moles of fresh feed.
Mole fractions of the various components of the fresh feed are: CO = 0.33, H 2 = 0.665
and CH 4 = 0.005. Let R be the moles of recycle stream and P be the moles purged. Let x be
the mole fraction of CO in the recycle stream. Then, the composition of the recycle stream
in mole fraction of the components is CH 4 = 0.03, CO = x, H 2 = 0.97 - x; the purge and recycle
streams have the same composition (refer to Figure 11.16 ).

Purge stream , P mol , CO = x,

CH4 = 0.03, H 2 = 0.97 - x
Recycle stream , R mol
CO = x, CH4 = 0.03, H2 = 0.97 - x
Feed , 100 mol Envelope 1
CO = 0.33
H 2 = 0.665
CH4 = 0.005 Reactor CO, H2, CH4
Separator Product ,
CO + 2H 2 -> CH3OH CH 30H CH3OH ,
M mol

Figure 11.16 Purging operation in Example 11.8.

Taking a methane balance over the entire system ( envelope 1 ), we get

0.5 = 0.03P => P = 16.67 mol

Taking carbon balance,
33.5 = M + P(0.03 + x)
Hydrogen balance gives

66.5 + 2 x 0.5 = 2 M + P( 2 x 0.03 + 0.97 - x )

Substituting P = 16.67 mol into the above equations give
M + 16.67x = 33.0 (A)
and
2M - 16.67x = 50.33 (B)
Solving Eqs. (A) and ( B) simultaneously, we get M = 27.78 and x = 0.3134.
Since the single pass conversion of CO is 20%, moles of methanol produced will be equal
to the moles of CO converted per pass. That is, a methanol balance over the reactor is
methanol entering + methanol produced = methanol leaving
 Bypass , Recycle and Purge Operations 383

Since no methanol is present in the stream entering the reactor, we have

(33 + Rx ) x 0.2 = M
Substituting the values of M and x in this equation , we get R = 337.91
(a ) Moles of recycle stream , R = 337.91 mol
( b ) Moles of purge stream, P = 16.67 mol
( c ) The mole fraction of CH4 = 0.03, mole fraction of CO = x = 0.3134; mole fraction of
H 2 = 0.97 - x = 0.6566. Therefore, the purge stream consists of 3% CH4, 31.34% CO
and 65.66% H 2.
( d ) Methanol produced, M = 27.78 mol

EXERCISES

Bypass
11.1 For using brackish water for irrigation, it is to be desalinated by evaporation. A fraction
of the feed water is sent through an evaporator and the other part is bypassed. The
fraction bypassed and the pure water leaving the evaporator are mixed together to give
the desalinated water of the desired quality. If the feed water has 500 ppm (parts per
million) of salt, and the salt content in the water used for irrigation is to be limited to
a maximum of 50 ppm, determine the fraction of the feed water bypassed.
11.2 It is desired that the concentration of /-pentane in the feed to a natural gasoline plant
should not be more than 10% by mole. This is prepared by passing a fraction of a
hydrocarbon feed stream made up of ^ -pentane and /-pentane in the mole ratio 4: 1
through an /-pentane recovery unit as a side-stream. The stream leaving this tower is
free of /-pentane. It is mixed with the fraction of the original mixture that is not passed
through the recovery tower to get the feed stock to the natural gasoline plant. What
percent of the original hydrocarbon mixture should be treated for removing the isopentane?
11.3 A process stream contains 4%(weight) salt and the rest water. This is prepared by
passing a part of pure water stream through a saturator containing the salt. The
solution leaving the saturator containing 20% salt is mixed with the pure water bypassed
to get the process stream. What fraction of the pure water available is to be passed
through the saturator?
11.4 The maximum allowable limit of impurities in the effluent from a processing unit is
100 ppm, whereas the discharge from the plant contains 500 ppm impurities. To
reduce the level of impurities to the allowable limit, a fraction of the effluent is sent
through a treatment plant which brings down the impurities to 10 ppm and mixes the
treated effluent with the fraction of the effluent that is bypassed. Determine the fraction
of the effluent that is bypassed.
11.5 Air at 313 K saturated with water vapour is dehumidified by cooling and condensation
of water vapour at 286K and by consequent condensation of water vapour. Air leaving
the dehumidifier saturated at 286 K is mixed with a part of the original air which is
384 Stoichiometry and Process Calculations

bypassed through the dehumidifier. The resulting air stream is reheated to 313 K. It is
desired that the final air contains water vapour not more than 0.02 kg/kg of dry air.
Calculate:
(a ) The mass of dry air bypassed (kg ) per each kg of dry air sent through the
dehumidifier
( b ) The mass of water vapour condensed (kg ) in the dehumidifier per 100 m 3 of air
sent through it
( c ) The volume of final air obtained per 100 m 3 of air passed through the dehumidifier.
The total pressure is atmospheric and the vapour pressures of water are 1.5 kPa at
286 K and 7.5 kPa at 313 K.
11.6 In a process for concentrating 1000 kg freshly extracted orange juice containing 15%
solids, the juice is strained, yielding 750 kg of strained juice and 250 kg of pulpy juice.
The strained juice is concentrated in a vacuum evaporator to give an evaporated juice
of 60% solids. The 250 kg of pulpy juice is bypassed around the evaporator and mixed
with the evaporated juice in a mixer to improve the flavour. The final concentrated juice
contains 40% solids. Calculate :
(a ) The mass of final concentrated juice (kg)
( b ) The concentration of solids in the strained juice
( c ) The concentration of solids in the pulpy juice.
Recycle and purge involving no chemical reaction
11.7 Dry salt is to be produced at a rate of 20000 kg/h by evaporating water from a feed
containing 20% NaCl. The brine (27% NaCl) leaving the evaporator may either be
recycled to the evaporator or may be discarded. If the brine produced is 25% of the
weight of dry salt, calculate:
(a ) The feed rate if the brine is recycled
( b ) The percent excess of the feed rate if the brine is discarded over that required
when the brine is recycled.
11.8 Ten thousand kilograms of an equimolar mixture of benzene and toluene is subjected
to fractionation (distillation) so as to produce a distillate having the composition of 95%
benzene and the bottom product with a composition of 96% toluene. The column is
provided with a condenser in which the vapour product leaving the top is totally
condensed. It was found that the vapour flow rate was 8000 kg/h. A part of the
condensate is recycled to the column as reflux and the other part is removed as the
distillate product. The vapour, reflux and the distillate have the same composition. All
compositions are on mole basis. Determine the reflux ratio of the column if it is defined
as the quantity of condensate recycled to the quantity withdrawn as distillate product.
11.9 For the preparation of potassium nitrate, 10000 kg/ h of a 20% KN03 solution is mixed
with a recycle stream and sent to an evaporator. The rate of evaporation is 1.25 times
the rate of introduction of recycle stream. The concentrated solution leaving the
evaporator contains 50% KN03. This is admitted to the crystallizer which yields
 Bypass , Recycle and Purge Operations 385

crystals containing 4% water. At the crystallization temperature, the solubility is 60 kg/

100 kg of water. Major part of the mother liquor leaving the evaporator is returned to
the evaporator as recycle. Calculate:
(a ) The concentration of KN03 in the stream entering the evaporator
( b ) kg/h of recycle stream
( c ) The rate of production of crystals.
11.10 In a wood drier, the hot air must contain at least 2.5% water to prevent the wood from
drying too rapidly and splitting or warping. The original fresh air fed contains 1%
water. Wood is dried from 25% water to 5% water. The wet air leaving the drier
contains 4% water. Calculate the amount of wet air that must be returned to the drier
if 1000 kg per hour of wet wood is dried. All moisture contents are on wet basis.
11.11 Final purification stage in the preparation of vitamins from natural sources requires
centrifuging and continuous filtration, as depicted in Figure 11.17.

Recycle, 0.4 kg vitamin/kg water

Centrifuge Filter
Feed, 100 kg/h 60% vitamin, Product,
(20% vitamin in water) 40% water 95% vitamin,
Water 5% water

Figure 11.17 Recycle operation in Exercise 11.11 .

Determine the flow rate of the recycle stream in kg/ h .

11.12 Fresh atmospheric air mixed with recycled air is heated to 349 K admitted to a drier
at 101.3 kPa at a rate of 100 m3/min. The relative humidity of air entering the drier
is 7.5%. Atmospheric air is at 302 K and has a relative humidity of 30%. The air leaves
the drier at 306 K and 90% relative humidity, a portion of which is recycled and the
other portion is discarded. The vapour pressures of water are 4 kPa at 302 K, 5 kPa
at 306 K and 40 kPa at 349 K. Calculate:
(a ) The ratio of wet recycle stream to wet fresh stream
( b ) The mass of dry air (kg ) to be fed to the drier to remove 1 kg water in the drier
( c ) The rate at which water is removed in kg/min.
11.13 Wet solid containing 75% water is mixed with recycled dry solid to reduce the water
content to 50% before being admitted into the granulator. The solid leaving the granulator
is fed to a drier where it is brought into contact with dry air initially containing 0.3%
water by weight. In the drier, the air picks up moisture and leaves with a moisture
content of 6%. The solids leaving the drier contains 15% water. A portion of this solid
is recycled.
386 Stoichiometry and Process Calculations

50% water,
50% solid Moist air, 6% water Dry Air, 0.3% water

/ t I
Granulator Dryer
Wet solid, 5000 kg/h, 15% water,
75% water, 25% solid 85% solid

Figure 11.18 Recycle operation in Exercise 11.13.

For 5000 kg/h of wet solid sent to the granulator as fresh feed , determine:
(a ) The amount of solid recycled
( b ) The circulation rate of air in the drier on a dry basis.
11.14 Fresh air with a dew point of 290 K is used in an adiabatic dryer which recycles a
portion of the wet air. The combined mixture of fresh air and recycled air is passed
through a heater which raises its temperature to 365 K before admitted to the dryer.
The wet bulb temperature of the air entering the dryer is 310 K and the air leaving the
dryer is 95% saturated. Calculate:
(a ) The fraction of waste humid air recycled
( b ) The kilograms of water evaporated from the wet feed per 100 m3 of hot air
entering the dryer at 101.3 kPa.
11.15 Wet air at 365 K and 101.3 kPa has a relative humidity of 15%. It is to be dried at
the rate of 500 m3/h by using sulphuric acid to absorb the moisture from air in a
packed tower. The dried air will leave the tower at 327 K and 101.3 kPa and its relative
humidity will be 10%. The spent acid (65% H 2S04) is partly withdrawn and partly
recirculated after making up with fresh 98% H 2S04 so that the acid entering the tower
has a concentration of 75% H 2S04. Calculate:
(a ) Cubic meters of wet air leaving the scrubber per hour
( b ) Kilograms of make up acid per hour
( c ) Kilograms of acid entering the tower per hour.
Vapour pressure of water at 327 K = 15 kPa and at 365 K = 75 kPa.
11.16 A feed consisting of 30% benzene, 40% toluene, and 30% xylene is separated into a
distillate containing 93% benzene 5.5% toluene and 1.5% xylene and a bottom product
containing 2.0% benzene. All percentages are on mole basis. The reflux ratio is 3.0 and
the feed rate is 100 kmol/h. Calculate:
(a ) Composition of the residue
( b ) Masses of distillate and residue
( c ) Recovery of xylene plus toluene in the residue
( d ) Mass of vapour condensed in the condenser.
11.17 It is desired to produce 1000 kg/h of Na3P04.12H20 crystals from a feed solution
containing 6% (weight) Na3P04 and traces of impurity. The original solution is first
evaporated in an evaporator to a 40% (weight) Na3P04 solution and then cooled to
 Bypass , Recycle and Purge Operations 387

293 K in a crystallizer, where the hydrated crystals and mother liquor solution are
removed. One out of every 10 kg of mother liquor is discarded to waste to get rid of
the impurities, and the remaining mother liquor is recycled to the evaporator. The
solubility of Na3P04 at 293 K is 9.9% (weight). Calculate:
(a ) Feed rate (kg/h )
(b) Rate of evaporation of water (kg/h)
(c ) Rate at which the mother liquor is recycled (kg/h)
(d ) Concentration of the solution entering the evaporator
11.18 A solution containing 10% NaCl, 5% KC1 and 85% water is mixed with a recycle
stream and sent to the evaporator. In the evaporator is removed as vapour and NaCl
is removed as crystals. The concentrated solution leaving the evaporator (NaCl =
17.0%, KC1 = 22%, H20 = 61%) is sent to a crystallizer from which KC1 and NaCl
crystals are removed. The mother liquor leaving the crystallizer (NaCl = 15.86%, H20
= 84.14%) is sent back to the evaporator. Calculate the quantity and composition of
the combined stream entering the evaporator if the feed rate is 20000 kg/h.
11.19 A distillation column separates 10000 kg/h of a 55% benzene and 45% toluene mixture.
The product recovered from the condenser at the top of the column contains 97%
benzene and the bottoms from the column contains 98% toluene. The vapour stream
entering the condenser from the top of the column is 9000 kg/h. A portion of the
product is returned to the column as reflux, and the rest is withdrawn for use elsewhere.
Assume that the composition of the streams at the top of the column , the product
withdrawn and the liquid reflux are identical. All compositions are on weight basis. Find
the ratio of the amount refluxed to the product withdrawn.
11.20 A solid material containing 12% moisture is dried so that it contains 5% water by
blowing fresh warm air mixed with recycled air over the solid in the drier. The inlet
fresh air has a humidity of 0.01 kg of water/kg of dry air, the air from the drier that
is recycled has a humidity of 0.1 kg of water/kg of dry air, and the mixed air to the
drier 0.04 kg of water/kg of dry air. For a feed of 1000 kg solid/h fed to the drier,
calculate:
(a ) kg/h of dried product
( b ) kg of dry air/h in the fresh air
( c ) kg of dry air/h in the recycled air
11.21 Fresh air containing 0.01 kg of water/kg of dry air is mixed with recycled air containing
0.15 kg of water/kg of dry air and is blown over a wet solid in a drier. In a certain
operation, the wet solid contains 15% (weight) moisture and it is to be dried to a final
moisture content of 5% by evaporating moisture into the air blown over it. The fresh
air and recycled air are mixed in such proportions that the air blown over the solid
contains 0.03 kg of moisture/kg of dry air. A part of the air leaving the drier which
contains 0.1 kg of water is recycled. For 100 kg of wet material charged, determine:
(a ) The ratio of dry air in the recycled air to that in the fresh air
( b ) The quantity of dry air in the fresh air feed
( c ) The amount of dry air recycled.
388 Stoichiometry and Process Calculations

11.22 A solution containing 10% NaCl, 3% KC1 and 87% water is fed to the process shown
in Figure 11.19 at the rate of 20000 kg/h. The composition of the evaporator product
P is NaCl = 16.8, KC1 = 21.6, H20 = 61.6. Calculate :
(a ) Flow rate of stream P
(b) Flow rate of stream R
(c ) Rate of evaporation
(d ) Quantity and composition of stream entering the evaporator
R

Water vapour
evaporator

S P
Feed , F Crystallizer

N , Pure KC1

M , Pure NaCl

Figure 11.19 Recycle operation in Exercise 11.22.

11.23 A wet organic pigment containing 40% CC14 is to be dried to 5%. The drier can handle
only 200 kg/h of dry solid. The air used for drying is obtained by mixing fresh air
with recycled air. The fresh air is essentially free of CC14 and it enters the dryer at
373 K and 101.3 kPa with a dew point 288 K for CC14. The air leaving the drier has
a CC14 dew point of 298 K. Calculate:
(a ) The fresh air to be supplied to the drier ( kg/h)
( b ) The recycle ratio, CCl4-free basis
The vapour pressure of CC14 at 288 K = 7.60 kPa and at 298 K = 15.3 kPa.
11.24 Cloth is dried in a stenter (hot-air dryer) in a textile mill. In this machine, fresh air first
mixes with recirculated air. The mixture then passes through a heater. Hot air is jetted
over the cloth to evaporate the mixture. A major portion of the jetted air is recirculated
while the remaining small portion is exhausted. The operation is shown schematically
in Figure 11.20.

Stenter

Fresh air (3)

Evaporating
Heater
(1 ) (2) chamber Exhaust

Recycle stream

Figure 11.20 Cloth drying process in Exercise 11.24.

 Bypass , Recycle and Purge Operations 389

Test data on a particular run of a stenter are given below :

Cloth details: width: 1.1 m, density: 0.085 kg/m2 (dry basis), speed: 60 m /min, inlet
moisture: 83% (dry basis), outlet moisture: 10% (dry basis).
Air conditions: Moisture of air at point (1): 0.02 kg/kg of dry air, Moisture of air at
point (2 ): 0.09 kg/kg of dry air, Moisture of air at (3): 0.10 kg/kg of dry air.
Calculate:
(a ) The rate of evaporation in the stenter
( b ) The mass flow rate of fresh air
( c ) The volumetric flow rate of fresh air (m 3/min), if it is supplied at 300 K and
100 kPa
( d ) The mass flow rate of recirculating dry air.
11.25 In a process producing KN03 salt, 1000 kg/h of a feed solution containing 10% KN03
is fed to an evaporator which evaporates some water to produce a 50% KN03 solution.
This is then fed to a crystalliser, where crystals containing 95% KN03 are removed.
The saturated solution containing 35% KN03 is recycled to the evaporator. Calculate:
(a ) The amount of recycle stream (kg/h)
( b ) The amount of crystals (kg/h)
( c ) The quantity of water evaporated (kg/h)
11.26 Schematic diagram of a process is shown in Figure 11.21.

p K
F I J

Figure 11.21 Recycle operation in Exercise 11.26.

Composition of various streams are as follows:

Component Mol % F Mol % / Mol % J Mol % K

A 15 4 7 60
B 20 29.4 27 6.5
c 50 54 44.4 16.5
D 15 12.6 21.6 17

Given that 80% of A in J is present in K and the ratio of F to P is 1.63, calculate:

(a ) R / J
( b ) Composition of P.
390 Stoichiometry and Process Calculations

11.27 Schematic flow sheet of a process is shown in Figure 11.22.

The following table gives the composition of various streams in mole%.

Component Mol % F Mol % L Mol % M Mol % N

A 20 30 27.6 6
B 50 50 40.4 14
c 15 5 8 60
D 15 15 24 20

F
tP L M
t*

Figure 11.22 Recycle operation in Exercise 11.27.

It is known that stream N contains 75% of C present in stream M. The ratio of F/ P

is 5:3 on mole basis. Calculate:
(a ) RIM
( b ) Composition of R
( c ) Composition of P .
11.28 A boiler in a process plant is supplied with feed water containing 250 ppm solids.
Steam produced does not carry any solid particles. If the solids content in the boiler
at any time should not exceed 1500 ppm, calculate the percentage boiler blowdown
based on the quantity of steam produced when
(a ) The entire feed to the boiler is fresh feed water
( b ) 50% of the feed entering the boiler is constituted by the condensate recycled from
the boiler.
11.29 A boiler feed water contains 2000 ppm dissolved solids. The permissible limit of
dissolved solids in the water in the boiler is 1 part per 100 parts. What percent of the
feed water is to be blowndown?
11.30 High-pressure steam generated in a plant is sent to the power generation unit, 50% of
which is further utilized in the plant as process stream and the remaining 50% is sent
back to the boiler as condensate. The condensate carries with it dissolved solids to the
extent of 50 ppm. To keep the solid content in the boiler water within 1500 ppm, a
part of the boiler water is blowndown continuously. To make up for the blowdown as
well as for the water lost as the process steam , feed water containing 450 ppm solids
is fed to the boiler. Calculate the feed to blowdown ratio.
11.31 Seawater is desalinated by reverse osmosis, as shown in Figure 11.23. All compositions
are on mass basis. Calculate R/ E.
 Bypass , Recycle and Purge Operations 391

Recycle, R kg/h

Seawater,
1000 kg/h, F kg/h, B kg/h brine waste,
3% salt 4% salt 5% salt
Mixer Reverse
osmosis cell
E kg/h

D kg/h, desalinated
water, 0.05% salt
Figure 11.23 Reverse osmosis process in Exercise 11.31 .

11.32 Potable water containing not more than 500 ppm dissolved salt is made by desalinization
through reverse osmosis of seawater which contains 3.0% salt. Fresh seawater is
admitted at a rate of 1000 kg/h. Potable water is withdrawn from the reverse osmosis
cell as product while a fraction of the brine that leaves the cell and containing 5.25%
salt is recycled. The concentration of salt in the stream entering the cell after mixing
the recycle stream with fresh seawater is 4.0%. Determine:
(a ) The rate at which brine is removed from the plant (kg/h)
( b ) The rate at which potable water is produced (kg/h)
( c ) The fraction of the brine leaving the cell that is recycled.

Recycle and purge involving chemical reactions

11.33 Methanol is converted to formaldehyde according to:
2CH 3OH + 02 -> 2HCHO + 2H 20
CH 3OH HCHO + H 2

A mixture containing 80% methanol and 20% oxygen is supplied as fresh feed in a
formalin plant. The conversion of methanol per pass is 50% and all the oxygen is
converted. The exit stream from the reactor contains unconverted methanol, hydrogen,
water and formaldehyde. All the formaldehyde and water are removed from the separator.
The hydrogen is recovered from the recycle stream before it is sent to the reactor. For
a basis of 100 kmol methanol entering as fresh feed, determine :
(a ) The mass of formaldehyde produced (kg )
( b ) The mass of hydrogen produced (kg)
( c ) The mass of methanol recycled (kg ).
11.34 The process schematic of a propane dehydrogenation plant is shown below in
Figure 11.24. It is desired to set up a simplified version of the material balance for this
plant. Assume that the only reaction is the dehydrogenation of propane to propylene;
there are no side reactions. The yield of propylene per pass is 30%. Assume that the
amount of carbon formed on the catalyst is negligible. The product flow rate (stream
S5 ) is 60 kmol/h. Calculate the flow rates of all the other streams. Notice that all
streams except stream S3 are pure.
392 Stoichiometry and Process Calculations

*
4

H2

Absorber
S1 s2.
Catalytic 53 and s5
reactor distillation
C3H8 C3 H8, C3H6 towers C 3 H6

s1 56,
C3 H8
Figure 11.24 Propane dehydrogenation, Exercise 11.34.

11.35 Methanol is produced by the reaction of CO with H 2.

CO + 2H 2 -> CH 3OH
Only 15% of carbon monoxide entering the reactor is converted to methanol. The
methanol formed is condensed and recovered completely. The unreacted CO and H2
are recycled back to the reactor. The feed will contain H 2 and CO in the ratio 2:1. For
3200 kg/h of methanol produced, calculate
(a ) The amount of fresh feed (kmol/h)
( b ) The amount of recycle gas (kmol/h).
11.36 It is proposed to produce acetaldehyde by oxidation of ethanol in the gas phase.

C2 H 5OH(g) + % (g) -> CH CHO(g) + H 20(g)

2 3

the ratio of air to ethanol in the fresh feed (before it is mixed with recycle stream ) is
10 to 1 by mole. The conversion of ethanol on a single pass through the reactor is
25%. The unreacted ethanol is completely separated from the reaction products and
recycled.
(a ) What is the ratio of recycle stream to the fresh feed stream?
( b ) What is the composition of the outlet stream from the reactor in mass percent and
mole percent?
11.37 Glucose (C 6H 1206) is enzymatically converted to fructose (C 6H 1206) in a fixed-bed
reactor. Only a portion of the exit stream from the reactor is removed as product, the
other portion being recycled to the reactor. The ratio of the moles of product to recycle
stream is 8.5. The recycle stream is mixed with the fresh feed and the combined
stream containing 5% fructose is admitted to the reactor. The fresh feed is a 60%
glucose solution in water. What is the percent conversion of glucose to fructose on
one pass through the reactor?
11.38 Limestone containing 95 weight % CaC03 and 5% Si02 is calcined in a kiln.
CaC03 — > CaO + C02
 Bypass , Recycle and Purge Operations 393

The heat requirement in the kiln is met by burning coke which is essentially carbon
in a furnace and by admitting the hot flue gases into the kiln. The flue gas analysis at
the furnace exit shows 8% C02. This is mixed with a fraction of the gases leaving the
kiln so that C02 content at the kiln inlet is 10% C02. If the gases leaving the kiln
analyzed 12% C02, determine for 100 kg coke burned,

Limestone

Coke Kiln gas

Furnace Kiln
Air

Figure 11.25 Calcination of lime, Exercise 11.38.

(a ) The mass of lime produced (kg ) and its percent purity.

( b ) Recycle ratio
( c ) Moles of stack gases.
11.39 Methanol vapour can be converted into formaldehyde by the following reaction scheme:

CH3OH + % 2 -» HCHO + H,0

CH 3OH -> HCHO + H 2
The fresh feed to the process is 0.5 k mol/h of 02 and an excess methanol. All of the
oxygen reacts in the reactor. Formaldehyde and water are removed from the product
stream first, after which hydrogen is removed from the recycled methanol. The recycle
flow rate of methanol is 1 kmol/h. The ratio of methanol reacting by decomposition
to that by oxidation is 3. Calculate:
(a ) The fresh feed rate of methanol
( b ) The single pass conversion of methanol
( c ) The hydrogen produced.
11.40 The chlorination of methane to form methyl chloride results in the formation of some
polychlorinated methane also. A mixture of methane and chlorine in the mole ratio 10:1
is sent to a reactor. The products analyze 92.2% CH4, 6.2% CH3C1, 1.0%CH2C12, 0.4%
CHCI3, 0.1% CC14 on an HCl-free basis. The mixture is scrubbed with water to remove
HC1 gases. The chlorinated products in the gas leaving the scrubber are condensed and
removed from the excess methane which is recycled. Additional chlorine is added to
keep the methane: chlorine ratio in the feed to the reactor at 10:1. For a basis of
100 kg of chlorinated products per hour, determine :
(a ) Moles of methane and chlorine admitted as fresh feed.
(b) The mass of methane (kg) recycled per hour
(c) The percent excess chlorine in the fresh feed based on conversion to methyl chloride
(d ) The cubic metres of gas leaving the separator at STR
394 Stoichiometry and Process Calculations

11.41 In an attempt to provide a means of generating NO cheaply, gaseous ammonia is

burned with 02. It is desired that oxygen entering the reactor is 20% in excess of that
theoretically required. The reaction is 70% complete. The nitric oxide is separated from
the unreacted NH3, and the latter is recycled, as shown in Figure 11.26.
4NH 3 + 50 2 — > 4N0 + 6H 20
Calculate:
(a ) The moles of ammonia recycled per 100 moles of NO formed
( b ) The ratio of moles of ammonia to oxygen in the fresh feed.

Recycle ammonia
Water

Ammonia *
--
Reactor Separator NO
Oxygen — o2
Figure 11.26 Ammonia oxidation, Exercise 11.41.

11.42 Figure 11.27 shows the three main steps in the production of vinyl chloride from
ethylene— chlorination (A ), oxyhydrochlorination (B) and pyrolysis (C ).
The reactions occurring are:
Chlorination: (The yield on ethylene is 98%)
C 2 H 4 + CI 2 — ) C 2 H 4 CI 2
Oxyhydrochlorination: ( Yield on ethylene is 95%, on HC1 90%)

C 2 H 4 + 2HC1 + % 2 -> C 2 H 4 C12 + H 20

Pyrolysis: (Yield on dichloroethylene is 99%, on HC1 99.5%)

C 2 H 4C12 -> C 2 H 3C1 + HC1

Chlorine
Dichloroethane recycle ( DCE )
A
Chlorination
Vinyl
Ethylene C Chloride
Pyrolysis

B
Oxygen Oxyhydro-
chlorination
HC1 recycle

Figure 11.27 Vinyl chloride production from ethylene , Exercise 11.42.

 Bypass , Recycle and Purge Operations 395

The HC1 from the pyrolysis step is recycled to the oxyhydrochlorination step. The flow
of ethylene to the chlorination and oxyhydrochlorination reactors is adjusted so that the
production of HC1 is in balance with the requirement. The conversion in the pyrolysis
reaction is limited to 55%, and the unreacted dichloroethane is separated and recycled.
For the production of 25000 kg/h of vinyl chloride, determine (a) the flow of ethylene
to each reactor and (b) the total flow of dichloroethane to the pyrolysis reactor.
11.43 Methanol is produced by the reaction of CO with H 2.
CO + 2H 2 -> CH 3OH (A )
The side reaction is
CO + 3H 2 ^ CH 4 + H 20 (B)
The conversion per pass is 15%. Of this amount, 87.5% is assumed to react via equation
(A ) and 12.5% via equation (B). The stream leaving the reactor passes through a
condenser and a separator. The CO and H2 leaving these units are recycled. The ratio
of H to CO in the recycle is 2:1. The CH4 leaves as a gas and the liquid mixture of
methanol and water passes to a distillation column for the concentration of methanol.
The flow diagram is given in Figure 11.28.

Recycle CO + H2, 70 bar, 339 K

Compressor

Methane
Feed,
CO = 32% Reactor, Condenser
H 2 = 68% 70 bar, 573 K and Separator
Methanol , water

Figure 11.28 Methanol synthesis, Exercise 11.43.

For 100 moles of fresh feed, determine:

(a ) Moles of gas recycled
( b ) Composition of the stream leaving the reactor
( c ) Moles of methanol produced
11.44 In the production of ammonia from hydrogen and nitrogen , the conversion based on
either raw material is limited to 15%. The ammonia produced is condensed and separated.
The uncondensed gases are recycled. The argon in the recycle is to be limited to 5%.
If the feed contains 0.2% argon, calculate the purge required.
11.45 o-Xylene is oxidized to phthalic anhydride by oxygen according to:
C8 H10 + 302 — ^ C H403 + 3H O
8 2

A mixture of o-xylene and air containing 6% xylene is sent to a fixed -bed reactor at
625 K along with a recycle stream coming from the condenser in which the phthalic
anhydride and water produced in the reactor are separated and removed. The recycle
396 Stoichiometry and Process Calculations

is provided with a purge and the purge stream analyzed 78% N2. It is found that for
every mole of gas mixture entering as fresh feed, 1.2 moles leave the reactor. If 60%
conversion is achieved in a single pass and 100 kmol of a mixture of xylene and air
is admitted as fresh feed, determine: (a) the rate of production of pthalic anhydride
(kg/ h) and (b) xylene produced (kg/h).
11.46 A 1:3 nitrogen-hydrogen mixture is fed to a converter resulting in 20% conversion to
ammonia. After complete separation of ammonia, the remaining unconverted gases are
recycled to the converter. The initial reaction mixture contains 0.2% by volume argon.
If the limit of argon in the reactor is 5% by volume of the N2-H 2 mixture in the reactor,
estimate:
(a ) Fraction of the recycle that is purged
( b ) Moles of ammonia produced per 100 mole feed
( c ) Overall conversion of ammonia.
11.47 Methanol is made by the reaction of CO with H 2 according to the reaction
CO + 2H 2 CH3OH
The gas mixture entering the reactor is contaminated by small amounts of methane.
The composition of the gas mixture is as follows:
CO = 32.5%, H 2 = 67.3% and CH 4 = 0.2%
The single pass conversion of CO in the reactor is only 18%. The exit stream from
the reactor is sent to a separator in which methanol is separated and removed. The
unconverted gases are recycled and mixed with the fresh feed before being admitted
to the reactor. It is desired that the methane content in the recycle stream is not more
than 3.0%. This is achieved by bleeding off a portion of the recycle stream at the exit
of the separator. Calculate per 100 moles of fresh feed
(a ) The moles of recycle stream
(b) The moles of purge stream
(c) Composition of the purge stream
(d ) Moles of methanol produced.
11.48 Refer to Figure 11.29. Ethylene is oxidized to ethylene oxide by the reaction:

C2 H4 + —o 2 -> CH 2 CH 2 O

o2 Purge

CH2CH 2 Ethylene oxide product

Reactor Separator
C 2 H4, Air
^ ’ o ,C H
12 2 2 4

Figure 11.29 Oxidation of ethylene, Exercise 11.48.

 Bypass , Recycle and Purge Operations 397

Ethylene to air ratio in the stream entering the reactor is to be 1:10. The conversion
of ethylene is 25% per pass. Ethylene oxide is separated and the unconverted gas is
recycled. To maintain the ethylene-air ratio in the reactor, 25% by volume of the
recycle stream is purged off. Also, pure oxygen is supplied in addition to the ethylene-
air mixture supplied as fresh feed. For producing 100 kg of ethylene oxide per hour,
calculate:
(a ) Ethylene-air ratio in the fresh feed
(b) Moles of gas purged off
(c) kg/ h of ethylene to be supplied as fresh feed
(d ) kg/ h of pure oxygen supplied.
11.49 In the Haber process for the manufacture of ammonia, synthesis gas which analyzes
75.2% H 2, 24.5% N 2 and 0.3% Ar is sent to the converter after mixing with recycle
stream . The following reaction takes place in the converter:

N 2 + 3H 2 -> 2NH 3
To avoid building up of argon in the recycle stream, which will adversely affect the
equilibrium conversion after a certain concentration, a small purge is provided in the
recycle. The gas mixture entering the converter contains 79.5% H 2. Ammonia is
separated from the converter gases in a separator and the unreacted gases are recycled.
The gases leaving the separator are free from ammonia and contain 80.0% H 2 and the
product ammonia contains no dissolved gas. For a basis of 100 moles of fresh feed,
calculate:
(a ) The moles of recycle stream
( b ) The moles of purge stream
( c ) The percent conversion of hydrogen per pass.
11.50 A synthesis gas consisting of 24.3% N2, 75.2% H 2, and 0.5% Ar is fed to an ammonia
converter mixed with recycled stream. The single pass conversion of nitrogen is 10%.
Unconverted gases leaving the reactor is separated and returned to the reactor along
with fresh feed. In order to keep the concentration of Ar in the recycled stream below
1%, a portion of the recycled stream is purged off. For 100 kg of fresh synthesis gas,
determine:
(a ) Moles of recycle stream
( b ) Moles of purge stream
( c ) Ammonia produced (kmol).
11.51 A gas mixture containing nitrogen and hydrogen in the ratio of 1:3 by volume is sent
to the ammonia converter where its conversion to NH3 is 25% complete. The ammonia
formed is condensed and separated by passing the gases leaving the converter through
a condenser. The unconverted gases are recycled . To prevent the accumulation of
argon, a portion of the recycle stream is purged off. The fresh feed contains 0.003
mol argon per mole of N2-H 2 mixture, and the level of argon in the reactor should not
exceed 0.05 mol per mol of N2-H 2 mixture, determine:
398 Stoichiometry and Process Calculations

(a ) The fraction of the recycle stream that is purged off

( b ) The concentration of Ar in the recycle stream
( c ) Moles of N 2-H 2 mixture entering the reactor per 100 moles of gas admitted as
fresh feed.
11.52 Benzene is produced from toluene as per the following reaction :
C 7 H8 + H 2 -> C 6 H 6 + CH 4
The following side reaction is also found to occur:
2C 7 H 8 + H 2 — ^ CZ!1 2 H1 0 2CLI 4
The reaction is carried out according to Figure 11.30.
Make up Purge stream
hydrogen H2CH4
Moles H2
Moles of CH4
Vloles H
=5
Moles of toluene
Benzene
Mixer Reactor Separator
Toluene
feed

Liquid recycle ( toluene ) Biphenyl

Purifier

Figure 11.30 Production of benzene from toluene , Exercise 11.52.

It is known that conversion of toluene per pass is 75%. And 90% of the toluene reacted
is converted to benzene. For 100 moles of toluene entering the reactor, calculate:
(a ) Moles of gas purged
( b ) Composition of the purge stream
( c ) Moles of makeup hydrogen
11.53 N2 and H2 in the ratio of 1:3 constitute the synthesis gas for the manufacture of
ammonia. Synthesis gas is obtained by burning excess hydrogen in air. Since air
contains 0.95% Ar, the gas produced will be contaminated with Ar. The gas is fed to
a converter after mixing with recycle stream . The conversion of the gas to ammonia
is only 25% complete. The unconverted gases are separated from the product ammonia
and are recycled . The combined stream consisting of fresh synthesis gas and the
recycle stream should not contain Ar above 5%. To keep the level of Ar below this, a
portion of recycle is purged off. For 100 kmol of hydrogen in the fresh feed, determine:
(a ) The moles of ammonia produced
( b ) The percent of hydrogen in the fresh feed that is converted to ammonia
( c ) The moles of gas purged off.
 1Y 9u Energy Balance
Thermophysics

Chemical process industries in general are huge consumers of energy. Efficient and proper
conversion of the scarce resources into energy and the proper utilization of the energy so
obtained in the operation of the plant are naturally two major concerns in chemical engineering.
So, the engineer should be competent to identify cheap sources of fuel, choose proper operating
conditions to reduce loss of energy, design appropriate waste heat recovery systems, etc. An
energy balance helps the engineer in all these tasks. Energy balances are carried out in the
operation and the process design stages of chemical process industries. The energy requirements
for heating and cooling or the power requirement of a process are determined by carrying out
energy balance during the process design stage. An energy balance in plant operation helps us
to identify the pattern of energy consumption and suggest possible means for the conservation
of energy.
The energy balance principle can be made clear by considering the theory behind heat
exchangers, which is one of the most common and widely used process equipment. Almost all
process industries employ heat exchangers in one form or another, either for heating or cooling
of process streams or for the recovery of waste heat. A schematic sketch of a simple shell-and-
tube heat exchanger is shown in Figure 12.1.
A heat exchanger is typically a device that performs the transfer of heat between two fluids.
The shell-and-tube type heat exchanger consists of a large number of tubes welded into fixed
tube plates at each end. The tube bundle is housed in a cylindrical chamber known as shell.
Baffles are placed in the shell to ensure better transfer of heat. One fluid is passed through the
inside of the tubes and the other fluid outside the tubes. The former is called tube-side fluid and
the latter the shell-side fluid . In a parallel flow exchanger, both fluids enter at one end and
flows in the same direction throughout the length of the exchanger. In a counter-current
exchanger, the fluids are admitted at the opposite ends and flow in the opposite directions.
Heat is transferred from the hot fluid to the cold fluid. The hot fluid gets cooled, and the cold
fluid gets heated in the exchanger. The heat given out by the hot fluid is equal to the heat
absorbed by the cold fluid, if heat losses are negligible. This heat balance forms the basis for
399
400 Stoichiometry and Process Calculations

the calculation of the exit temperature of the fluids, the flow rates of streams and the size
of the exchanger.
Fluid 1 in Fluid 2 in

q.p'1
Fluid 1 out
—
Figure 12.1
1
TTir
Jr'
FluidJ 2 out
.
Shell-and-tube heat exchanger.
^
The heat balance is just a simple form of the general energy balance. We present here and
in the next chapter the basic principles of energy balance and illustrate the use and application
of energy balance through practical problems. Just as material balance is based on the law of
conservation of mass, energy balance is based on the law of conservation of energy, also
known as the first law of thermodynamics.

12.1 LAW OF CONSERVATION OF ENERGY

The law of conservation of energy states that although energy may be converted from one form
to another, it cannot be created or destroyed. Whenever a quantity of one form of energy is
produced, an exactly equivalent amount of another kind must be used up. Therefore, it is
impossible to construct a perpetual motion machine (PMM) of the first kind that would produce
mechanical work continuously without drawing energy from an external source and without
itself undergoing a change. In fact, the failure to construct such a machine formed the basis for
the law of conservation of energy (H. Von Helmholtz, 1847). When the law of conservation
of energy was proposed, heat was not considered to be a form of energy. It was a series of
experiments conducted by Joule between 1843 and 1847 that established heat as a form of
energy.
Joule’s classical experiment established a quantitative equivalence between heat and work.
This was achieved by doing mechanical work on a known quantity of water taken in an
insulated container by the following different methods:
1. Converting mechanical work into electricity and passing the resulting electric current
through water
2. Compressing a gas confined in a cylinder immersed in water mechanically
3. Agitating the water by means of a paddle wheel
4. Rubbing two metal pieces immersed in water against each other
 Energy Balance: Thermophysics 401

In all the above methods, mechanical work was converted to heat which was measured
by a rise in temperature. Irrespective of the way in which mechanical work was converted to
heat energy, it was found that an exact proportionality existed between the amount of work
expended on the water and the rise in temperature. Thus, Joule’s experiments established a
quantitative relationship between heat and work thus rejecting the earlier theory that treated heat
as a substance. The recognition that heat and later, internal energy as forms of energy led to
their inclusion in the law of conservation of energy along with work, potential energy and
kinetic energy, and the law came to be known as the first law of thermodynamics. Before we
embark on the general mathematical treatment of the first law of thermodynamics and formulate
energy balance equations applicable for different situations, we should be familiar with the
various forms of energy that appear in an energy balance. So, we defer the detailed mathemati-
cal treatment of energy balance to section 12.8.

12.2 COMPONENTS OF ENERGY BALANCE EQUATIONS

12.2.1 Heat and Work
Work: Energy is expended in the form of work when a force acts through a distance. Thus,
dW = F dZ (12.1 )
where W is the work done, F is the force acting and Z is the displacement. The unit of work
in the SI system is N m ( newton-metre) or J ( joule).
Let us consider the expansion or compression work in a cylinder, an important quantity in
engineering calculations. Assume that a gas is confined in a cylinder and let the pressure of the
gas be P and volume V. If the surface area of the piston exposed to the gas is A , the force acting
on the piston is
F = PA ( 12.2 )
The displacement of the piston in the direction of the force dZ is related to the change in
volume dV of the gas as
dV
dZ = — A— (12.3 )

Substituting Eqs. (12.2) and (12.3 ) in Eq. (12.1), we get

dW = P dV (12.4 )
If the volume of the gas changes from the initial value Vx to the final value Vl Eq. (12.4) may
9

be readily integrated to get the work done on the face of the piston:

W= f 2
PdV ( 12.5 )

The pressure-volume history of the gas undergoing the change in state is illustrated on the P-
V diagram of Figure 12.2. The integral of Eq. (12.5) is given by the area under the curve
between the limits Vx and V2 .
The area, and hence the work done in the compression or expansion of the gas depend on
the shape of the PF-curve, thus establishing that the work done in a process is a path function.
402 Stoichiometry and Process Calculations

PdV

Volume

Figure 12.2 Work of expansion on PF-diagram.

Power: The power is defined as the rate of doing work. Its unit in the SI system is J/s,
commonly designated as W (watts). In engineering calculations, power is sometimes expressed
as horsepower (hp ). 1 hp = 745.7 W.
Heat: Heat is that quantity which is transferred between bodies due to the difference in
temperatures existing between them. In the early years of the development of the science of
thermodynamics, this quantity was thought of as a substance called caloric. Heat is now recognised
as a form of energy that cannot be stored as such within the system . Heat is manifested only
during a change of state of the system; it is energy in transit, like work. Heat exchanged in a
process depends on the way in which the process is carried out, as pointed out earlier. Therefore,
just as work, heat is a path function. And like work, it is expressed in J. Two other units used
for heat are the calorie and the BTU (the British Thermal Unit):
1 calorie = 4.1868 J; 1 BTU = 1055.04 J

12.2.2 Kinetic Energy, Potential Energy and Flow Energy

Kinetic and potential energy: Energy is a quantity that can be stored within the system and
can be exchanged between the system and the surroundings. The exchange of energy occurs
either as heat or as work. Heat and work are called energy in transit; they cannot be stored
within the system. The energy stored within the system due to its position above some arbitrary
reference plane is referred to as its potential energy (PE). If a body of mass m is at an elevation
z above the ground, the potential energy of the mass is
PE = mgz ( 12.6 )
where g is the acceleration due to gravity. The energy possessed by the body by virtue of its
motion is called its kinetic energy (KE). If a body of mass m is moving at a velocity w , the
kinetic energy of the body is

(12.7 )
 Energy Balance: Thermophysics 403

Flow energy: A fluid element in a flow system possesses an additional energy which is
known as the flow energy. Consider a fluid entering a tube with a pressure P , and let its specific
volume be V. A mass of fluid entering the system is being pushed by the fluid behind it by a
certain force. This force multiplied by the distance through which the force acts is equal to the
Flow energy or entrance work . The force acting on the fluid equals the pressure times the
cross-sectional area of the tube. Since a unit mass of the fluid at pressure P occupies a volume
V , the distance through which the force acts in order to move the fluid into the system is equal
to VIA , where A is the cross-sectional area of the tube. This work which is equal to PV for
unit mass of the fluid is done by the flowing fluid and therefore is called “ flow energy.”

EXAMPLE 12.1 A body of mass 75 kg is lifted through a distance of 10 m. What is the work
done? If it takes 2.5 minutes for lifting the mass, calculate the power. (Take g = 9.81 m/s2)
Solution Work is done when the force is undergoing a displacement. Force is measured
as mass times acceleration.
Here,
force = mg = 75 x 9.81 = 735.75 kg m /s2 = 735.75 N
Work done = F x AZ
= 735.75 x 10 = 7357.5 N m (= 7357.5 J)
Power is the work done in unit time.
7357.5
Power required
4 =
2.5 x 60
= 49.05 J/s (= 49.05 W )

EXAMPLE 12.2 The potential energy of a body of mass 10.0 kg is 1.5 kJ. What is the height
of the body from the ground? If a body of mass 10 kg is moving at a velocity of 50 m /s, what
is its kinetic energy?
Solution The potential energy (PE) is given by Eq. (12.6), i.e.
PE = mgz
1.5 x 103 = 10 x 9.8067 x z
Thus, the elevation z = 15.3 m.
Kinetic energy ( KE) is given by Eq. (12.7), i.e.

KE = —2 mu 2

=
^ xl 0 x (50) 2 = 12 500 N m = 12.5 kJ

EXAMPLE 12.3 A gas confined in a cylinder is maintained at a constant pressure by means

of a weight placed on the piston. The piston is frictionless. The diameter of the piston is 100
mm and the mass of the piston and the weight together is 50 kg. The atmospheric pressure is
1.0133 bar (take g = 9.8 m/s2). Determine
404 Stoichiometry and Process Calculations

(a ) The pressure of the gas

(b) The work done by the gas in J if the gas is allowed to expand pushing up the piston
and the weight by 500 mm
Solution
(a) Force exerted by the atmosphere
= pressure x area

= 1.0133 x 105 x tLx (100 x 10 3 )2 = 795.84 N

~

Force exerted by the piston and weight is

m x g = 50 x 9.81 = 490.5 N
Total force acting on the gas is
795.84 + 490.5 = 1286.34 N
1286:34
Pressure = force/area = r— r = 1.6378 x 105 N /m 2 (= 1.6378 bar)
(;r / 4 ) x (100 xl 0 3 ) 2
“

(b) Work done = force x displacement = 1286.34 x (500 x 10-3) = 643.17 J

( Note: The work done can be calculated using Eq. (12.5). The change in volume due
to the expansion of gas is

^
AV = - x (lOOx 1(T3 ) 2 x 500 x 10-3 = 3.927 xl (T3 m 3
The work done against a constant external pressure by the gas inside the cylinder is

W = jpdV = PAV
= 1.6378 x 105 x 3.927 x 10 “ 3
= 643.16 J )

EXAMPLE 12.4 Liquid benzene of specific gravity 0.879 flows at a rate of 5 m3/h with a
pressure differential of 3500 kPa. What is the power requirement of the pump in W ?

Solution Energy input by the pump per unit mass of fluid is —APP where AP is the pressure

differential against which the fluid is being pumped. The power requirement of the pump is

calculated as the energy to be supplied in unit time. This is obtained by multiplying —APP by m

where m is the mass flow rate of the fluid. Here,

AP = 3500 x 103 N/m2
p = 879 kg/m 3
5 x 879
m- kg/s
3600
 Energy Balance: Thermophysics 405

Therefore, the power requirement of the pump is

3500 x 103 x 5
W=— = 4861 W
p 3600

12.2.3 Internal Energy

Heat and work represent energy in transit. Energy exchange between the system and the
surroundings occurs either as heat or as work. Heat and work are thus external effects of
changes occurring within the system or are external manifestations of stored energy. What
happens to the state of the system after heat is supplied to it and before work is extracted from
it? The system undergoes a change because energy gets stored within it. The energy stored in
the system by virtue of the configuration and motion of the molecules constituting the system
is called its internal energy. It is a definite property of the system and is denoted by U .
The molecules constituting the system possess kinetic energy of translation, rotation and
vibration. They also possess potential energy due to the forces of attraction existing among
them. These molecular potential and kinetic energies contribute to the internal energy of the
system. These are different from the energy due to the mass motion of the system as a whole
(the kinetic energy), and that due to its external position in a gravitational, electrical or magnetic
field (the potential energy) which we have defined earlier. The addition of heat to the system
results in the increase of its molecular kinetic energy and thus increases the internal energy of
the system.
A given system under a given set of conditions has a definite internal energy. In a cyclic
process the internal energy of the system after a series of changes remains the same as it was
before. The heat and work involved in a non-cyclic process are not equal. Consequently, during
a non -cyclic process some energy gets stored in the system or some stored energy gets removed
from the system. These changes in the stored energy are measured as the change in the internal
energy of the system. The change in internal energy At/ in a closed system is equal to the heat
added to the system (Q) minus the work done by the system ( W ).
AU = Q - W (12.8)
Equation (12.8) is the mathematical statement of the first law of thermodynamics for a
closed system.
The internal energy which a system possesses by virtue of the molecular configuration and
motion of molecules is a property of the system and is solely determined by the thermodynamic
state and not by the path by which that state was arrived at. That is to say, internal energy is
a state function. As is obvious, the kinetic energy and potential energy are not thermodynamic
properties of the system. They do not change with change in the temperature or pressure of the
body. It should be borne in mind that it is impossible to measure the total internal energy of a
substance and therefore absolute values of internal energy are not known.

12.2.4 Enthalpy
For a system kept at constant volume in which no work of expansion or any other kind of
work is done, the entire heat supplied goes to change its internal energy. When the system is
free to change its volume against a constant external pressure, the change in internal energy
406 Stoichiometry and Process Calculations

is no longer equal to the energy supplied as heat. In effect, a part of the energy supplied is
utilized by the system for occupying a new volume; the energy thus utilized is equal to the work
required to ‘push’ the surroundings against a constant pressure. Consequently, AU < Q. However,
the heat supplied at constant pressure can be measured as the change in another thermodynamic
property of the system which we call the enthalpy. Enthalpy is denoted by H and is perhaps,
the most widely used of all thermodynamic functions. It is defined as
H = U + PV ( 12.9 )
Here U is the internal energy of the system, P the absolute pressure and V the volume of the
system . Since t/, P and V are all state functions, any combination of them also must be a state
function . Enthalpy is, therefore, a state function. Enthalpy may be treated as ‘total energy ’
because it includes both the intrinsic energy it possesses ( U ) and the energy due to the expan-
sion possibilities of the system or the energy that the system possesses because of it occupying
a space ( PV ).
In differential form Eq. (12.9) can be written as
dH = dU + d( PV ) ( 12.10 )
which on integration gives
AH = AU + A( PV ) (12.11)
Equation (12.11) is applicable for any finite change occurring in the system.
We can show that the change in enthalpy for a reversible, non-flow process at constant
pressure is equal to the heat supplied . Equation (12.10) can be expanded as
dH = dU + P dV + V dP ( 12.12 )
Substituting Eq. ( 12.8) into Eq. (12.12 ) we get
dH = dQ - dW + P dV + V dP
Since dW = P dV and V dP = 0 for constant pressure process, the above equation simplifies to
dH = dQ (for constant pressure process) (12.13 )
That is, when a system is heated at constant pressure, and only expansion work can occur,
the change in enthalpy is equal to the heat supplied. On the other hand, for a process occurring
at constant volume, work of expansion is zero, and Eq. (12.8) reveals that the change in internal
energy is equal to the heat supplied.
dU = dQ (for constant volume process) (12.14 )

EXAMPLE 12.5 A spherical storage tank of 3 m in diameter is half-filled with 12 500 kg of

an organic liquid at 7000 kPa. If the total internal energy in the tank is 5.3 x 106 kJ, what is
the specific enthalpy of the fluid in the tank?
Solution The internal energy U of the fluid referred to some arbitrary reference state is
5.3 x 106 kJ. The enthalpy of the fluid is given by Eq. (12.9), i.e.
H = U + PV
P = 7000 kPa (= 7 x 106 N/m2)
 Energy Balance: Thermophysics 407

Volume of the tank = — nr* = — n(1.5) 3

= 14.137 m3
Volume occupied by the liquid, V = 0.5 x 14.137 = 7.0685 m 3
Thus H = U + PV = 5.3 x 109 + 7 x 106 x 7.0685
= 5.3495 x 109 J (= 5.3495 x 106 kJ)
Specific enthalpy = 5.3495 x 106/12 500 = 427.96 kJ/kg

EXAMPLE 12.6 Calculate AU and AH in kJ for 1 kmol water as it is vaporized at a constant

temperature of 373 K and a constant pressure of 101.3 kPa. The specific volumes of liquid and
vapour at these conditions are 1.04 x 10-3 and 1.675 m3/kmol respectively. 1030 kJ of heat is
added to water for this change.
Solution During vaporization the specific volume of water increases at constant pressure,
doing work of expansion which is equal to PAV.
The expansion work done by the system against 101.3 kPa pressure is
W = PAV = 101.3 x 103(1.675 - 1.04 x 10 3) x 10 3 = 169.57 kJ/kmol
" ~

Q = 1.03 x 103 kJ/kmol

By Eq. (12.8)
AU = Q - W = 1.03 x 103 - 169.57 = 860.43 kJ/kmol
By Eq. (12.11)
AH = AU + A( PV )
For the constant pressure process, this becomes
AH = AU + PAV = 860.43 + 169.57 = 1.03 x 103 kJ/kmol
which is the same as the heat added.

EXAMPLE 12.7 The contents in a stirred tank reactor are being agitated by means of a 2-hp
stirrer. The heat generated due to stirring is dissipated to the surroundings at a rate of 3000 kJ/h.
Determine the change in internal energy.
Solution Work W is positive when work is done by the system. Here, work is done on
the system by means of the stirrer. Therefore, the work done W is negative.
W = -2 hp = -1491.4 W (= -1491.4 J/s)
Similarly, the heat transferred is positive when heat is transferred to the system . Here, heat is
transferred to the surroundings. Therefore, Q is negative.
3000 X 10
Q = - 3000 kJ /h =- = - 833.33 J/s
3600
By Eq. (12.8),
AU = Q - W= - 1491.4) = 658.07 J/s
833.33 - (-

The internal energy of the system increases by 658.07 J in one second.

408 Stoichiometry and Process Calculations

EXAMPLE 12.8 Iron reacts with hydrochloric acid at 300 K according to

Fe(s) + 2 HCl(aq)
Determine the work done when 1 kg
—of iron
> FeCl aq
2( ) + H 2(g)
filings reacts with HC1 in a closed vessel
maintained at a constant pressure. Assume that hydrogen behaves as an ideal gas.
Solution The atomic weight of iron is 55.845.
The number of moles of iron reacted is
l x l O3
55.845
= 17.906 mol
Since one g-atom of Fe produces 1 mol hydrogen, the number of moles of hydrogen produced
= 17.906 mol.
The work done during the process is PAV. Since the volumes of solids and liquids are
negligible in comparison with the volume of gases, the volume change during the reaction is
the volume occupied by the hydrogen produced during the reaction . Since hydrogen behaves

as an ideal gas, the volume of hydrogen is . Therefore, the work done is

P
PAV = ( An )RT = 17.906 x 8.314 x 300
= 44 661.15 J = 44.661 kJ

12.3 HEAT CAPACITIES

The heat capacity of a substance is the quantity of heat to be supplied to cause a temperature
rise of one degree. Thus,
dQ = C dT
where C is known as heat capacity of the substance. The heat capacity of the unit mass of a
substance is also known as specific heat of the substance. Heat capacity depends on the way
in which the heat is supplied. When heat is supplied to a system at constant volume, the system
is unable to do any work and the quantity of heat required is given by
dQ = Cv dT (constant volume) ( 12.15 )
where Cv is known as the heat capacity at constant volume. Thus,
dQ
Cy ~ ( 12.16 )
dT
According to Eq. ( 12.8), dU = dQ for a constant volume process, so that we can write
Eq . ( 12.16) as

If heat is supplied to a substance at constant pressure, it is free to expand doing work against
the constant pressure. A part of the heat supplied to the system is utilized for the work of
 Energy Balance : Thermophysics 409

expansion and more heat will be required to raise the temperature than that required in a
constant volume process for the same temperature change . The amount of heat required is
related to the temperature rise as
dQ = CP dT (constant pressure) (12.18)
where CP is called the heat capacity at constant pressure. Thus,
' dQ\
CP = ydT JP
(12.19)

For a constant pressure process, Eq. (12.8) becomes

dU = dQ - P dV
or dQ = dU + P dV = dH (constant pressure)
Equation (12.19) may be written as
'dH_\
CP = ydT
(12.20)
JP
Since for a given temperature change, the heat required is more in a constant pressure process
than that in a constant volume process, generally CP > Cv. However, the difference between CP
and Cv for solids and liquids are very small compared to that for gases, as the change in volume
of solids and liquids during heating is not very significant.
Equations (12.17) and (12.20) give
dU = Cv dT (constant volume) (12.21)
dH = CP dT (constant pressure) (12.22)
The change in enthalpy in a constant pressure process or a process in which the initial and final
pressures are the same, can be evaluated by Eq. (12.22) whereas Eq. (12.18) determines the
heat supplied in a true isobaric process only.
Generally, the heat capacity of a substance is not constant; but varies with temperature .
For convenience in engineering calculations, it is usually expressed by a polynomial equation
such as
CP = a + bT + cT 2 (12.23)
= a + bT + cT 2
CP ~
(12.24)
where a, b and c are constants which are determined by standard methods for curve fitting.
Table 12.1 gives the heat capacities of different gases at constant pressure .
The enthalpy change in a constant pressure process occurring between temperature limits
Tx and T2 can be evaluated by integrating Eq. (12.22).

AH = f CP dT = f ( a + bT + cT ) dT
2
2

If the heat capacity versus temperature data is available as an experimentally measured result
and not expressed in the form of a mathematical expression such as the ones presented above,
410 Stoichiometry and Process Calculations

the enthalpy change is to be determined by graphical integration . This is done by plotting CP

as the ordinate against temperature as the abscissa (Figure 12.3).
Table 12.1 Heat capacities of gases at constant pressure ( Pressure = 0)
CP = a + bT + cT 2 (CP in kJ/kmol K and T in K )
Valid in the range of 300 K to 1500 K

Gas a b x 103 c x 106

Air 26.737 7.377 -1.1120
Ammonia 24.786 37.526 -7.3855
Carbon dioxide 26.540 42.454 -14.2979
Carbon monoxide 26.586 7.582 -1.1200
Chlorine 32.042 9.299 -3.6563
Ethane 9.722 159.266 - 45.9292
Ethylene 12.640 118.110 -35.7427
Hydrogen 29.082 -0.821 1.9917
Hydrogen chloride 28.194 1.717 1.5127
Methane 13.415 77.079 -18.7569
Nitric oxide 26.963 8.663 -1.7610
Nitrogen 27.034 5.815 -0.2889
Oxygen 25.611 13.260 -4.2077
Sulphur dioxide 29.077 41.910 -15.8847
Sulphur trioxide 31.208 80.093 -27.7501

Area = AH = CpdT
J l1
\ K

cd
8o-

X
—
4 1

<D

Temperature, T
Figure 12.3 Graphical integration to find the change in enthalpy.

The area under the curve between the temperature limits T { and T2 gives the enthalpy
change, i.e.

= J[7 CP
2
AH dT
i

EXAMPLE 12.9 1000 kg/h of a thermic fluid, to be used as a heat transfer medium , is being
indirectly heated in a heater from 380 K to 550 K. Calculate the heat load on the heater in kW.
The heat capacity equation for the thermic fluid is
 Energy Balance: Thermophysics 411

CP = 1.436 + 2.18 x 10-3 T

where CP is in kJ/kg K and T is in K.
Solution The amount of material being heated in unit time is
1000
3600
= 0.278 kg/s
The heat required in unit time for heating the fluid from 380 K to 550 K is
55
m
J
f ThCP dT = 0.278 f ° (1.436 + 2.18 xl 0-3 T ) d T
J 380

= 115.77 kJ/s (= 115.77 kW)

EXAMPLE 12.10 The heat capacity of carbon dioxide is given by the following relation
3 6
CP = 26.540 + 42.454 x 10 ~
T - 14.298 x 10 ”

T2
where CP is in kJ/kmol K and T is in K.
(a) How much heat is required to heat 1 kg of C02 from 300 K to 1000 K ?
(b) Obtain the relation expressing the heat capacity in kcal/kmol °C and temperature in °C.
(c) Obtain the relationship giving heat capacity in Btu/lb-mol °F and temperature in °F.
Solution
(a) The heat requirement can be computed using the equation
dQ = CP dT (constant pressure)
which on integration gives
T2
Q= m \ i CpdT
J 7

Here m = 1/44 kmol. Therefore,

1 r 1000 a
-3
.
-6
Q=—
44 J
\ 300 ( 26.540 + 42.454 x 10 T - 14.298 x 10 T 2 ) dT

= 755.86 kJ
(b) Let us use the given equation to evaluate the heat capacity at temperature t °C. The
specific heat at this temperature is evaluated by the given equation as
+ 42.454 x 10 3 ( t + 273.15) - 14.298 x 10 6 ( t + 273.15)2
CP = 26.540 " "

3 -
= 37.068 + 34.643 x 10 ~
14.298 x \0 6 t2
^
in the above equation t is in °C and the specific heat is given in kJ/kmol K . By dividing
the equation by 4.1868, the specific heat evaluated is in kcal/kmol K . Hence the desired
equation is
3 6
CP = 8.854 + 8.274 x 10 "

t - 3.415 x 10 "

t2
412 Stoichiometry and Process Calculations

By replacing t in °C in the above equation by ( f - 32)/ 1.8 the equation becomes

= 8.7058 + 4.6642 x 10 3 f 1.0540 x 10 6 t' 2
CP "

- “

In the above equation t' is in °F and CP is in kcal/kmol K. Since 1 Btu/lb-mol °F =

1 kcal/kmol °C, the above equation gives CP in Btu/lb-mol °F as well, when the
temperature is in °F.

EXAMPLE 12.11 The heat capacity of chlorine at 101.3 kPa varies with temperature as
follows:

T { K) 273 373 473 573 673 773 873 973 1073 1173 1273
Cp (kJ/kmol K) 33.6 35.1 36.0 36.6 37.0 37.3 37.5 37.6 37.7 37.8 37.9

Calculate the enthalpy change when chlorine gas is heated from 273K to 1273K at 101.3 kPa .
Solution At constant pressure, the enthalpy change is given by

AH =J pc„
71
dT

Since the exact functional relationship is not available as a mathematical equation , the integration
is carried out graphically. For this purpose, a graph is plotted taking CP as the ordinate against
T as the abscissa . The area under the curve between the limits 273 K and 1273 K gives
p 1273
Cp dT . Refer to Figure 12.4.
J 273

39.0

_
o
£
38.0

37.0

M 36.0
o Area =
S3
1273
S3 35.0
U

<L>
AH = j C p d T = 36 828 kJ /kmol
273
X
34.0
/
33.0
273 373 473 573 673 773 873 973 1073 1173 1273
Temperature , K
Figure 12.4 Determination of enthalpy change in Example 12.11.

The area is found to be 36 828 kJ/kmol. Therefore,

AH = 36 828 kJ/ kmol
 Energy Balance: Thermophysics 413

12.3. 1 Mean Heat Capacity

For calculating the heat interaction and enthalpy changes in processes involving gases, it is
sometimes convenient to use a mean or average heat capacity in the temperature range of
interest. The mean heat capacity at constant pressure may be denoted by CPm and can be
obtained as

cPm ( T2
o
- Tx )
IhTx*
( T2 - )
( 12.25 )

If CP is expressed as a power series such as the one given by Eq . (12.23), then

1
CPm = —
02 ~
—1V \JT\a + bT + cT 2
) dt
'
1
|T
a( T2 - Tx ) + ( 2 ~
Tx
2 C
) + - ( T2 - Tx ) (12.26)

Mean heat capacities at various temperatures are evaluated and are available in standard references.
These values are evaluated between the given temperature and a reference temperature ( TR ).
Therefore, in the calculation of heat requirement or the enthalpy changes, their use is limited
to temperatures lying between these two values. To calculate the heat required to heat a gas from
temperature Tx to temperature 72, and if TR is outside these limits, it is necessary to calculate
the quantity of heat required for heating from the reference temperature to these temperatures
separately and subtract one quantity from the other as detailed below:
Q = Qx - Qi = CpmA ( 7 i - Tr )
Tr ) - CPm2 ( r2
( 12.27 ) -

where CPmy and CPmj2 are the mean specific heat values at temperatures Tx and T 2 respectively.

EXAMPLE 12.12 The molal heat capacity of CO is given by

6
CP = 26.586 + 7.582 x 1(T3 T - 1.12 x 10 T2
where CP is in kJ/kmol K and T is in K.
(a) Calculate the mean molal heat capacity in the temperature range of 500-1000 K.
(b) CO enters a heat exchanger at a rate of 500 cubic metres per hour at STP. Calculate
the heat to be supplied to the gas to raise its temperature from 500 to 1000 K.
(c) CO is to be heated from 500 to 1500 K. What percent error is expected if the heat
requirement is calculated using the mean heat capacity value determined in part (a)?
Solution
(a) Mean molal heat capacity
1 T2
CPm - —
O2 ~
—
1v f
J 7i
( a + bT + cT 2 ) dt

1 b
( T2 - T, )
a( r2 - r, ) + - cr22 - T{ ) + |(T 2 -T ?)
414 Stoichiometry and Process Calculations

1 7.582 x 10-3
26.586(1000 - 500) +
1000 - 500 2
1 12 10-6 k

x (10002 - 5002 ) -

= 31.293 kJ/kmol K
( b ) Moles of gas to be heated = 500/22.4 = 22.32 kmol/h
^
(10003 - 5003 )

Heat to be supplied = m x CPm x ( T2 - Tx )

= 22.32 x 31.293 x 500 = 3.4923 x 105 kJ/h
( c ) The mean heat capacity calculated in part (a) is valid for the temperature range of 500-
1000 K. The heat required for heating from 500 to 1500 K calculated using this value
will not be accurate. For this calculation, we must use the mean heat capacity valid for
the temperature range of 500-1500 K.
Heat requirement calculated using the mean heat capacity calculated in part (a) is
m x 31.293 x (1500 - 500) = 31293 m kJ
Actual heat requirement is

m
J 500
(26.586 + 7.582 xlO-3 T — lllxlOT 6
T 2 ) dT = 32955 mkJ
( 32955 31293)
Percent error = x 100 = 5.0%
32955
EXAMPLE 12.13 Calculate enthalpy change for one mole of a gas when it is heated from
400 K to 1500 K at 1 atm pressure given that the mean specific heat of the gas at the reference
temperature of 273 K are 35 kJ/ kmol K at 400 K and 50 kJ/ kmol K at 1500 K .
Solution A//400_ 1500 K = A//150O _273 - A7/400_273 K
= CPm \ ( T2 - Tr) - CPm 2 ( Tx - Tr )
= 50( 1500 - 273) - 35(400 - 273) = 56905 kJ/ kmol

12.3.2 Heat Capacity of Mixtures of Gases

The heat capacity of an ideal gas mixture can be evaluated as the sum of the heat capacities
of the individual constituents each weighted according to the mole fraction in the mixture. Thus

Cp, mixture =
^ yfipj
/ =1
( 12.28 )

where yt represents the mole fraction of component i in the mixture of n components and CPi
is its specific heat in the pure state. If the heat capacity can be expressed as a quadratic function
of temperature, i .e.
 Energy Balance: Thermophysics 415

Cp = a + pT + yT 2 (12.29)
the heat capacity of the mixture is
n
Cp,mixture — X
i =1
yfipi

= lO'A ) + I ( y, A )^ + XO', y, )r 2 ( 12.30 )

EXAMPLE 12.14 Combustion of solid wastes produces a flue gas of the following analysis:
C02 = 9.0%, CO = 2.00%, 02 = 7.00% and N2 = 82.0%. Find the difference in enthalpies for
this gas between the bottom and top of the stack if the temperature of the gas at the bottom is
600 K and that at the top is 375 K. The heat capacities of the gas are:
CO CP = 26.586 + 7.582 x 10 3 T - 1.12 x 10 6 T 2
" "

C02 CP = 26.540 + 42.454 x 10 3 T - 14.298 x 10r* T 2"

02 CP = 25.74 + 12.987 x 10 3 T - 3.864 x 10 6 T 2 " "

N2 CP = 27.03 + 5.815 x 10 3 T - 0.289 x 10 6 T 2

" "

Cp is in kJ/kmol K and T is in K.
Solution The heat capacity of the mixture is
n
C/'.mixture E ,
I =1
= E ( y i a, ) + E ( y, AF +1( y, y , )T 2
I(y x 26.540 + 0.02 x 26.586 + 0.07 x 25.74 + 0.82 x 27.03
^ ) == 0.09
26.8867
3
I ( » A ) = ( 09 x 42 454 + 0 - 02 x 7.582 + 0.07 x 12.987 + 0.82 x 5.815) x 10
°
“

3
= 9.6499 x lO "

6
X ( yji) = - (0.09 x 14.298 + 0.02 x 1.12 + 0.07 x 3.864 + 0.82 x 0.289) x 10
6
= - 1.8167 x 10 ~

Therefore,
3 6
Cp,mixture = 26.8867 + 9.6499 x 10 "

T - 1.8167 x 10 “

T2
Enthalpy difference between the bottom and top of the stack is
375
AH =
J
f 600
( 26.8867 + 9.6499 xlO-3 T - 1.8167 xl 0 6 T 2 ) dT
~
= - 6656.29 kJ/kmol
The enthalpy of the gas at the top of the stack is less than that at the bottom by 6656.29 kJ per
kmol of gas.
416 Stoichiometry and Process Calculations

12.4 PREDICTION OF HEAT CAPACITIES OF SOLIDS AND LIQUIDS

12.4.1 Heat Capacity of Solids
It has been proposed ( Dulong and Petit ) that the constant volume atomic heat capacities of
crystalline solid elements are almost constant and equal to 6.2 cal/g-atom K (25.96 J/g-atom K).
Though this observation was based on a very few experimental evidence then available, this rule
applies satisfactorily to elements having atomic weights above 40 at room temperature. For
low-atomic weight elements such as carbon, boron, silicon, phosphorous, sulphur, etc., the
atomic heat capacities at room temperature are lower than 25.96 J/g-atom K. On increasing
the temperature, the atomic heat capacities of even these elements approach the value of
25.96. The atomic heat capacities of all solid elements decrease greatly with decrease in
temperature, and finally for crystalline solids at absolute zero of temperature, the heat capacity
approaches zero. For accurate heat balance calculations, therefore, experimental data on the
specific heats of solids should be used. Table 12.2 adapted from Chemical Engineer ’s Handbook
gives constant pressure atomic heat capacities of certain elements in the crystalline state at
300 K.
Table 12.2 Atomic heat capacities of elements at 300 K, J/g-atom K

Element Heat capacity,

CP (J/g-atom K at 300 KJ
Aluminium 24.141
Antimony 25.305
Arsenic 24.585
Bismuth 25.791
Cadmium 25.958
Calcium 26.415
Carbon, graphite 9.039
Carbon, diamond 6.833
Chromium 23.969
Cobalt 25.619
Copper 24.614
Iron 25.305
Lead 26.695
Lithium 25.456
Magnesium 25.476
Manganese 25.125
Nickel 25.874
Phosphorous, yellow 23.027
Phosphorous, red 23.488
Potassium 28.910
Silicon 20.109
Sodium 27.708
Sulphur, rhombic 25.237
Sulphur, monoclinic 23.865
Tin 27.172
Titanium 18.593
 Energy Balance: Thermophysics 417

Kopp’s rule: When experimental data are lacking, Kopp’s rule may be used for making a
rough estimation of the heat capacity of solids. Kopp’s rule predicts that the heat capacity of
a solid compound at room temperature is approximately equal to the sum of the heat capacities
of the individual elements. The atomic heat capacity values of the elements given in Table 12.3
may be used for estimating the heat capacity of compounds using this rule.
Table 12.3 Atomic heat capacity values for use in Kopp’s rule
( Heat capacity at 293 K, J/g-atom K )

Element Solids Liquids

Carbon 7.5 11.7
Hydrogen 9.6 18.0
Boron 11.3 19.7
Silicon 15.9 24.3
Oxygen 16.8 25.1
Fluorine 20.9 29.3
Phosphorus or sulphur 22.6 31.0
All others 25.96 33.5

According to Kopp’s rule, the heat capacity of potassium permanganate may be estimated as
equal to the heat capacity of potassium + heat capacity of manganese + 4 times the heat capacity
of oxygen . This is equal to 25.96 + 25.96 + 4 x 16.8 = 119.12 J/mol K. This compares well
with the experimental value of 117.2 J/mol K. The deviation is less than 2%. For CaS04 - 2H20,
the experimental heat capacity value is 195.9 J/mol K, whereas the value estimated using
Kopp’s rule is 25.96 + 22.60 + 6 x 16.80 + 4 x 9.60 = 187.80 J/mol K. The deviation in this
case is about 4%.
Generally the heat capacities of compounds are higher in the liquid than in the solid state.
The heat capacity of a heterogeneous mixture of solids is equal to the sum of the heat capacities
of the component parts.

12.4.2 Heat Capacities of Liquids

In the absence of experimental data on heat capacities of liquids, Kopp’s rule may be used to
evaluate heat capacities of liquids at room temperature with a modified set of atomic heat
capacities of constituent elements. These modified heat capacity values are given in Table 12.3.
The heat capacities of most liquids increase with increase in temperature. An empirical
equation of the form CP = a + bT + cT 2 + dP usually represents heat capacity data of many
liquids satisfactorily. Table 12.4 gives the constants a, b , c and d for use in this equation for
a number of liquids (CP is in J/mol K and T in K). For petroleum fractions heat capacity can
be correlated to the specific gravity in API scale.
Heat capacities of heterogeneous mixtures of liquids can be computed as the weighted
average of the heat capacities of the constituent pure liquids. This is found to be approximately
valid even for miscible systems made up of chemically similar materials and for systems with
small heats of mixing (ideal solutions). Thus for hydrocarbon mixtures, heat capacity may be
calculated as
418 Stoichiometry and Process Calculations
Table 12.4 Constants in the heat capacity equation for liquids
CP = a + bT + cT 2 + dT 3
(Cp in J/mol K and T in K)

Liquid Temperature a b x 102 c x 105 d x 109

range ( K )
Acetaldehyde 150-324 16.8842 81.0208 -308.085 4425.9
Acetic acid
Aniline
-
290 421 -36.0814
-13.6683
60.4681
93.1971
-39.3957
-160.401
-561.602
1367.15
Benzene 279 350
- -7.27329 77.054 -164.82 1897.9
Carbon disulphide 17.4151 55.4537 -172.346 15501.9
Carbon tetrachloride 273 343
- 12.285 0.01095 -318.26 3425.2
Ethyl acetate 4.2905 93.4378 -264.0 3342.58
Ethyl alcohol 250 400
- -325.137 0.041379 -1403.1 1.7035 x 104
Ethylene glycol 31.0224 110.034 -284.571 2889.21
Formaldehyde 25.099 79.3671 -382.691 6104.92
Hydrogen peroxide 273-698 63.2314 17.07533 -38.99272 372.4104
Methyl alcohol 273^400 -259.25 0.03358 -11639 1.4052 x 104
w -Hexane 273-400 31.421 0.97606 -235.37 3092.7
Nitric acid 298 110.0
w -Pentane 270-350 33.24 192.41 -236.87 17944
Phenol -36.1614 115.354 -212.291 1741.83
Styrene -38.0191 119.721 -219.565 1933.12
Sulphuric acid 283 318
- -4119.31 15.59
Toluene 270 370
- 1.8083 81.222 -151.27 1630
Water 273 373
- 18.2964 47.212 -133.88 1314.2

where is the weight fraction of the

Cp
^ WgCpj
constituent i
and CPi is its heat capacity at constant
( 12.31 )

pressure.
Heat capacities of aqueous solutions, in the absence of experimental data may be taken as
equal to the heat capacity of water at the same temperature. Thus, one kilogram of a 20%
aqueous solution contains 0.8 kg of water and therefore the heat capacity of the solution is
roughly equal to 0.8 x 4.1868 = 3.35 kJ/kg K.

EXAMPLE 12.15 Determine the heat capacity of Na 2SO410H2O at room temperature using
Kopp’s rule. The atomic heat capacities of elements (J/g-atom K ) are 26.04 for Na, 22.6 for
S, 16.8 for O , and 9.6 for H . Compare the result with the experimental value of the heat
capacity of 592.2 J / mol K ) .
Solution According to Kopp’s rule, the heat capacity of Na2SO410H2O is 2 times the
atomic heat capacity of sodium + atomic heat capacity of sulphur + 14 times the heat capacity
of oxygen + 20 times the atomic heat capacity of hydrogen.
 Energy Balance: Thermophysics 419

Therefore,
heat capacity of Na 2SO410H2O = 2 x 26.04 + 22.6 + 14 x 16.8 + 20 x 9.6
= 501.9 kJ/mol K
The heat capacity predicted using Kopp’s rule deviates from the experimental value by
592.2 - 501.9
x 100 = 15.25%
592.2

12.5 ENTHALPY CHANGE OF PHASE CHANGES

Consider pure water at atmospheric pressure. At temperatures below 273 K, water cannot exist
in the liquid state; it will be in the solid state called ice. When ice is heated at constant pressure
the temperature rises to 273 K, the melting point of water at atmospheric pressure. At this
temperature ice melts, the temperature remains constant at 273 K till the solid is completely
converted to liquid water. We see that a phase change occurs from the solid state to the liquid
state. This change of state from the solid to the liquid occurs at constant temperature and
constant pressure. The enthalpy change accompanying this process is known as heat of fusion
or latent heat of fusion . On further heating the temperature of water increases until it becomes
equal to 373 K, the normal boiling point of water. The heat absorbed by water that resulted in
its temperature rise is its sensible heat. On further heating, the heat supplied is not utilized as
sensible heat for a temperature rise, rather, the heat supplied is used for a change of phase from
the liquid state to the vapour state. The heat required to change the state of unit mass of a
substance from the liquid to the vapour state is known as the heat of vaporization or the latent
heat of vaporization . The heat given out when unit mass of vapour condenses to liquid is known
as the heat of condensation . The heat of vaporization is numerically equal to the heat of
condensation . For water this is 2256.1 kJ/kg at standard atmospheric pressure. Besides the heat
of vaporization and the heat of fusion, enthalpy change accompanying other phase changes
such as change from one solid form to another and change from solid phase to gas phase
(sublimation ) are also important.

EXAMPLE 12.16 Enthalpy of steam at 75 kPa and 573 K is 3075 kJ/kg referred to liquid
water at 273 K. If the mean heat capacity of liquid water and water vapour are 4.2 kJ/kg K and
1.97 kJ/kg K respectively, calculate the heat of vaporization of water at 75 kPa. The saturation
temperature of water at 75 kPa is 365 K.
Solution Since the boiling point of water at 75 kPa is 365 K, the vapour at 573 K and
75 kPa is superheated steam . The process of converting liquid water at 75 kPa and 273 K to
superheated steam at 75 kPa and 573 K can be assumed to take place along the following route
( Figure 12.5):
Step 1: Water is heated from 273 K to 365 K at constant pressure. Enthalpy change, AHx is
equal to the heat required to raise the temperature of water from 273 to 365 K = mCPAT
= 1 x 4.2 x ( 365 - 273) = 386.4 kJ/kg
420 Stoichiometry and Process Calculations
Step 1 Step 2 Step 3

Water at Water at Steam at Steam at

75 kPa, 75 kPa, 75 kPa, 75 kPa,
273 K 365 K 365 K 573 K

Figure 12.5 Process of converting liquid water to superheated steam (Example 12.16).

Step 2: The liquid is vaporized at constant pressure and constant temperature. The enthalpy
change for this process is AH2 and is equal to the heat of vaporization at 75 kPa, AHv.
Step 3: The saturated vapour at 365 K is heated to 573 K at constant pressure. The enthalpy
change for this process,
AH 3 = mCpAT = 1 x 1.97 x (573 - 365) = 409.76 kJ/kg
Assuming that the enthalpy of liquid water at 273 K to be zero, then the enthalpy of
the superheated steam in the final state is
0 + AHx + AHv + A H3
Therefore,
AHx + AHv + AH3 = 3075 kJ/kg
or AHv = 3075 - AHx - AH 3
= 3075 - 386.4 - 409.76 = 2278.84 kJ/kg
Therefore, the heat of vaporization of water at 75 kPa is 2278.84 kJ/kg.

EXAMPLE 12.17 One kg of water is heated from 250 K to 400 K at one standard atmosphere
pressure. How much heat is required for this? The mean heat capacity of ice between 250 K
and 273 K is 2.037 kJ/kg K, the mean heat capacity of water between 273 K and 373 K is
75.726 kJ/kmol K and the heat capacity of water vapour (kJ/kmol K) is

CP = 30.475 + 9.652 x 10 "

3 T + 1.189 x 10 "
6 T1
where T is in K . The latent heat of fusion and vaporization of water are, respectively, 6012 kJ/
kmol and 40608 kJ/kmol.
Solution The heat required (Q = AH ) for the proposed change is evaluated as the sum of
the following quantities:
1. Sensible heat for raising the temperature of ice from 250 K to 273.15 K, AHx
2. Latent heat of fusion of ice, AHy
3. Sensible heat of raising the temperature of water from 273.15 K to 373.15 K, AH2
4. Latent heat of vaporization of water, AHv
5. Sensible heat of raising the temperature of water vapour from 373.15 K to 400 K, AH3
AHx = 2.037 x (273.15 - 250 ) = 47.16 kJ

AH if
18.016
— 333.70 kJ
AH 2 —
= 18.016 x (373.15 - 273.15)
- 420.3 kJ
 Energy Balance: Thermophysics 421

40, 608
AH V
18.016
= 2254 kJ
1 c 400 _, , „
AH , = (30.475 + 9.652 xl 0 37’ + 1.189 X 10-6 T 2 ) dT = 51.24 kJ
18.016 J 373.15
Q = AH = A// j + AHf + AH 2 + AHv + AH3 = 3106.4 kJ

EXAMPLE 12.18 A high boiling organic liquid at 650 K is mixed with carbon tetrachloride
at 295 K in the weight ratio 1 : 1 . The pressure is one standard atmosphere. What will be the
equilibrium temperature of the mixture? The heat capacity of the organic liquid is given by the
relation:
CP = 0.16 + 4.78 x 10 3 T
"

Assume that the heat capacity of CC14 liquid varies linearly with temperature as
CP = 0.7935 + 1.298 x lCT4 T
In the above relations CP is in kJ/kg K and T is in K. The boiling point of carbon tetrachloride
is 349.9 K and the heat of vaporization is 195 kJ/kg. The mean heat capacity of CC14 vapour
is 0.4693 kJ/kg K.
Solution Suppose that the heat given out by cooling of the organic liquid is absorbed by
CC14 to raise its temperature and that there is no phase change. Let T be the final temperature
attained. Then
r 650 , cT
JT
(0.16 + 4.78 xl 0
~
Vr = J 295 (0.7935 + 1.298 x 10-4 71) dT
This relation yields a quadratic equation in T
3
2.4549 x 10 "

T2 + 0.9535 T - 1353.51 = 0
which is solved to give T = 573.3 K. This temperature is above the boiling point of CC14.
Therefore, the CC14 liquid gets converted to the vapour state using the heat given out by the
organic liquid. Let Tbe the final temperature attained which is above 349.9 K, the boiling point
of CC14. To find T , the heat balance is written as follows:
r 650 (0.16 + 4.78 xl 0 ,3 ) rfr = r 349-9 (0.7935 + 1.298 xlO-4 T ) dT + rT 0.4693 / r
AHV
“

+ j 349.9
<
JT J 295

Substitute AHv = 195 kJ/kg in the above equation. The resulting equation is quadratic in T which
is solved for T . The temperature attained by the system T = 540.1 K.

12.5.1 Estimation of Heat of Fusion

No accurate methods are available for the estimation of heat of fusion, AHf . The Clausius-
Clapeyron equation is applicable, but its use to calculate the heat of fusion requires data on the
variation of melting point with pressure, which is seldom available. A rough estimate of heat
of fusion is made using the following approximation:
A Hf
= constant ( 12.32 )
422 Stoichiometry and Process Calculations

where AHy is in J/mol and Ty is the melting point in K. The values of the constant lie between
8.4 and 12.6 for elements, between 21 and 29.4 for inorganic compounds, and between 37.8
and 46.2 for organic compounds.

12.5.2 Estimation of Heat of Vaporization

The heat of vaporization or the latent heat of vaporization is the difference between the enthalpy
of saturated vapour and the enthalpy of saturated liquid at a given pressure. The latent heat of
vaporization decreases steadily with increase in temperature and is zero at the critical point. The
heat of vaporization at the normal boiling point of a few compounds are listed in Table 12.5.
Table 12.5 Heat of vaporization at normal boiling point (kJ/mol )

Liquid Normal boiling point AHv (kJ/mol)

( K)

Acetic acid 390.4 24.4

Acetone 329.2 30.2
Ammonia 239.73 23.35
Benzene 353.26 30.76
Carbon disulphide 319.41 26.8
Carbon tetrachloride 349.9 30.0
Cyclohexane 353.90 30.1
Diethyl ether 307.76 26.05
Ethyl alcohol 351.7 38.6
Ethylene glycol 470.4 56.9
Formaldehyde 253.9 24.5
Hydrogen chloride 188.11 16.15
Methyl alcohol 337.9 35.3
Methyl cyclohexane 374.10 31.7
w -Heptane 371.59 31.69
«-Hexane 341.9 28.85
Nitric acid 359 30.30
^-Pentane 309.23 25.77
Toluene 383.78 33.5
Water 373.16 40.65

There are several techniques for estimating enthalpy of vaporization , the one based on the
Clapeyron equation being an exact thermodynamic relationship.
Clapeyron equation: The Clapeyron equation predicts the dependence of vapour pressure on
the temperature. It is given by
dPs AHv
_~ ( 12.33 )
dT TAV
where AHv is the latent heat of vaporization, and AV is the volume change accompanying
vaporization. The left-hand side of Eq. (12.33) is the slope of the vapour pressure-temperature
plot . Experimental vapour pressure data or a correlation of vapour pressure with temperature
will provide this value. The ( dPs/ dT ) at a given temperature and the volume change occurring
on vaporization are substituted into Eq. (12.33) to calculate the latent heat of vaporization . If
 Energy Balance: Thermophysics 423

the temperature is not too near the critical point, the volume of the liquid is small in comparison
with the volume of the vapour. The volume change accompanying vaporization AV = VG - VL is
therefore approximately equal to VG , the molar volume of vapour. Equation ( 12.33) now
becomes
dPs _ AH „ ~ ( 12.34 )
dT TVG
The vapour pressure in regions well below the critical point is relatively small so that the vapour
can be assumed to behave as an ideal gas. The molar volume VG can now be replaced by
RT / PS so that Eq. ( 12.34) becomes
dPs s AHv
dT
= RT 2
( 12.35)

or
dPs _ AHv dT
(12.36)
Ps R T2

Equation (12.36) can be rewritten as

< 12 37 )
or
dlnPs _ AHv ( 12.38 )
/
R
d
V
T
The slope of In Ps versus ( 1/ 7) at any temperature gives AHv at that temperature . The
integration of Eq. (12.38) assuming that the heat of vaporization remains constant gives the
Clausius-Clapeyron equation which after substituting the limits takes the following form in the
temperature range of 7) to 7).

Ps (1 1
In 2S AHV
P1 R T T2 [ , (12.39)

where p{ s and p are the saturation pressures at temperatures Tx and T 2 respectively. Over
25
small temperature intervals, the heat of vaporization remains essentially constant and may be
estimated using Eq. (12.39).
The Clapeyron equation in the reduced form can be combined with the Antoine equation
to yield the following relation for heat of vaporization in terms of Antoine constants.

A// y B_ Tr ( 12.40 )
ZRTC Yc Tr - ( C/ Tc )
where B and C are Antoine constants.
424 Stoichiometry and Process Calculations

Watson equation: Watson proposed [K.M. Watson , Ind. Eng. Chem. , 23, 360(1931 ), 35,398
(1943)] the following empirical equation for calculating latent heat of vaporization in terms of
latent heat of vaporisation at the normal boiling point .
( \0.38
AH v 2 1 - Zrl
( 12.41 )
AH vl v
1 - Tr l
/

where AHvl and AHvl are the heat of vaporization at temperature Tx and T2 respectively, and
TrX and Trl are the respective reduced temperatures.
Trouton’s rule: It is observed that the ratio of the molal heat of vaporization at the normal
boiling point to the boiling point in absolute units is constant, or
AH v b
=K ( 12.42 )
Zb
where AHv b is the heat of vaporization at the normal boiling point Tb . K is known as Trouton s
ratio. This ratio is approximately equal to 87.9 J/mol K (=21 cal/mol K ). For non-polar liquids,
this ratio increases slightly with increase in the normal boiling point. For polar liquids, this ratio
is much greater than 87.9 J/mol K. For water and lower alcohols, this value is found to be
108.9 J/mol K (=26 cal /mol K ).
Kistyakowsky equation: The Kistyakowsky equation is an exact thermodynamic equation
that can be utilized for estimating the enthalpy of vaporization of non-polar liquids at their
normal boiling points. Expressing the heat of vaporization at the normal boiling point in J/mol
and temperature in K, the equation takes the following form :
AH v b
zb =
36.63 + 8.31 In Tb ( 12.43 )

The Kistyakowsky equation is not applicable to polar liquids.

Reference substance plots: Two such plots are in common use. the equal -pressure reference-
substance plots and the equal-temperature reference-substance plots. Duhring’s plot is an equal-
pressure reference-substance plot. In this plot the temperature of a substance is plotted against
the temperature of a reference substance (usually water) having equal vapour pressure. The

slope of the resulting straight line is equal to AHV rvf where AHv is the latent heat of
AHVR { T j

vaporization at temperature T and AHvR is the latent heat of vaporisation of the reference
substance at temperature TR where TR is the temperature at which the reference substance has
the same vapour pressure as the substance in question. On the other hand, in equal temperature
reference-substance plots, the logarithm of the vapour pressure of the substance is plotted
against the logarithm of the vapour pressure of a reference substance at the same temperature.

The slope of the resulting straight line is AHv . (A detailed discussion of these plots is given
AHvR
in Chapter 6.)
 Energy Balance: Thermophysics 425

EXAMPLE 12.19 The vapour pressure of water at 363 K and 373 K are respectively 70.11
kPa and 101.3 kPa. Estimate the mean heat of vaporization of water in this temperature range.

f
Solution Refer to Eq. (12.39). Tx = 363 K, T2 = 373 K, / = 70.11 kPa, P2 = 101.3
kPa, R = 8.314 kJ/kmol K, AHv = ? Substituting the values in Eq . ( 12.39), we get
10 E3 l_\
ln =
J
or
70.11 8.314 363
^ 373
AHV = 41 428 J/mol (= 2302 kJ /kg)
From steam tables, the heat of vaporization of water at 368 K is 2270 kJ /kg, indicating that the
value estimated is higher than this by 1.4%.

EXAMPLE 12.20 Estimate the heat of vaporization of methyl chloride at 243.15 K from the
Clapeyron equation assuming ideal behaviour for the vapour phase. The vapour pressure (kPa)
is given by
2137.72
In Ps = 14.2410 -
T - 26.72
where T is in K.
Solution Equation ( 12.36 ) can be written as
d In Ps _ AHv
dT RT 2
Differentiating the given relationship for vapour pressure with respect to T, we get
dlnPs _
~
2137.72
dT ( T - 26.72) 2
Comparing Eq. (A ) with Eq . ( B), we see that
AHv _ 2137.72
2
RT ( T - 26.72) 2
or
2137.72 RT 2
AH .. = ~ (C )
( T - 26.72) 2
To find the heat of vaporization at 243.15 K, substitute T = 243.15 K into Eq . (C ). Thus,
2137.72 X 8314 X (243.15). 2
( 243.15 - 26.72 ) 2 = 22 43233 -
kJ
kmol

EXAMPLE 12.21 Using the Watson equation, find the latent heat of vaporization of water at
473 K given that the latent heat of vaporization at 373 K is 2256 kJ/kg. The critical temperature
of water is 647 K.
426 Stoichiometry and Process Calculations

Solution The following values in the Watson Equation are known:

T 373
=—
AHvX = 2256 kJ/kg,

T2 = 473 K’, Trlr2

T { = 373 K,

T2
= — =—
473
= 0.7311
Trl =
^Tc 647
= 0.5765 ,

Tc 647
Substitute these values in the Watson equation
/ 0.38
AH,2 1 - Tr. l \
A HvX 1 - Tr1
V /

\ 0.38
A Hv 2 1 - 0.7311
= 0.8415
2256 1 - 0.5765
/

Therefore, A//v2 = 0.8415 x 2256 = 1898 kJ/kg

So, the latent heat of vaporization of water at 473 K = 1898 kJ /kg.
EXAMPLE 12.22 Heat capacity of liquid benzene is given below :

T ( K) 293 323
CP ( J/molK) 131.05 138.04

( a) Fit the data into an equation of the form

CP = a + bT
(b ) Calculate the heat required to convert 100 kg of liquid benzene from 293.15 K into
saturated vapour at the normal boiling point of 353.25 K. The latent heat of vaporization
may be estimated using the Kistyakowsky equation.
Solution
(a) If the variation of heat capacity of benzene with temperature is represented by CP = a
+ bT , then
a + 293 b = 131.05
a + 323 b = 138.04
Solving these two equations simultaneously, we get a = 62.781 and b = 0.233
The desired equation for heat capacity of benzene is
CP = 62.781 + 0.233 T
( b ) Kistyakowsky equation is

— = 36.63 + 8.31 In 71
Tb
Substituting Tb = 353.25 K into the above equation, we get AHvb = 30163 J/mol.
 Energy Balance: Thermophysics 427

The total heat required for the desired process is the sum of ( 1 ) heat required to heat
the liquid from 293.15 K to 353.25 K and (2) the heat of vaporization, i.e.
T2
Heat required = m f I dT + mAHv

1 00 X 1 03 rr 353.25 100 x UV3

\
78.048 293.15
(62.781 + 0.233T ) dT +
78.048
— x 30163

= 1.0633 x 107 + 3.8647 x 107 = 4.928 x 107 J

12.6 STEAM TABLES

Steam tables provide a tabular representation of the thermodynamic properties of water in the
saturated liquid state or in the saturated or superheated vapour state. Usually steam tables are
given in two parts ( Refer to steam tables given in Appendix A ). The first one gives the
thermodynamic properties of saturated steam and the second one gives the thermodynamic
properties of superheated steam. The saturated steam tables give the enthalpy, entropy, and
specific volume of saturated water and saturated steam as functions of saturation temperature
and/or saturation pressure. The phase rule predicts that only one property, either the temperature
or the pressure is sufficient to define the state of the saturated water-water vapour system in
equilibrium . The tables give these properties in the temperature range of 273.15 K to 647.30 K
(0°C to 374.15°C ) the temperature range in which the liquid and vapour can coexist in equilibrium.
The changes in these property values when the unit weight of liquid water is vaporized is also
provided in the saturated steam tables. For example, let us consider the thermodynamic properties
of saturated liquid and saturated vapour at 200 kPa. Refer to the saturated steam table
(Table A .3) given in Appendix A. The table gives the following values in the horizontal row
corresponding to 200 kPa:
Saturation temperature, Ts = 393.38 K
Specific volume of saturated water, F/ = 1.061 x 10-3 m3/kg
Specific volume of saturated steam, Vg = 885.7 x 10-3 m3/kg
Internal energy of saturated liquid, Ui = 504.49 kJ/kg
Internal energy of saturated vapour, Ug = 2529.50 kJ/kg
Enthalpy of saturated liquid, H / = 504.70 kJ/kg
Enthalpy of saturated vapour, Hg = 2706.70 kJ/kg
Entropy of saturated liquid, S / = 1.5301 kJ/kg K
Entropy of saturated vapour, Sg = 7.1271 kJ/kg K
The volume change accompanying the vaporization and the internal energy, enthalpy and
entropy of vaporization can be obtained as the difference between the respective property
values of saturated vapour and saturated liquid. Thus enthalpy of vaporization at 200 kPa is
2706.70 - 504.70 = 2202 kJ/kg
These values are also given in some steam tables.
In a system made up of saturated liquid and saturated vapour, the weight fraction of the
mixture that is dry steam is called the quality or dryness fraction of steam. Denoting the
428 Stoichiometry and Process Calculations

fraction of dry steam or the quality of the mixture by y the specific volume and enthalpy of
9

wet steam can be determined by the following relationships :

V = (1 - y )Vt + yVg ( 12.44 )
H = (1 y )Ht + yHg
- ( 12.45)
In the superheat tables (Table A.4), the specific volume, internal energy, enthalpy and entropy
of steam at a particular pressure are given for various degrees of superheat . In addition, these
tables also give the values of these properties for saturated liquid and saturated vapour at that
pressure.

EXAMPLE 12.23 The quality of wet steam is determined using steam calorimeters. The wet
steam is throttled in a steam calorimeter, and the enthalpy of the resulting super heated steam
is measured by noting its temperature and pressure. Throttling is a constant enthalpy process.
If wet steam at 700 kPa enters the throttling calorimeter and the discharged steam is at 10 kPa
and 358.15 K. Using steam tables find the quality of steam.
Solution The enthalpy of superheated steam at 10 kPa and 358.15 K is determined from
steam tables. From Table A.4:
At 10 kPa, 323.15 K, H = 2592.6 kJ/kg
At 10 kPa, 373.15 K, H = 2687.5 kJ/kg
The enthalpy of superheated steam at 10 kPa and 358.15 K is found by interpolation.
2687.5 - 2592.6
H = 2592.6 + (358.15 - 323.15) = 2659 kJ /kg
373.15 - 323.15
Since throttling is a constant enthalpy process, the enthalpy of the original wet steam at 700 kPa
is also 2659 kJ /kg. At 700 kPa, enthalpies of saturated liquid and saturated vapours are 697.061
and 2762.0 kJ/kg respectively. The enthalpy of the mixture is
H = (1 - y )Hf + yHg = 697.061( 1 - y ) + 2762.0y
Since H = 2659 kJ/kg, we have
697.061( 1 - y ) x 2762.0 + y = 2659
which is solved to give y = 0.9501 or the quality or the dryness fraction = 0.9501.
The wet mixture contains 95% dry saturated steam and 5% moisture.

EXAMPLE 12.24 A large main contains 100 kg of steam at 3500 kPa and 673.15 K . It is
closed at both ends , (a) Find the temperature and pressure in the main after half the steam has
condensed , (b) How much heat is removed from the system during this process?
Solution
( a) The specific volume of superheated steam at 3500 kPa and 673.15 K is, from the steam
tables (Table A.4), 0.084 53 m 3/kg . When half the vapour is condensed, the volume
occupied by the 100 kg of the original superheated steam is now being occupied by
50 kg of vapour and 50 kg of condensate. Since the volume of liquid is negligible in
comparison with the volume of vapour, the specific volume of the saturated vapour is
 Energy Balance: Thermophysics 429

100 x 0.084 53
V = = 0.1690 m3/kg
50
Referring to saturated steam tables, we see that the saturated steam having this specific
volume for the vapour is at 1158 kPa and the saturation temperature is 459.5 K.
( Note: If we consider the volume of liquid also, the temperature and pressure is to be
determined using the following relation:
50( V / + Vg ) = 100 x 0.0845
But Vf is very small in comparison with Vg, and therefore no appreciable error is
introduced by the assumption that V ~ Vg ).
(b ) The heat liberated in the process is obtained from the relation
AU = Q - W
Since this is a constant volume process, W = 0; therefore,
Q = AU = U2- Ux
where U2 is the internal energy of the system in the final state and Ux is the internal
energy in the initial state.
The internal energy of superheated steam at 3500 kPa and 673.15 K = 2928.4 kJ/
kg (from Table A.4)
Ux = 100 x 2928.4 = 292 840 kJ
The internal energies of saturated vapour and liquid at 1158 kPa (459.5 K ) are also read
from saturated steam tables,
£ // = 790 kJ/ kg
Ug = 2585.9 kJ/ kg
U 2 = 50 x 790 + 50 x 2585.9 = 168 795 kJ
Q = AU = U2 - Ux = 168 795 - 292 840 = -124 045 kJ
The amount of heat removed from the system during this process is 124 045 kJ.

12.7 HEAT OF MIXING

The environment of a molecule in a solution is different from that in the pure state. Since the
energy of interaction between like molecules is different from that between unlike molecules,
the energy of a solution is different from the sum of the energies of its constituents. This
difference between the energy of the solution and the energy of the constituents leads to the
absorption or evolution of heat during the mixing process. The heat of mixing (or the enthalpy
change of mixing) is the enthalpy change when pure species are mixed at constant pressure and
temperature to form one mole (or unit mass) of solution. For binary mixtures,
AH = H - ( xxHx + X 2H2 ) ( 12.46 )
430 Stoichiometry and Process Calculations

Here x\ and x2 are the mole fractions of components 1 and 2 in the solution . Knowing the
enthalpies of the pure constituents H { and H2, and the heat of mixing at the given concentration,
the enthalpy of the solution can be computed as
H = ( x XHX + X 2H2 ) + AH ( 12.47)
When solids or gases are dissolved in liquids, the accompanying enthalpy change is usually
measured as heats of solution , which is defined as the enthalpy change when one mole of the
solute dissolves in the liquid. Thus,
AH
A Hs = ( 12.48 )
X[

where AHS is the heat of solution per mole of solute (component 1 ) . When the constituents
are all liquids and solutions of all proportions are possible, the heat effect is usually termed
heat of mixing. Figures 12.6 and 12.7 illustrate the two types of presentation of heat of mixing.

600
383 5 K

400 363 5 K
c
o
3
o 200 343 15 K
o 34 5K
E

W)
.£ 200 323.15 K
x
E
°
3
400
298.15 K
<D
X
600 -

800

0 0.2 0.4 0.6 0.8

Mole fraction , ethanol
Figure 12.6 Heat of mixing of ethanol in water.

In Figure 12.6 is shown the heat of mixing of ethanol-water from which it is clear that
the mixing process at low temperatures and low concentration of ethanol is exothermic and
at high temperatures and high concentrations it is endothermic. In Figure 12.7 heats of
solution of various substances in water are plotted with moles of water per mole of solute
as the abscissa.
Using the heat of mixing at one temperature and heat capacity data of pure species and the
solution (Table 12.6), the heat of mixing at any temperature can be calculated. The method of
calculation is similar to the one employed for the calculation of standard heat of reaction at any
temperature from the values at 298 K.
 Energy Balance: Thermophysics 431
- 80 000
HC1 ( g )
=s
S - 60 000 h H2SO4(1 )
o
S
NaOH ( c )
c
o
- 40 000 -
3
O
c /i ,
HNO ( l )
O
03
- 20 000 -
PC

4 8 12 16
«, moles of water per mole of solute

Figure 12.7 Heat of solution at 298 K.

Table 12.6 Heat of solution data in aqueous systems (kJ/mol ) at 298 K

( n = moles of H20/mole of material )

n Na 2C03(s) NaOH(s) NH4N03(S) HN03(1) H2SO4(1) HCl( g)

1 -13.10 -28.09 -26.25
2
4 -34.46 +17.04
-20.10
-27.00
-11.95
-54.09
-48.86
-61.25
8 41.95 +19.18 -31.15 64.64 68.29
--
- - -

15 - 32.78 12.87 +21.19 -32.49 -70.21 -71.05

25 -31.07 12.83 +23.15 -32.78 -72.35 -72.31
50 -28.43 - 42.54 +24.20 -32.78 -73.39 -73.31
100 -26.25 - 42.37 +25.00 -32.78 -74.02 -73.90

EXAMPLE 12.25 Caustic soda is concentrated from 10% to 50% in a single effect-evapo-
rator. The feed at 305 K enters at a rate of 1000 kg/h . The concentrated solution leaves the
evaporator at 380 K and the vapour leaves at 373.15 K. Determine the heat to be supplied
in the evaporator. The mean heat capacity applicable to the solutions are 3.67 kJ / kg K for the
feed and 3.34 kJ /kg K for the product. The heat of solution of 10% and 50% NaOH solution
at 298 K are, respectively - 42.85 kJ/mol and - 25.89 kJ/mol . The latent heat of vaporization
of water at 298 K is 2442.5 kJ/kg and the mean heat capacity of water vapour is 1.884 kJ/kg K.
Solution Basis: 1000 kg/h of 10% NaOH solution
The product is 50% NaOH solution. Let P be the weight of the product . Take an NaOH
balance:
0.5P = 0.1 x 1000
Therefore,
P = 200 kg/h
432 Stoichiometry and Process Calculations

Let W be the quantity of water vaporized. Then the total material balance gives
1000 = P + W
The amount of water vaporized,
W = 1000
200 = 800 kg/h
-

The process can be assumed to take place along the paths shown in Figure 12.8.

800 kg water AH 4 800 kg water

vapour at vapour at
298 K 373.15

AH 3

100 kg
1000 kg /h of AH I 1000 kg /h of AH 2
NaOH + 900
10 % NaOH 10 % NaOH * kg water at
at 305 K at 298 K
298 K

AH 5

200 kg 50 % 200 kg 50 %
NaOH at NaOH at
298 K AH 6, 380 K

Figure 12.8 Enthalpy balance for the evaporation process in Example 12.25.

Step 1. Cooling 1000 kg/ h of 10% solution from 305 K to 298 K.

AHx = 1000 x 3.67 x (298 - 305) = -25 690 kJ
Step 2. Separation of the solution into the pure constituents at 298 K. The enthalpy change
in this step is the negative of the heat of solution. The heat of solution is - 42.85
kJ/mol. The number of moles of NaOH in the solution is

40
= 2.5 kmol = 2500 mol
AH2 = — (— 42.85 x 2500) = 107 125 kJ
Step 3. 800 kg of water at 298 K is converted to water vapour at 298 K.
AH 3 = 2442.5 x 800 = 1 954 000 kJ
Step 4. Water vapour at 298 K is heated to 373.15 K.
AHA = 800 x 1.884 x (373.15 - 298) = 113 266 kJ
Step 5 . Formation of 200 kg of 50% NaOH solution at 298 K .
AHS = 2500 x (- 25.89) = 64 725 kJ
Step 6 . Heating the solution from 298 K to 380 K .
AH6 = 200 x 3.34 x (380 - 298) = 54 776 kJ
 Energy Balance: Thermophysics 433

The enthalpy change accompanying the complete process is

AH = AHX + AH 2 + AH3 + AH4 + AH5 + AH6
= - 25 690 + 107 125 + 1 954 000 + 113 266 - 64 725 + 54 776
= 2 138 752 kJ

EXAMPLE 12.26 Calculate the mean heat capacity of a 20-mole percent solution of alcohol
in water at 298 K given the following:
Heat capacity of water: 4.18 x 103 J/kg K; heat capacity of ethanol: 2.18 x 103 J/kg K; and
heat of mixing for 20 mole-percent ethanol-water at 298 K: -758 J/mol; heat of mixing for
20 mole- percent ethanol -water at 323 K: - 415 J/mol. Assume that the heat capacities of pure
liquids are constant between 298 and 523 K.
Solution The enthalpy change when 0.8 moles of water and 0.2 moles of ethanol both
at 323 K are mixed together is given by the heat of mixing at 323 K which is equal to - 415 J/
mol of solution.
—
0.8 mol water at 323 K + 0.2 mol ethanol at 323 K » 1.0 mole 20 percent ethanol-water,
AH = - 415 J/mol.
This change can be assumed to be taking place in four steps as detailed in Figure 12.9.
Basis: 1 mol ethanol-water solution at 298 K

0.8 mol AH l 0.8 mol

water water
323 K 298 K
AH 3 1 mol ethanol- AH 4 1 mol ethanol-
water solution water solution
at 298 K at 323 K
0.2 mol AH 2 0.2 mol
ethanol ethanol
323 K 298 K

Figure 12.9 Mean heat capacity of ethanol-water solution (Example 12.26 ).

Step 1. 0.8 moles of water is cooled from 323 K to 298 K. Let AHx be the enthalpy of cooling.
Then
AHx = 0.8 x 18.016 x 4.18 x (298 - 323) = -1506.1 J
Step 2. 0.2 mol ethanol cooled from 323 K to 298 K. Let AH2 be the enthalpy of cooling.
AH 2 = 0.2 x 46.048 x 2.58 x (298 - 323) =
594.0 J -

Step 3. 0.8 mol water and 0.2 mol ethanol at 298 K are mixed together. The heat of mixing is
AH3 = -758 J/mol
Step 4. 20 percent ethanol-water solution is heated to 323 K . The enthalpy of heating is
AH4 = CP w(323 - 298)
where Cp m is the mean specific heat of solution.
434 Stoichiometry and Process Calculations

AH = AHX + AH2 + AH 3 + AH4

= -1506.1 - 594.0 - 758 + CP m (323 - 298)
- 415
Thus the mean heat capacity of a 20 percent solution is CP m = 97.72 J/mol K

12.7.1 Enthalpy-Composition Diagrams

In enthalpy-concentration diagrams, the enthalpy of a binary solution is plotted against the
composition with temperature as parameter. The pressure is constant and usually the diagrams
at one atmosphere pressure are in common use. The composition is represented by mole fraction
or mass fraction of the solute. As shown earlier, the enthalpy of a binary solution is given by
Eq. (12.47), i .e.
H = (.xxHx + X 2H2 ) + AH
At a given temperature and pressure, enthalpy H depends on the composition, enthalpies of the
pure components Hx and H2, and the heat of mixing AH . Pure components are arbitrarily
assigned an absolute enthalpy of zero at a certain reference state. For water, the reference state
chosen is the triple point of water (- 273.16 K), same as that used in steam tables. This choice
permits the use of enthalpy values read from the steam tables along with the values from the
enthalpy-concentration charts without any corrections. The reference temperature at which the
enthalpy of the solute is assigned zero value need not be the same as that adopted for water.
For solutes such as NaOH, H2S04, etc. 298.15 K is used as the reference temperature at which
the component has zero enthalpy. Enthalpies of the pure components will not be zero at
temperatures other than the reference temperatures. These enthalpies are estimated using the
heat capacities of the pure components. The enthalpy of a solution of these constituents at any
temperature is the concentration-weighted average of the enthalpies of the pure components plus
the heat of mixing at that composition. However, for ideal solutions, the heat of mixing is zero
and enthalpy of the solution is the concentration-weighted average of the enthalpies of the pure
components, which can be represented by a straight line joining the pure component enthalpies
as shown in Figure 12.10. The heat of mixing (the heat evolved or absorbed when the solution
is formed from its constituents) is given by the vertical distance between this straight line and
the enthalpy-concentration curve. Figure 12.11 gives the enthalpy-concentration curve for
NaOH-water solution.

0 0.5
Weight fraction
Figure 12.10 Enthalpy of solution versus concentration .
 Energy Balance: Thermophysics 435
1100

000

900

c
800
478 K
478
m
o
700
o
in
_450
W) 600
422 -
3 500
a. 394 .::
"

73
JS 400
c
W
300
367
339
^^55
31
339
200
3TI
100
283
0
0 0.2 0.3 0.4 0.5 0.6 0.7
Mass fraction of NaOH in water
Figure 12.11 Enthalpy-composition diagram for NaOH-water.

EXAMPLE 12.27 Caustic soda is concentrated from 10% to 50% in a single-effect evapo-
rator. The feed at 305 K enters at a rate of 1000 kg/h. The concentrated solution leaves the
evaporator at 380 K and the vapour leaves at 373.15 K . Determine the heat to be supplied in
the evaporator. Take the necessary data from the enthalpy-concentration diagram and steam
tables. Assume that the pressure inside the evaporator is one atmosphere.
Solution
Steam, 373.15 K,
1 atm, 800 kg/h

Evaporator
Feed solution, Product , 50% NaOH,
10% NaOH, 380 K, 200 kg /h
305 K, 1000 kg/h

Heat supplied,
Q kJ /h

Figure 12.12 Evaporation of NaOH solution ( Example 12.27).

436 Stoichiometry and Process Calculations

From enthalpy-composition diagram:

Enthalpy of feed solution (10% NaOH, 305 K) = 116.3 kJ /kg
Enthalpy of thick liquor (50% NaOH, 380 K) = 560.57 kJ/kg
From steam tables:
Enthalpy of steam ( 1 atmosphere, 373.15 K) = 2676 kJ/kg
As shown in Example 12.25, the material balance is written for the evaporator and the following
values are calculated:
Weight of product = 200 kg/h
Weight of water vaporized = 800 kg/h
Enthalpy balance on the evaporator yields
1000HF + Q = 800//$ + 200HP
where HF, HP and Hs are the enthalpies of feed, product and steam respectively. Substituting
the values, we get
1000 x 116.3 + Q = 800 x 2676 + 200 x 560.57
Therefore,
Q = 2 136 614 kJ/h.

12.8 ENERGY BALANCE IN CYCLIC PROCESSES

The first law of thermodynamics is a generalization based on our experiences such as the failure
to construct a perpetual motion machine, the constancy of mechanical equivalent of heat, etc.
It is stated in a number of ways, but essentially it means that energy is indestructible. Any loss
or gain of energy by the system must be exactly equivalent to the gain or loss of energy of the
surroundings.
In a cyclic process the system is brought back to its original state after a series of changes.
Energy exchange between the system and the surroundings occur through the mechanism of
heat and work since these are the energies in transit . Work is done on the system by forces
acting from the surroundings, and heat is transferred between the system and the surroundings
during the process. Since there is no change in the internal energy of a system in a cyclic
process, by the first law of thermodynamics, the algebraic summation of all work effects
exactly equals the summation of all heat effects. Let Q denote the heat added to the system
and W denote the work done by the system ( Q is negative when heat is rejected by the system
and W is negative when work is done on the system) and if both are measured in consistent units,
IW = IQ

12.9 ENERGY BALANCE IN NON-FLOW PROCESSES

12.9.1 First Law of Thermodynamics for Non-flow Process
The first law of thermodynamics requires that the change in the total energy of the system be
compensated by an equal but opposite change in the total energy of the surroundings, so that
 Energy Balance: Thermophysics 437

there is no net change in the energy in any process. For a closed system undergoing only
changes in the kinetic , potential and internal energies, the total energy change of the system
(A£)sys is given by
( AE )sys = A(KE) + A(PE) + A U (12.49)
A( KE) and A( PE) denote changes in kinetic energy and potential energy respectively, and AU
is the change in the internal energy. The change in the total energy of the surroundings occurs
only through the exchange of heat or work with the system. Then the change in the total energy
of the surroundings (AE)sur must be equal to the energy transferred to or from it as heat and
work .
(AE)sur = - Q + W ( 12.50 )
By the first law of thermodynamics,
(A£)sys + (A£)sur = 0 ( 12.51 )
Substituting Eqs. (12.49) and (12.50) into Eq. (12.51 ) and rearranging the resulting equation,
we get
A(KE) + A(PE) + AU = Q - W ( 12.52 )
Equation (12.52) means that the total energy change in a closed system is equal to the heat
added to the system minus the work done by the system. For a steady-state non-flow process
in which there are no changes in the kinetic energy and potential energy, the above equation
simplifies to
AU = Q - W ( 12.53 )

EXAMPLE 12.28 A rigid tank holds one kilogram of air at 300 K. The air has an internal
energy of 0.25 x 103 kJ with reference to the fixed datum conditions. Heat is added to the air
until the internal energy is 0.35 x 103 kJ. Calculate the heat transferred to the air.
Solution Since the tank is rigid, the volume of the gas does not change during heating.
Under constant volume, the change in internal energy is equal to the heat supplied. Therefore,
Q = AU = U2 -
Ux = 0.35 x 103 - 0.25 x 103 = 100 kJ
EXAMPLE 12.29 A system consisting of some fluid is stirred in a tank. The work done on
the system by the stirrer is 2.25 hp. The heat generated due to stirring is dissipated to the
surroundings. If the heat transferred to the surroundings is 3400 kJ/ h, determine the change in
internal energy.
Solution The work done on the system can be obtained as:
-W = 2.25 hp = 2.25 x 745.7 = 1677.825 W = 1677.825 J/s
Heat transferred to the surroundings is
-Q = 3400 kJ/h = 3400 x 103/3600 = 944.444 J/s
By Eq. (12.53),
AU = Q - W = -944.444 - (-1677.825) = 733.381 J/s
Therefore, the internal energy of the system increases by 733.481 J in one second .
438 Stoichiometry and Process Calculations

EXAMPLE 12.30 Iron filings are contained in a cylinder in an atmosphere of oxygen. It

combines with oxygen according to the following reaction.

2Fe + § 02 Fe203
The pressure inside the cylinder is maintained at 101 kPa. The temperature is kept constant at
298 K by removing heat. For 2 mol iron reacted, calculate Q, W and AU given that 831.08 kJ
of heat is liberated in the process.
Solution The heat liberated when 2 mol iron reacts with oxygen is 831.08 x 103 J.
Therefore,
Q = - 831.08 x 103 J
Neglecting the volume occupied by the solids, the volume change accompanying the process
is equal to the change in the volume of oxygen. Assuming the ideal gas behaviour for the gas,
PAV = ( An ) RT
where AV is the volume change and An, the increase in the number of moles accompanying the
reaction. Here An = -1.5. Therefore, the work done by the system ,
W = PAV = ( An )RT = -1.5 RT
= - 1.5 (8.314) 298 = - 3716.4 J
The change in the internal energy is
AU = Q - W = - 831.08 x 103 - (- 3716.4) = - 827.364 x 103 J
EXAMPLE 12.31 A mixture of saturated steam and saturated water is contained in a rigid
tank of volume 0.1 m3 at a pressure of 2 bar. The liquid occupies 10% of the total volume. How
much heat must be added in order that the tank contains only saturated steam? What will be
the pressure in the tank? At a pressure of 2 bar, the specific volumes of saturated liquid and
saturated vapour are 1.061 x 10-3 m3/kg and 0.8857 m3/kg respectively, and the internal energy
of saturated liquid and saturated vapour are respectively 504.5 kJ / kg and 2529.5 kJ/kg.
Solution The volume occupied by the gas is 0.09 m3 and the volume occupied by the
liquid is 0.01 m 3. Since the specific volumes are 1.061 x 10-3 m 3/kg and 0.8857 m3/ kg
respectively,

mass of vapour
F =
0.8857
= 0.1016 kg

mass of liquid =
1.061 x 10-3
7 = 9.425 kg
The internal energy of the initial mixture Ux = Ut + Ug . Substituting the values,
C/ j = 9.425 x 504.5 + 0.1016 x 2529.5 = 5012 kJ
In the final state the entire liquid is vaporized and the tank contains only saturated vapour. That
is, a volume of 0.1 m3 is occupied by a mass of (9.425 + 0.1016 = 9.5266 kg ) of vapour.
Therefore, the specific volume of the vapour is
 Energy Balance: Thermophysics 439

0.1
= 0.0105 m 3/kg
9.5266
From steam tables, we can see that this specific volume for saturated vapour corresponds
to a pressure of 148.6 bar and the internal energy of saturated vapour under this condition is
2464.6 kJ/ kg. Therefore, the total internal energy in the final state is
9.5266 x 2464.6 = 23 479 kJ
AU = Q - W
But W = 0; therefore,
Q = AU = U2 - Ux = 23 479 - 5012 = 18 467 kJ

12.9.2 Energy Changes in Ideal Gas Processes

Constant volume process: For a constant volume process, there is no work of expansion and
dW = 0. The heat supplied is equal to the product of heat capacity and rise in temperature, i.e.
dQ = Cv dT
Since for differential changes, the first law of thermodynamics is mathematically expressed as
dU = dQ - dW ( 12.54 )
for constant volume process, the first law reduces to
dU = dQ = Cv dT ( 12.55)
This equation is applicable to all gases, whether ideal or real, in a constant volume process.
Since the internal energy of an ideal gas depends upon the temperature only, the change in
internal energy of an ideal gas in any process is
dU = CydT ( 12.56 )
Constant pressure process: In a constant pressure process, the heat supplied is the product
of heat capacity CP and the rise in temperature: dQ = CP dT. The work involved is the work
of expansion as given by dW = P dV . Equation (12.54) now becomes
dU = CP dT - P dV ( 12.57)
For a constant pressure process, the change in enthalpy is
dH = dU + P dV ( 12.58 )
Combining Eqs. (12.57) and (12.58), we get
dH = CP dT ( 12.59)
Thus, for the process occurring at constant pressure, we have the following general result
applicable for all gases whether ideal or not.
dH = dQ = CP dT ( 12.60 )
Again, as the enthalpy of an ideal gas depends on temperature alone, the change in enthalpy
for all processes involving ideal gases is given by
dH = CP dT ( 12.61)
440 Stoichiometry and Process Calculations

Constant temperature process: Internal energy of an ideal gas will change only with change
in temperature. In an isothermal process, the change in internal energy and the change in
enthalpy of an ideal gas would be zero. Put dU = 0 in Eq. ( 12.54) so that
dW = dQ ( 12.62)
The above equation can be integrated to determine the heat and work effects in an isothermal
process involving ideal gases.

Q =W = jpdV
Since P = RT/V , the above equation gives

Q =W = RT InE ( 12.63)
M

where Vl and V2 are the initial and final volumes of the gas in an isothermal process. Let Px
and P2 be the pressures in the initial and final states respectively. Then the ideal gas equation
leads to the following relation:

VL = PL ( 12.64 )
V\
Substituting Eq. (12.64) into Eq. (12.63), the latter can be modified as
V, R
Q =W = RT In — = RT \n —P ( 12.65)
Vi 2

Adiabatic process: In an adiabatic process, there is no heat interaction between the system
and the surroundings. dQ is zero in Eq. ( 12.54) so that we have
dU = - dW = -P dV ( 12.66 )
for an adiabatic reversible process. The pressure and volume in an adiabatic process are related
as
PV ? = Constant
where y = CP/ CV, which is assumed constant for an ideal gas.
Since CP - Cv = R , a constant, it follows that both CP and Cv are also constant. Also,
R= Cv ( y - 1) ( 12.67)
Using Eq . ( 12.56) in Eq. (12.66), we see that
dW = P dV = - Cv dT ( 12.68 )
The work done in the adiabatic process is given by Eq. (12.68). Since Cv is constant,
Eq. (12.68 ) can be readily integrated.
W = CV ( TX - T2 ) ( 12.69)
Eliminating Cv from this equation in terms of / using Eq. (12.67),

w_ , _
RT - RT2 PM - P2V2
( 12.70)
7 -1 7 -1
 Energy Balance: Thermophysics 441

Equation (12.70) gives the work done in an adiabatic process involving ideal gas. Equation
(12.70) can be put into a more useful form as follows:
r
V 2\ pyy Pl f
*P Ir
py
w= 1- * 2 1-
7 -1 V Wi /
7 -1 R1 V 2
z
/

That is,
P
( y -UY
W = PiVi 1- 2 ( 12.71 )
-1 7 P1
V

The following relationships between temperature and volume, and temperature and pressure in
adiabatic processes can be easily derived:
f y -i
12 ( 12.72)
Ti V
v2
/
R2
v -i / y
l\ ( 12.73 )
Tx V
1

EXAMPLE 12.32 Heat is transferred to 10 kg of air which is initially at 100 kPa and 300
K until its temperature reaches 600 K. Determine the change in internal energy, the change in
enthalpy, the heat supplied and the work done in the following processes:
( a) Constant volume process
(b) Constant pressure process
Assume that air is an ideal gas. Take CP = 29.099 kJ/kmol K and Cv = 20.785 kJ /kmol K.
Solution The number of moles of the gas = 10/29 = 0.3448 kmol.
Px = 100 kPa, Tx = 300 K. Hence,
Vx = nRTx!Px = 0.3448(8.314) 300/100 = 8.6 m3
(a) V2 = 8.6 m3 and T2 = 600 K.
The change in internal energy:
AU = n\Cv dT = (0.3448)20.785(600 - 300) = 2150 kJ
Heat supplied:
Q = AU = 2150 kJ
Work done :
W=Q - AU = 0
Change in enthalpy :
AH = AU + A( PV ) = AU + nR AT
= 2150 + (0.3448) 8.314 (600 - 300 ) = 3010 kJ
442 Stoichiometry and Process Calculations

(b ) P2 = 100 kPa and T2 = 600 K.

Change in enthalpy:
r 600
AH = n J 300 CP dT = (0.3448) 29.099 (600 - 300) = 3010 kJ
Heat supplied:
Q = AH = 3010 kJ
Change in internal energy:
AU = AH - A( PV ) = AH - nR AT
= 3010 - (0.3448) 8.314 (600 - 300) = 2150 kJ
Work done:
W = Q - AU = 860 kJ
{ Note: The work done may also be calculated as
W = P{y2 _ Vl)
V2 = nRT2/ P = 0.3448 (8.314) 600/ 100 = 17.2 m3
Therefore, W = PAY = 100 (17.2 - 8.6) = 860 kJ)

EXAMPLE 12.33 An ideal gas is undergoing a series of three operations as detailed below:
The gas is heated at constant volume from 300 K and 1 bar to a pressure of 2 bar. It is
expanded in a reversible adiabatic process to a pressure of 1 bar. It is cooled at a constant
pressure of 1 bar to 300 K. Determine the heat and work effects for each step. Assume CP =
29.3 kJ/kmol K.
Solution The difference between CP and Cv of an ideal gas is equal to R, the ideal gas
constant. Hence, Cv is given by
Cv = CP - R = 29.3 - 8.314 = 20.986 kJ/kmol K
Step 1. Volume remains constant. Therefore, the work done is zero and the heat supplied is Cv
( T2 - Tx ). Also, T2 / Tx = P2 / Px = 2. That is,
T2 = 2 x 300 = 600 K
where T2 is the final temperature attained in Step 1. The heat supplied is
20.986 x (600 - 300) = 6295.8 kJ /kmol
Step 2. The process is adiabatic. Therefore heat supplied is zero. The work done is given by
Eq. ( 12.69), i.e.
W = Cv ( Tx - T2 )
where Tx and T2 are the initial and final temperatures in the adiabatic process which
are related to the initial and final pressures by Eq. (12.73 ), i.e.
/
h P2
Tx \
P1 /
 Energy Balance: Thermophysics 443

( - /
f p \7 0 7 \ ( 0.4 / 1.4 )

= 6 0 0 x 1 -2 1
l'
2
Therefore, T2 = t\ = 492.2 K
V
R1 /

So, W = 20.986 (600 - 492.2) = 2262.3 kJ /kmol. Since W is positive, the work is done
by the system.
Step 3. The process is isobaric. The heat supplied is calculated as
CP( T2 - Tx ) = 29.3(300 - 492.2) = -5631.5 kJ/kmol
( Heat is given out by the system.)
AU = Cy{ T2 - Tx ) = 20.896 (300 - 492.2 ) = - 4016.2 kJ /kmol
The first law states that AU = Q - W. Hence,
W = Q - AU = -5631.5 + 4016.2 = - 1615.3 kJ / kmol
(Work is done on the system.)

EXAMPLE 12.34 Calculate the change in internal energy, the change in enthalpy, the work
done and the heat supplied in the following processes:
(a) An ideal gas is expanded from 5 bar to 4 bar isothermally at 600 K.
(b ) An ideal gas contained in a vessel of 0.1 m3 capacity is initially at 1.01325 bar and 298 K.
It is heated at constant volume to 400 K.
(Assume that CP = 30 J/mol K.)
Solution
(a) Since the internal energy and enthalpy of ideal gas depend only on temperature, in an
isothermal process, they remain constant. AU = AH = 0. Equation (12.65) is used to
calculate the work done and heat supplied, i.e.

Q = w = RT In E = 8.314 x 600 x In - = 1113.13 kJ/kmol

P2 4
(b ) The number of moles of the gas is
PVIRT = ( 1.01325 x 105) 0.1/(8.314 x 298) = 4.04 mol
Cy = Cp — R = 30 — 8.314 = 21.686 J /mol K
AU = Cy( T2 - Tx ) = 21.686(400 - 298) = 2212 J/mol = 2212( 4.04) = 8936 J
AH = CP( T2 - Tx ) = 30(400 - 298) = 3060 J /mol = 12,362 J
Being a constant volume process, W = 0, and Q = AU + W = AU = 8936 J.

12.10 ENERGY BALANCE FOR FLOW PROCESSES

The energy balance in steady-state flow processes become important when we consider flow
through equipment such as pumps, fans, compressors, turbines, nozzles, heat exchangers,
reactors, etc. where energy is transferred or is converted from one form to another. Consider
an idealized flow system as shown in Figure 12.13. A fluid is flowing through the apparatus
from section 1 to section 2. The velocity, specific volume, pressure and height above the datum
444 Stoichiometry and Process Calculations

level are represented by w, V P and Z respectively. Suffix 1 indicates conditions at section 1

9

and suffix 2 the conditions at section 2. Per unit mass of the fluid, heat Q is added by means
of the heat exchanger and shaft work Ws is extracted by means of a turbine or any other
suitable device.
Section 1
Uv Vv Pv Zp ux

Heat exchanger

/
< * Q

Section 2
P 2'
^’P’^’ ^
2 2 2 2

O-p
Turbine z2
Reference line I
Figure 12.13 Steady-state flow processes.

The total energy of the fluid entering and leaving the system is made up of the internal
energy possessed by the molecules, the potential energy due to its elevation above the datum
level , the kinetic energy due to the velocity of the fluid and the flow energy which is equal to
the product of pressure P and specific volume V of the fluid. Between sections 1 and 2, the
change in the total energy of the unit mass of fluid is therefore equal to

AU + A ( PV ) + gAZ + - Au 2
2
By the first law, this should be equal to Q - Ws, the energy imparted to the fluid externally
through heat or work. Therefore,

A U + A ( PV ) + gAZ + - AU 2 = Q - WS ( 12.74 )
2
Substituting Eq. (12.11), i.e. AH = AU + A( PV ) into Eq. (12.74), we get

AH + gAZ + - Au 2 = Q - WS ( 12.75)

Equation (12.75) is the mathematical statement of the first law of thermodynamics for flow
processes and can be used for solving problems involving flow of fluids, power required for
pumps and compressors, etc. Equation ( 12.75) is known as the total energy balance . For most
applications in thermodynamics, the kinetic energy and potential energy terms in Eq. ( 12.75)
are negligibly small compared with the other terms so that the equation can be written as
AH = Q - W ( 12.76 )
This equation is analogous to Eq. (12.8) developed for non-flow processes.
 Energy Balance: Thermophysics 445

12.10.1 Mechanical Energy Balance

The total energy balance considers only the input and output from the system. For fluid mechanics
calculations, it is customary to express this equation in the form of mechanical energy balance.
The mechanical energy balance takes irreversible effects such as fluid friction also into account.
From the definition of enthalpy of a fluid, we get
dH = dU + P dV + V dP [from Eq. (12.12)]
From the first law of thermodynamics [Eq. (12.54)],
dU = dQ - dW
For a reversible process, the work done by the fluid is
dW = P dV
Substituting this into Eq. (12.54) and combining the resulting equation with Eq. (12.12), we get
dH = dQ + V dP ( 12.77)
Integrate Eq. ( 12.77) between the entrance and exit points.

AH = Q + \Pl V dP
i
( 12.78 )

Utilizing this equation, Eq . ( 12.75) can be modified to the following form:

A Cp2
- Ws = — + gAZ +

^ VdP

If the changes in kinetic and potential energies are negligible, the shaft work is given by
( 12.79)

Ws = -

^ VdP

The above equations are developed assuming reversible processes. On including the work lost
due to the irreversibilities, Eq. (12.79) takes the following form :
AU ?2
+ gAZ + [ V dP + WS + F = 0
( 12.80)

( 12.81)
2 JPi
Here, F represents the lost work due to friction or mechanical energy dissipated to heat due
to irreversibilities in the system . Equation (12.81) is known as the mechanical energy balance .

12.10.2 Bernoulli’ s Equation

Bernoulli’s equation is a special form of the mechanical energy balance applicable only to non-
viscous incompressible fluids, which do not exchange shaft work with the surroundings. For
non-viscous fluids, F = 0. The integral in Eq. (12.81 ) can be evaluated if the functional
relationship between pressure and volume is known. For incompressible fluids volume is
independent of pressure, and hence
R2 AP
i. -
p
V dP = VAP =
P
( 12.82)
446 Stoichiometry and Process Calculations

where p is the density of the fluid. Since no shaft work is exchanged, Ws = 0. Using these
simplifications, Eq. ( 12.81) can be written as

Au 2
~
Y + gAZ + —APP = 0 ( 12.83 )

_
—u2 + gZ + —rP = constant ( 12.84 )

Equation (12.84) is known as Bernoulli’s equation.

EXAMPLE 12.35 Steam at 610 K and 3500 kPa is expanded in a turbine for power generation
and then condensed. The steam at a velocity of 60 m /s enters the turbine at an elevation of
7.5 m. The condensate leaves as saturated liquid at 305 K with a velocity of 0.5 m/s at an
elevation of 2 m. The work done on the turbine by steam is 800 kJ/kg, and the enthalpy of steam
in the turbine is greater than the enthalpy of the condensate by 3000 kJ/kg. Calculate the amount
of heat that is removed in the condenser per kg of steam expanded (take g = 9.81 m /s2).
Solution For a steady-state flow process we can use Eq. (12.75), i.e.

AH + gAZ + - Au 2 = Q - WS

For 1 kg of steam undergoing the specified change of state, AH = - 3000 kJ/kg.

= — 2 —2
Au U
— = 0.5
Wj — 60 .
nn
= -1799.875
„
1 o 1 T i
JT //1kg = -1.8 kJ /kg /

2 2
gAZ = 9.81 x (2 - 7.5) = - 53.955 J/kg = - 0.054 kJ/ kg
Ws = 800 kJ /kg
Heat added to the fluid in the system is

Q = AH + gAZ + - Au 2 + Ws
2
Substituting the values,
Q = - 3000 1.8 + 800 =
- 0.054 - - 2201.85 kJ/kg
Heat removed from the fluid, - Q = 2201.85 kJ/kg.

EXAMPLE 12.36 Steam flowing at 3 m/s is throttled down from 6000 kPa and 623 K to
1000 kPa by passage through an insulated needle valve. What is the temperature after expan-
sion?
Solution We can show that the throttling process is essentially a constant enthalpy
process. In the steady-state energy balance equation

AH + gAZ + - Au 2 = Q - WS
2
gAZ = 0; Q = 0; Ws = 0, so that we have
 Energy Balance: Thermophysics 447

AH + —12 A
\i
9
=0
The velocity of steam increases according to the relation u\V \ = u2v2 where ux is the velocity
and vj is the specific volume of steam at inlet, and u2 and v2 are the corresponding values at

the exit. But the contribution of the kinetic energy term —2 Au 2

is negligibly small in comparison

with the enthalpy values involved. Therefore, it is justifiable to assume

AH = 0
for the process, or throttling can be considered as a constant enthalpy process.
Enthalpy of superheated steam at 6000 kPa and 623 K = 3045.8 kJ / kg. Hence the enthalpy
of the steam leaving the throttling process is 3045.8 kJ / kg. At 1000 kPa, the temperature of
superheated steam for which this enthalpy value corresponds to is 570 K (from steam tables).

EXAMPLE 12.37 Water at 288 K is pumped from a depth of 5 m at the rate of 1.5 x 10-2
m3/min. The motor for the pump supplies work at the rate of 2 hp. Only about 60% of the
rated horsepower is available as work of pumping, and the rest is dissipated as heat. The water
passes through a heat exchanger, where it receives heat at the rate of 500 kJ/min and is
delivered to a storage tank where the level of water is maintained at an elevation of 50 m above
the ground. Heat loss from the whole system is estimated to be at a constant rate of 400
kJ/ min . What is the temperature of the water delivered to the tank ? Assume that the
specific heat of water is constant at 4.2 kJ / kg K (take g = 9.81 m /s2).
Solution Consider Figure 12.14.

- ©
*

50 m

> 500 kJ /min

2 hp

5m

Figure 12.14 Energy balance ( Example 12.37).

Point 1 is considered at the surface of water which is at a depth of 5 m from the ground
and point 2 at the storage tank. Applying the steady-state energy balance equation,
448 Stoichiometry and Process Calculations

AH + gAZ + - AU 2 = Q - WS
2
The surface at point 1 is the reference plane for estimating the potential energy. Z2 = 55 m and
Zx = 0. Therefore,
gAZ = 9.81 x 55 = 539.55 J/kg
Neglecting the kinetic energy contribution,
1 7
- Aw 2 =0
2
The flow rate of water = 1.5 x 10-2 m 3/min. Assuming a density of 1000 kg/ m3 for water, the
mass flow rate of water = 1.5 x 10-2 x 1000 = 15 kg/min. Heat supplied = 500 kJ/min; heat
lost = 400 kJ/min. Therefore, the net heat transferred to the system

Q= - r = 6666.67 J/kg
^
The work done by the pump on the unit mass of water, taking into consideration its efficiency
of 60%, is
2 x 745.7 x 0.60
15 / 60
= 3579.36 J/kg
( Note: The work done by the water is positive and the work done by the pump on the water
is negative, by the sign convention we have adopted.)

AH = Q - WS - gAZ - — Au 2 = 6666.67 + 3579.36 - 539.55 = 9706.5 J/kg

The enthalpy of water leaving is greater than the enthalpy of water in the well by 9706.5 J /kg.
Therefore, the temperature of water leaving will be greater than that of water in the well by
AT. Assuming a constant heat capacity of 4.2 kJ/kg K,
AH = 9706.5 = mCpAT = 1 x 4200 x AT
Therefore, AT = 2.31 K.
Since water is originally at 288 K, the temperature of exit water = 288 + 2.31 = 290.31 K.
EXAMPLE 12.38 Ammonium sulphate is dried from 4.0% to 0.2% moisture in a counter-
current rotary drier. Hot air at 363 K and containing 0.01 kg of water per kg of dry air admitted
at one end of the drier flows countercurrently in contact with the solids and leaves at the other
end at 305 K. The solid enters at 298 K and leaves at 333 K. The heat lost from the drier is
estimated to be at the rate of 40000 kJ/h. The heat capacity of the dry air is 1.005 kJ/kg K. The
heat capacity of water vapour is 1.884 kJ/kg K. The heat capacity of dry ammonium sulphate
is 1.507 kJ/kg K. The heat capacity of water is 4.2 kJ/kg K. The latent heat of vaporization
of water at 273 K is 2502.3 kJ/kg. Estimate the air requirement for the drier for producing
ammonium sulphate product at the rate of 1000 kg/h.
Solution Basis: 1000 kg/ h of dried product
 Energy Balance: Thermophysics 449

Let S kg be the amount of dry solid in the product stream. Since the product contains 0.2%
moisture,
5 = 1000( 1 - 0.002) = 998 kg
This remains constant in the solid stream as only water is removed from the solid on drying.
Heat loss
40,000 kJ/h

Ammonium sulphate, 1000 kg/ h

Ammonium sulphate
0.2 % moisture, 333 K
4% moisture , 298 K

Air, 305 K Hot air, 363 K

Y 2 kg moisture/kg dry air 0.01 kg moisture/kg dry air
Figure 12.15 Energy balance on rotary dryer (Example 12.38).

Let Xx be the moisture content in weight ratio in the entering solid and X2 that in the exit
solid. Then
4
Xx = — = 0.0417 kg water per kg dry solid
0.2
X2 = 99.8 = 0.002 kg water per kg dry solid
Let G be the weight of dry air in the air stream passing through the drier which is constant
throughout the dryer. Let Yx be the humidity in the air entering the drier and Y2 be the humidity
in the air leaving the drier. Y ] = 0.01 kg water per kg dry air.
The enthalpies of the streams entering and leaving the drier can now be calculated. A datum
temperature of 273 K is assumed for enthalpy calculation.
Enthalpy of solid entering the drier,
Hsi = ( CP + XxCw ){ Tx - T0 )
= (1.507 + 0.002 x 4.2) x (298 - 273) = 37.89 kJ/kg of dry solid
Enthalpy of solid leaving the drier,
Hs2 = ( CP + X2CW )( T2 - T0 )
= (1.507 + 0.0417 x 4.2) x (333 - 273) = 100.93 kJ/kg of dry solid
Enthalpy of wet air can be evaluated as
HG = CS( TG - T0 ) + Yko
where Cs is the humid heat of air, TG is the temperature of air and X 0 is the latent heat of
vaporization of water at T0 .
Cs = 1.005 + 1.8847
where 7 is the humidity of air. For air entering the drier,
450 Stoichiometry and Process Calculations

HGX = ( 1.005 + 1.884 x 0.01)(363 - 273) + 2502.3 x 0.01 = 117.17 kJ/kg dry air
For exit air, the enthalpy is
HG 2 = ( 1.005 + 1.884 x 7)(305 - 273 ) + 2502.3 x 7 = 32.16 + 2562.597 kJ/kg dry air
Taking an enthalpy balance on the drier,
AH = Q (A)
where AH is the difference in enthalpy between the stream leaving the drier and the streams
entering the drier and Q is the heat supplied to the drier. Here, Q = - 40 000 kJ/h.
Enthalpy of streams entering the drier is
Hx = SHsl + GHGX = 998 x 37.89 + G x 117.17 = 37,814.22 + 117.17 G
Enthalpy of streams leaving the drier
H2 = SHsl + GHG 2 = 998 x 100.93 + G(32.16 + 2562.597)
= 100 728.14 + G(32.16 + 2562.59 7)
AH = H 2 - Hx = 629 13.92 + G(- 85.01 + 2562.597)
Substituting this in Eq. (A ),
62 913.92 + G(- 85.01 + 2562.597) + 40 000 = 0
or
102 913.92 + G(-85.01 + 2562.59 7) = 0 (B )
A moisture balance on the drier gives

SXx + G 7j = SX2 + G 72
998(A , - X2 ) = G( 7 - 0.01)
or
998(0.0417 - 0.002) = G( 7 - 0.01)
which on simplification gives
G( 7 - 0.01) = 39.62 (C )
Equations (B) and (C ) are solved simultaneously to obtain G, the circulation rate of dry air, i.e.
G = 3443 kg/h.
Since the air supplied contains 0.01 kg of water vapour per kg of dry air, the rate at which
wet air is supplied is
G(1 + 0.01) = 3477.4 kg/h

EXAMPLE 12.39 A solution of 10% (weight) acetone in water is subjected to fractional

distillation at a rate of 1000 kg/ h to produce a distillate containing 90% acetone and a bottom
product containing not more than 1% acetone. The feed enters at 340 K, distillate and residue
leave the tower at 300 K and 370 K respectively. A reflux ratio (ratio of the weight of reflux
to the weight of distillate product) of 8 is employed. The rise in temperature of 30 K is
permitted for the cooling water circulated in the condenser employed for condensing the
 Energy Balance: Thermophysics 451

vapours into the distillate product and the reflux. Saturated steam at 276 kPa is available for
supplying the heat of vaporization in the reboiler.
Heat losses from the column may be neglected. The heat capacity of acetone is 2.2 kJ/kg K
and that of water is 4.2 kJ/ kg K. The boiling point of 90% acetone-water solution is 332 K.
The latent heat of acetone at 332 K is 620 kJ /kg and that of water is 2500 kJ/kg. The latent
heat of steam at 276 kPa is 2730 kJ/kg. Calculate the following:
(a) The cooling water circulation rate
(b) The rate of circulation of steam
Solution Basis: 1000 kg/h of feed solution.
Refer to Figure 12.16.

Condenser

Distillate , D kg/h
90 % acetone ,
300 K

Reflux , L = 8 D kg/ h
Feed , F = 1000 kg/h
340 K , 10 % acetone >

4-

Residue , W kg /h
>> m > < 1 % acetone, 370 K
Reboiler
Sat. steam 276 kPa
Figure 12.16 Energy balance on the fractionator (Example 12.39).

Let F, D, and W be the mass of feed distilled, mass of distillate and bottom product
produced in one hour. Let xF , xD and xw be the weight fractions of acetone in the feed, distillate
and the residue respectively. The total material balance is:
F= D + W
Acetone balance is:
FXF = DXD + Wxw
Here, F = 1000, xF = 0.10, xD = 0.90 and xw = 0.01. Substitute these values in the above
equations and solve the resulting equations for D and W . Hence, we get D = 101.12 kg/h and
W = 898.88 kg/h.
(a) The reflux ratio

R= — =8
D
452 Stoichiometry and Process Calculations

Therefore,
L = SD = 808.96 kg/h
Taking a total material balance around the condenser,
G = L + D = 808.96 + 101.12 = 910.08 kg/h
where G is the vapour reaching the condenser from the column. This is the quantity
of vapour condensed to saturated liquid at 332 K and further cooled to 300 K to be
taken as distillate and reflux.
The latent heat of condensation of the vapour is
X = 0.9 x 620 + 0.1 x 2500 = 808 kJ / kg
The heat capacity of the liquid is
CP = 0.9 x 2.2 + 0.1 x 4.2 = 2.4 kJ/kg K
Thus, heat given out by the condensation and cooling of 1 kg of vapour reaching the
condenser is
X + CP( 332 - 300) = 808 + 2.4 x 32 = 884.8 kJ/ kg
Taking an enthalpy balance on the condenser, we have, in the absence of heat losses,
heat given out by the condensation of vapour = heat absorbed by the cooling water
910.08 x 884.8 = mcCPcAT
where mc is the rate of circulation of cooling water, CPc is its specific heat and AT is
the allowable temperature rise of the cooling water. CPc = 4.2 kJ/kg K and AT = 30 K.
Solving the heat balance equation, mc = 6390.8 kg/h.
The rate of circulation of cooling water = 6390.8 kg/h.
(b) Denoting the heat removed in the condenser in unit time by Qc, the heat added in the
reboiler through steam by QB, the enthalpies of the distillate and the residue to be HD
and Hw respectively, we have the energy balance for the column as
FHF + QB = DHD + WHw + Qc
In the above equation, Qc = 910.08 x 884.8.
Taking 300 K to be the reference temperature for evaluating the enthalpy,

HD = enthalpy of distillate = 0
Hw = CPW (370 - 300) = (0.01 x 2.2 + 0.99 x 4.2) x 70 = 292.6 kJ/kg
HF = CPF (340 - 300) = (0.1 x 2.2 + 0.9 x 4.2) x 40 = 160 kJ/kg
Substituting these values in the energy balance equation
QB = DHD + WHw + Qc - FHF
= 0 + 898.88 x 292.6 + 910.08 x 884.8 - 1000 x 160
= 908 251.07 kJ/h
This is the heat that is to be supplied to the reboiler by the condensation of steam. The
heat of condensation of steam is 2730 kJ/kg.
 Energy Balance: Thermophysics 453

Therefore, the amount of steam supplied is

908 251.07
2730
= 332.69 kg/h

EXERCISES
Components of energy balance equations
12.1 The potential energy of a body of mass 20.0 kg is 3.5 kJ. What is the height of the
body from the ground? If a body of mass 20 kg is moving at a velocity of 50 m/s,
what is its kinetic energy?
12.2 Nitrogen gas, 0.1 cubic metres in volume, is confined in a cylinder at a pressure of
200 kPa and a temperature of 300 K is expanded at constant temperature to double its
volume. What is the work done by the gas on the piston? Assume that nitrogen behaves
as an ideal gas.
12.3 A man circling the earth in a spaceship weighed 300 N at a location where the local
gravitational acceleration was 3.35 m /s2. Calculate the mass of the man and his weight
on the earth where the gravitational acceleration is 9.81 m/s2.
12.4 A spherical balloon of diameter 0.5 m contains a gas at 1 bar and 300 K. The gas is
heated and the balloon is allowed to expand. The pressure inside the balloon is found
to vary linearly with the diameter. What would be the work done by the gas when the
pressure inside reaches 5 bar.
12.5 A car having a mass of 1200 kg is running at a speed of 60 km /h. What is the kinetic
energy of the car in kJ? What is the work to be done to bring the car to a stop.
12.6 A body of mass 50 kg is lifted through a distance of 15 m . What is the work done?
If it took 2 min for lifting the mass, calculate the power.
12.7 A 100-kg ball initially at a height of 15 m is dropped to the ground .
(a ) Find the initial potential energy and kinetic energy of the ball.
(b) Find the final potential energy and kinetic energy of the ball .
(c ) If the initial potential energy is converted to heat and the entire heat is transferred
to 100 kg of water, what would be the temperature rise of water?
12.8 A man whose weight is 700 N takes 2.5 minutes for climbing up a staircase. What is
the power developed in him, if the staircase is made up of 20 stairs, each 0.18 m in
height?
12.9 A balloon filled with hydrogen lifts a mass of 150 kg including its own mass. If the
density of hydrogen is 0.09 kg/m 3 at the prevailing conditions, what would be the
volume of the balloon?
12.10 Nitrogen gas is confined in a cylinder and the pressure of the gas is maintained by a
weight placed on the piston. The mass of the piston and the weight together is 100 kg.
The acceleration due to gravity is 9.81 m /s2 and the atmospheric pressure is 1.01325
bar. Assume that the piston is frictionless. Determine the following:
454 Stoichiometry and Process Calculations

( a ) The force exerted by the atmosphere, the piston and the weight on the gas if the
piston is 200 mm in diameter
(b) The pressure of the gas
(c ) If the gas is allowed to expand pushing up the piston and the weight by 500 mm ,
what is the work done by the gas in joules?
(d ) What is the change in the potential energy of the piston and the weight after the
expansion in part (c)?
12.11 A body of mass 20 kg is dropped from a height of 15 m. What is the potential energy
of the body at the time of its release? Assume that the potential energy gets converted
into kinetic energy when the body strikes the ground . At what velocity does it strikes
the ground?
12.12 Water at a rate of 1 x 10-3 m3/s is pumped from a storage tank into a tube of 30 mm
diameter.
(a ) Determine the kinetic energy of water in J/kg.
(b) If the water is discharged into a tank at a height of 15 m , what is the increase in
the potential energy of water from that in the original tank ?
12.13 A spherical balloon of diameter 0.5 m contains a gas at 1 bar and 300 K. The gas is
heated and the balloon is allowed to expand . The pressure inside the balloon is directly
proportional to the square of the diameter. What would be the work done by the gas
when the pressure inside reaches 5 bar?
12.14 The steam supplied to an engine liberates 5000 J of heat . If the engine efficiency is
only 40 percent, to what height a body of mass 10 kg can be lifted using the work
output from the engine?
12.15 A vertical cylinder is separated into two compartments by means of a piston , the
compartments being filled with two different gases. If the whole cylinder were filled
with any one of these gases, it would support a pressure equal to three eighth of the
weight of the piston. What would be the position of the piston separating the two gases?
12.16 A balloon which was originally empty is being filled by hydrogen from a cylinder at
a constant temperature of 300 K. The atmospheric pressure is 1.01325 bar. What is the
work done by the balloon-cylinder system when the balloon attains a spherical shape
with a diameter of 6 m?
12.17 Five kilograms of C02 gas is contained in a piston-cylinder assembly at a pressure of
7.5 bar and a temperature of 300 K. The piston has a mass of 6000 kg and a surface
area of 1 m2. The friction of the piston on the walls is significant and cannot be
ignored. The atmospheric pressure is 1.01325 bar. The latch holding the piston in
position is suddenly removed and the gas is allowed to expand. The expansion is
arrested when the volume is double the original volume. Determine the work appearing
in the surroundings.
12.18 An elevator is initially resting at a height of 7.5 m above the base of the elevator shaft .
It is then raised to a level of 75 m above the base when the cable holding it breaks.
It falls freely to the base where it is brought to rest by a strong spring . The mass of the
 Energy Balance: Thermophysics 455

elevator is 2500 kg and the acceleration due to gravity is 9.81 m/s2. Neglecting the
effect of friction, calculate
(a ) The potential energy of the elevator in its initial position
(b) The potential energy of the elevator in its highest position
(c ) The work done in raising the elevator
(d ) The kinetic energy and velocity of the elevator just before it strikes the spring
(e) The potential energy of the spring when the elevator rests on it
12.19 Water is being vaporized by passing an electric current of 0.5 A from a 12 V supply
through a resistance immersed in saturated water at atmospheric pressure . If the
current is passed for 5 minutes and water evaporated is 0.798 g, calculate the change
in molar internal energy and molar enthalpy during this process. Assume that the water
vapour behaves ideally.
12.20 Liquid C02 at 233 K has a vapour pressure of 1.005 x 103 kPa and a specific volume
of 0.9 x 10-3 m3/kg. Assume that C02 is a saturated liquid at these conditions and its
enthalpy is zero. The latent heat of vaporization of C02 is 320.5 kJ /kg and the specific
volume of saturated vapour is 38.2 x 10-3 m3/kg. Calculate the internal energy of
saturated liquid and both internal energy and enthalpy of saturated vapour.
12.21 A gas expands from an initial volume of 0.2 m3 to a final volume of 0.4 m 3 in a
reversible steady flow process. During the process the pressure varies as
P=5x 105 F + 7 x 104
where P is in N/ m and V is in m . The inlet line is 4 m below the outlet line, and the
2 3

gas enters with a negligible velocity. The internal energy of the gas decreases by 30 kJ
during the process. Determine the heat transferred.
12.22 Liquid water at 373 K and 101.3 kPa has an internal energy of 420 kJ/kg on an
arbitrary basis. The specific volume at these conditions is 1.04 x 10-3 m3/ kg . The
water is brought to the vapour state at 473 K and 700 kPa . At this condition , its
specific volume is 0.3 m 3/kg and its enthalpy is 2844 kJ/kg. Calculate the enthalpy of
the liquid and the changes in internal energy and enthalpy accompanying the vaporization
process.
12.23 A sample of 10 g of liquid benzene at its boiling point is vaporized using a 12 V, 0.5 A
electric supply. The normal boiling point and the latent heat of vaporization of benzene
are 353.2 K and 30.8 x 103 kJ/kmol respectively. Determine
( a ) The change in internal energy
( b) The time required for complete vaporization

Heat capacities
12.24 The heat capacity of carbon dioxide gas is given by
3 6
CP = 26.540 + 42.454 x 10 "

T - 14.298 x 10 “

T2
where CP is in J/mole K and T in K.
(a ) Find the amount of heat needed to heat one mole from 350 to 450 K.
(b) Find the constants for CP in cal/mol °C and T in °C.
456 Stoichiometry and Process Calculations

12.25 Carbon dioxide has a molal heat capacity of CP = 26.54 + 42.454 x 10 3 T - 14.298
x 10-6 T 2 where Cp is in J/mol K and T in K .
(a ) Calculate the heat capacity at 400 K.
(b) Calculate the mean heat capacity between 400 and 300 K .
(c ) Calculate the heat requirement for heating 88 kg of the gas from 300 K to 400 K.
12.26 The molal heat capacity of C02 gas is given by
CP = 26.540 + 42.454 x 10 3
"

r - 14.298 x 10 6
~
T2
where CP is in kJ/kmol K and T in K. Calculate the following:
(a ) The mean molal heat capacity between 500 and 1000 K
( b) The heat required to raise the temperature of 200 m3 per hour of C02 gas at STP
from 500 to 1000 K.
12.27 A 5 kg mass of a gas undergoes a process in which its temperature rises from 10°C
to 30°C. The specific heat of the system is
262.9
CP = 3.505 +
T
where CP is in kJ/kg K and T is in K. Determine the following:
(a ) The heat interaction
( b) The mean heat capacity of the system
12.28 The heat capacity of HC1 for the temperature range of 300 to 1500 K is given by
CP = 28.194 + 1.805 x 10-3 r + 1.513 x 10-6 r 2
where CP is in kJ/kmol K and T in K . Calculate the following:
(a ) The mean heat capacity at 1300 K with reference to 300 K
( b) The enthalpy change of HC1 when it is heated from 300 K to 1300 K
12.29 Determine the specific heat of a gas at 800 K for which CP varies with temperature
as CP = a + bT + cT 2 where a , b and c are constants. The following data are available.

T ( K) 300 600 900

CP (kJ/kmol K) 28.788 30.417 32.033

12.30 The heat capacity of ethylene gas at different temperatures are given below.
T (K) 298 500 700 1000
CP (J/mol K) 43.6 63.5 78.5 94.5

( a ) Fit the data into an equation of the form CP = a + bT + cT 2.

( b ) Calculate the heat required to raise the temperature of one mole of ethylene gas
from 400 to 1000 K.
12.31 Calculate the amount of heat given off when 5 m3 of S03 gas at STP cools from 773 K
to 400 K at a constant pressure of 101 kPa. The heat capacity is given as CP = a + bT
+ cT 2 where a , b and c are constants. The values of the constants are : a = 34.33,
b x 103 = 42.86 and c x 106 = - 14.298. CP is in kJ/kmol K and T in K .
 Energy Balance: Thermophysics 457

12.32 The heat capacity of silicon carbide is given by

CP = 37.221 + 1.22 x 10-2 r - 1.189 x lO5 -2
^
where CP is in kJ /kmol K and T is in K. Estimate the following:
(a ) The mean heat capacity of silicon carbide in the range of 0 to 1000°C
( b) The enthalpy change in silicon carbide in the temperature range between 0 to 1000°C
12.33 A gas mixture contains species A (MW=30) 15%, species B (MW = 45) 45% and
species C (MW = 80) 40% by weight. Calculate the quantity of heat necessary to heat
one kilomole of the mixture from 300 K to 2700 K. The constants of the molar heat
capacity equation CP = a + bT + cT 2 are as follows where CP is in kJ / kmol K and T
is in K.

Species a b c x 103
A 25 0.05 - 0.01
B 30 0.009 - 0.05

C 21 0.08 - 0.001

12.34 The gas leaving a pyrites roaster in a sulphuric acid plant has the following compo-
sition. S02 = 7.00%, 02 = 10.50%, S03 = 0.80%, N 2 = 81.70%. The heat capacity
of the gases varies with temperature as given below where CP is in kJ /kmol K and T
is in K.
02: CP = 25.74 + 12.987 x 10 3 T - 3.864 x 10 6 T2
" "

N2: CP = 27.03 + 5.815 x 10 3 r - 0.289 x 10-6 r 2

~

S03: CP = 34.33 + 42.86 x 10 3 r - 14.298 x 10 6 r 2

- -

S02: CP = 25.74 + 57.96 x 10 3 r - 38.11 x 10 6 r 2

- "

Calculate the enthalpy of the gas mixture at 750 K with reference to a base temperature
of 298 K .
12.35 The analysis of natural gas showed the following: Methane, 40.00%; Hydrogen , 40%;
carbon monoxide, 4.0%; carbon dioxide, 3.0%; oxygen, 2.0% and the rest nitrogen. A
1-kw heater is used to supply heat to the gas so that its temperature increases by 0.2°C.
Estimate the flow rate of the gas in cubic metres per minute at 300 K and 100 kPa . The
specific heats of the gases in kJ/kmol K are 35.91 for methane, 28.95 for hydrogen,
29.25 for carbon monoxide, 37.31 for carbon dioxide, 29.47 for oxygen and 29.24 for
nitrogen.

Enthalpy change of phase changes

12.36 One kg of ice at 273 K and 5 kg of water at 300 K are mixed and kept in an open
container till all the ice melts and the temperature of the mixture becomes 295 K. Given
that the heat of fusion of ice is 335 kJ/kg, calculate the heat added or removed to or
from the water and ice.
12.37 One kilogram of ice at 0°C is heated so that it is completely converted to steam at
150°C and 101.3 kPa. What is the enthalpy change accompanying the process?
458 Stoichiometry and Process Calculations

The heat of fusion of water at 101.3 kPa and 0°C is 335 kJ /kg and heat of
vaporization of water at 101.3 kPa and 100°C is 2256 kJ / kg. The heat capacity
equation of liquid water is
CP = 18.296 + 47.212 x 10-2 r - 133.88 x 10-5 r 2 + 1314.2 x 10 "
9 r3
and the heat capacity equation of water vapour at 101.3 kPa is
CP = 30.475 + 9.652 x 10 3 T + 1.189 x 10 6 T 2
" "

where T is in K and specific heat is in (kJ/kmol K ).

12.38 The vapour pressure of water at 473 K is 1554.3 kPa . The normal boiling point of
water is 373 K. Determine the latent heat of vaporization of water assuming that it is
independent of temperature.
12.39 The vapour pressure of ethyl ether at 273 K is 25 kPa and at 293 K is 63.5 kPa.
Estimate the latent heat of vaporization of ether in kJ/kg in this temperature range.
12.40 Using the Watson equation, calculate the latent heat of vaporization of ^ -butane at
373 K given that the heat of vaporization at the normal boiling point of 272.7 K is
385 kJ /kg. The critical temperature of ^ -butane is 425 K .
12.41 Using Trouton's rule, find the approximate heat of vaporization of benzene boiling at
80°C.
12.42 The vapour pressure of zinc is given by the Clapeyron equation
6160
log Psc = — + 8.1

where pressure is in mm Hg and temperature is in K . Estimate the heat of vaporization

of zinc at the normal boiling point of 1180 K, and compare the result with the value
estimated using the Kistyakowsky equation.
12.43 Calculate the enthalpy of zinc vapour at 1500 K and standard atmospheric pressure with
reference to the solid at 273 K. The melting point and the boiling point of zinc at
atmospheric pressure are 592 K and 1180 K respectively. The mean heat capacity of
the solid between 273 K and 592 K = 0.441 kJ/kg K; the mean heat capacity of liquid
= 0.458 kJ/kg K; the mean heat capacity of the vapour from 1180 K to 1500 K =
20.874 kJ/ kg K; the heat of fusion = 6972 J/g -atom. Use the Kistyakowsky equation.
12.44 Methyl chloride is obtained from the vapour-phase catalytic reaction between methanol
and hydrogen chloride. The liquid methanol is vaporized in a separate vaporizer, and
the vapours are continuously mixed with HC1 gas in equimolar proportions. The mixed
gases are preheated in a tube furnace to 200°C before entering the catalytic reactor. The
heat capacity of liquid methanol 2.62 kJ/kg K . The mean heat capacity of methanol
vapour is 53.47 kJ/kmol K. The mean heat capacity of HC1 gas is 41.70 kJ/kmol K. The
normal boiling point of methanol is 337.9 K. The heat of vaporization of methanol at 101.3
kPa is 35.3 kJ/mol. On the basis of 400 kg/h of alcohol feed at 25°C, find the following:
(a ) The heat duty of methanol vaporizer operating at one standard atmosphere
(b) The heat duty of the tube furnace if the methanol vapour enters saturated at 1 atm,
the HC1 enters at 30°C, no chemical reaction occurs in the furnace, and heat losses
are negligible.
 Energy Balance: Thermophysics 459

12.45 The following table gives the vapour pressures of benzene and water. Plot the reference
temperature vapour pressure curve with the logarithm of vapour pressure of benzene on
the y-axis and the logarithm of vapour pressure of water on the Jt-axis.

T (K ) 288.6 299.3 315.4 333.8 353.3 377.0 415.7 452

PB (kPa) 8.0 13.3 26.7 53.3 101.3 202.7 506.6 1013.0
Pw (kPa) 1.8 3.4 8.3 26.1 49.0 116.3 382.5 980.0

( b ) Determine the vapour pressure of benzene at 373 K.

(c ) Determine the latent heat of vaporization of benzene at 298 K given that the latent
heat of vaporization of water at 298 K is 2443 kJ /kg . Compare your result with
the experimental value of 434 kJ/kg .

Steam tables
12.46 A steam-jet ejector is used to entrain saturated water vapour at 25 kPa { H = 2618.2 kJ/kg)
leaving an evaporator by high pressure saturated steam at 1000 kPa ( H = 2778.1 kJ/kg).
It is estimated that with every kilogram of high-pressure steam, 0.75 kg of the vapour
from the evaporator can be entrained. If the mixed stream leaving the ejector is at
100 kPa what is its temperature?
12.47 A valve on a well-insulated steam pipe carrying saturated steam at 1000 kPa is found
leaking. The temperature of the steam escaping from the leak is measured to be 398 K.
Determine the quality of steam flowing through the pipe.
The following data are taken from steam tables: the enthalpy of saturated vapour at
1000 kPa =2778 kJ/ kg, the enthalpy of saturated liquid at 1000 kPa = 763 kJ / kg and
the enthalpy of superheated steam at 398 K and 101.3 kPa = 2726 kJ/kg.
12.48 Wet steam containing 5% by weight of liquid at a pressure of 500 kPa is mixed at a
rate of 1 kg/s with superheated steam at 500 kPa and 473 K { H = 2855 kJ /kg ) to obtain
dry saturated steam at 500 kPa ( Hx = 640 kJ/kg; Hv =2749 kJ/ kg ). Determine the rate
of addition of superheated steam if mixing is done adiabatically.
12.49 An evacuated tank is connected to a pipe carrying steam at 1400 kPa and 598 K
(enthalpy = 3097 kJ/kg) through a valve. The valve is opened and the tank fills with
steam until the pressure is 1400 kPa, and then the valve is closed . Assume that the
process is adiabatic and the kinetic and potential energies are negligible. Determine the
final temperature of the steam.
12.50 Using steam tables, find the enthalpy change when (a) one kilogram of water is heated
from 293.15 to 323.15 K at 101.3 kPa and (b) when one kilogram of water at 293.15
K is heated and vaporized at 200 kPa.
12.51 A closed tank contains 10 kg of water in equilibrium with 2 kg of steam at 349 K. Heat
is added until 8 kg of the water is vaporized.
( a ) What was the original pressure?
( b ) What is the final pressure?
( c ) How much heat was added?
460 Stoichiometry and Process Calculations

12.52 A mixture of saturated steam and saturated water is contained in a rigid tank of volume
0.1 m3 at a pressure of 2 bar. The liquid occupies 10% of the total volume. How much
heat must be added in order that the tank contains only saturated steam? What will be
the pressure in the tank?
12.53 A steam boiler is one-fourth filled with liquid water at 101.3 kPa and 373.15 K and
three-fourth filled with steam. If it is brought to a pressure of 6817 kPa with all the
valves closed, how much heat must be supplied in kJ per kilogram of water in the
boiler?
12.54 A vessel of volume 1 m 3 initially contains one percent by volume saturated liquid water
and the rest saturated vapour at 1 bar. How much heat is to be supplied so that the
vessel gets filled with vapour?
12.55 A steam boiler of volume 2.3 m 3 initially contained 1.7 m3 liquid water in equilibrium
with 0.6 m3 of vapour at 100 kPa. The boiler is heated keeping the inlet and discharge
valves closed. The relief valve is set to lift when the pressure in the boiler reaches
5500 kPa. Determine the amount of heat supplied to the contents in the boiler before
the relief valve lifts.
12.56 A cylinder fitted with a piston has a volume of 0.1 m 3 and contains 0.5 kg of steam
at 500 kPa. How much heat is to be supplied to bring the temperature of the steam
to 823 K, keeping the pressure constant? What is the work done in the process?

Heat of mixing
12.57 Fifty kilograms of NH 4N03 is dissolved in 108 kg of water at 298 K. Find (a) the heat
absorbed if the process is isothermal and (b) the temperature of the mixture if the
dissolution is carried out adiabatically. Take the heat capacity of the mixture to be 3.35
kJ/kg K.
12.58 The heat of formation of LiCl is - 408.610 kJ /mol at 298 K. The heat of solution for
1 mol LiCl in 12 mol water is - 33.614 kJ at 298 K . Calculate the heat of formation
of LiCl in 12 mol water at 298 K.
12.59 One hundred kilograms of pure H2S04 is mixed with 110 kg of water at 25°C and
101.3 kPa. Calculate the following:
( a ) The heat evolved under isothermal conditions
( b) The final temperature of the mixture if it was formed under adiabatic conditions.
Assume the heat capacity of the final mixture is 2.5 kJ/kg K.
12.60 What temperature will be attained when a 20 mole percent ethanol-water mixture is
adiabatically formed from the pure liquids at 298 K ? The heat of mixing for 20 mole
percent ethanol-water at 298 K is - 758 J/mol . The mean heat capacity of a 20 mole
percent solution of alcohol in water at 298 K is 97.65 J/mol K.
12.61 A solution of NaOH in water is prepared by diluting a concentrated solution in an
agitated, jacketed vessel. 2500 kg of 5% NaOH solution is prepared by diluting 50%
NaOH solution. If the concentrated solution is available at 298 K and the solution
discharged is also at 298 K, calculate the heat removed by the cooling water.
 Energy Balance: Thermophysics 461

Heat of solution varies with concentration as:

mol H 20/mol NaOH 2 4 5 10 <*>

AHS , kJ/mol NaOH - 22.9 - 34.4 - 37.7 - 42.5 - 42.9

12.62 Water at a rate of 54 x 103 kg/h and Cu(N03)2 - 6H20 at a rate of 64.8 x 103 kg/h are
mixed together in a tank. The solution is then passed through a heat exchanger to bring
the temperature to 298 K, same as the components before mixing. Determine the rate
of heat transfer in the exchanger. The following data are available. The heat of formation
at 298 K of CU( N03)2 is - 302.9 kJ and that of Cu(N03)2 - 6H20 is - 2110.8 kJ . The heat
of solution of Cu(N03)2 « H20 at 298 K is - 47.84 kJ per kmol salt and is independent
of n .
12.63 Hydrogen chloride gas at 373 K containing 10% (weight) water vapour is absorbed in
25% hydrochloric acid at 313 K yielding 28% (weight) acid . The enthalpy of HC1 gas
at 373 K is 2065 J/kg and the enthalpy of the 25% acid at 313 K is 163 J /kg. Calculate
the enthalpy of product.
12.64 If pure liquid H 2S04 is added to pure water both at 300 K to form a 20 per cent
(weight) solution, what is the final temperature of the solution? The heat of solution of
sulphuric acid in water is H 2S04 (21.8 H20) = - 70 x 103 kJ/kmol of sulphuric acid.
The standard heat of formation of water is - 286 kJ /mol.
12.65 LiCl - H20(c ) is dissolved isothermally in enough water to form a solution containing
5 mol of water per mole of LiCl. What is the heat effect? The following enthalpies of
formation are given:
LiCl(c ) = - 409.05 kJ , LiClH20(c) = - 713.054 kJ
LiCl (5 H 20) = - 437.232 kJ, H20(1) = - 286.03 kJ
12.66 1000 kg/h of FeS04 - 7H 20 crystals are to be produced in a Swenson-Walker crystal-
lizer by cooling a saturated solution at 323 K (solubility is 140 parts FeS04 - 7H20 per
100 parts water) to 300 K (solubility is 74 parts FeS04 - 7H 20 per 100 parts water ).
The feed solution has an average specific heat of 2.93 kJ/kg K . The heat of solution
of FeS04 - 7H20 at 300 K is -18 400 kJ/kmol. How much heat is evolved during the
process?
12.67 Calculate the heat effects when 1.0 kmol of water is added to a solution containing
1.0 kmol sulphuric acid and 3.0 kmol of water. The process is isothermal and occurs
at 298 K.
Data: Heat of mixing for H2S04(3H20) = - 49 000 kJ per kmol H 2S04. Heat of
mixing for H 2S04( 4H20) = - 54 100 kJ per kmol H 2S04.
12.68 A single-effect evaporator is used to concentrate a 15 percent (weight) solution of LiCl
in water to 40 percent. The feed enters the evaporator at 298 K at the rate of 2 kg/s.
The normal boiling point of a 40 percent LiCl solution is 405 K and its specific heat
is 2.72 kJ/kg K. For what heat transfer rate in kJ /h, should the evaporator be designed?
462 Stoichiometry and Process Calculations

The heat of solution of LiCl in water per mole of LiCl at 298 are:
AHs for LiCl (13.35 H20) = - 33.8 kJ, for LiCl (3.53 H20) = - 23.26 kJ, the enthalpy of
superheated steam at 405 K = 2740.3 kJ/kg, the enthalpy of water at 298 K = 104.8 kJ/
kg, and the molecular weight of LiCl = 42.39.

Energy balance in non-flow processes

12.69 A gas mixture consists of 60% methane and 40% nitrogen. Calculate the heating value
of this mixture when it is metered at 300 K and 105 kPa if the partial pressure of water
vapour in the gas is 4 kPa. The calorific value of methane gas is 40000 kJ/m 3 measured
at standard temperature and pressure.
12.70 Sulphur dioxide is circulated as the refrigerant in a small refrigerator. S02 gas at a
pressure of 5 bar and a temperature of 340 K is to be cooled at a constant volume of
0.142 m 3, to 293 K as part of the refrigeration cycle. Calculate
(a ) The heat liberated
( b ) The work done by the gas on cooling
(c ) The final pressure attained on cooling
(d ) The change in enthalpy
Sulphur dioxide may be treated as an ideal gas. The specific heat (J/mol K ) is found
to vary with temperature ( K) according to
CP = 25.736 + 5.796 x 10 2 T - 3.8112 x 10
" "
5 r2 + 8.612 x 10 9 T 3
"

12.71 10 kg of an equimolar mixture of CO and H 2 at 1500 K and 1 bar is cooled at constant

pressure to 350 K. Assuming that the gases are ideal determine the following:
( a ) The heat given off during cooling,
( b) The change in internal energy,
(c ) The work done on the gas
The specific heats in J/mol K are as follows:

CP ll = 29.086 - 8.3694 x
2
lO^ T + 2.0130 x 10 ~
r
6 2

Cpco = 26.553 + 7.6882 x 10-3 r - 1.1727 x 10-6 r2

12.72 One cubic metre of an ideal gas is confined in a cylinder provided with a frictionless
piston at 300 K and 250 kPa. The gas is allowed to expand till its volume is doubled
in a process occurring (a) at constant pressure and (b ) at constant temperature.
Calculate the work done by the gas on the piston in the above processes.
12.73 Consider 1 kg of water in a waterfall which is flowing down from a height of 100 m.
At the bottom of the fall, it joins a river whose downstream velocity may be assumed
negligible. Neglecting any energy exchange between the water and the surroundings,
calculate
(a ) The potential energy at the top of the falls
(b) The kinetic energy just before the water strikes the bottom
(c ) The change in temperature of the water when it enters the river.
 Energy Balance: Thermophysics 463

12.74 A car riding downhill at a speed of 20 m/s was applied brake when it was at a height
of 30 m vertically above the bottom of a hill. When the car comes to a halt at the bottom
of the hill, how much energy as heat must be dissipated by the brakes, if wind and other
frictional effects are neglected? The car weighed 1400 kg.
12.75 A system consisting of a gas confined in a cylinder is undergoing the following series
of processes before it is brought back to the initial conditions:
Step 1. A constant pressure process when it receives 50 J of work and gives up 25 J
of heat.
Step 2. A constant volume process when it receives 75 J of heat .
Step 3. An adiabatic process.
Determine the change in internal energy during each step and the work done during the
adiabatic process.
12.76 A 10-g lead ball at 300 K is dropped from a height of 10 m. Calculate (a) the kinetic
energy and speed of the ball as it reaches the ground and (b) the temperature rise of
the ball if all its kinetic energy is transformed into internal energy as the ball is suddenly
stopped after 10 m, given that the specific heat of lead is 125.6 J /kg K and its volume
change is negligible.
12.77 ( a ) Three kmol nitrogen gas (CP = 29.1 kJ/kmol K and Cv = 20.8 kJ/kmol K ) at 350 K
is taken in a rigid container and is heated to 550 K . How much heat must be
supplied if the mass of the vessel is 100 kg and its specific heat is 0.5 kJ/kg K?
( b ) Two kmol nitrogen is taken in a piston/cylinder arrangement at 500 K . Determine
the quantity of heat extracted from the gas to cool it to 350 K at constant pressure
if the heat capacity of the container is negligible.
12.78 An insulated rigid container contains air at 5 bar and 375 K . The volume of the
container is 1 m 3. Air may be assumed to behave as an ideal gas. The specific heat Cv
of air is 20.785 kJ /kmol K. The temperature of the air is increased by a rotating paddle
wheel. Calculate the work done to rise the temperature of the air to 425 K.
12.79 100 m 3 of C02 initially at 423 K and 50 bar is to be isothermally compressed in a
frictionless piston and cylinder device to a final pressure of 300 bar. Write a general
expression for the energy balance for the gas within the piston and cylinder device as
the system and define all terms. Also calculate the heat flow on compression .
12.80 A 14-m3 storage tank contains 13 m 3 liquid oxygen in equilibrium with its vapour at
100 kPa. The tank is provided with a pressure relief valve which is set at 250 kPa.
(a ) Determine the mass of total material in the tank and (b) the fraction of the total
material that is vapour (c) When will the pressure relief valve operate if heat leaks into
,

the tank at the rate of 5000 kJ/h? The specific volume of gas and liquid oxygen at
100 kPa are, respectively, 7.15 m3/kmol and 2.81 x 10 2 m 3/kmol . The enthalpies are
~

- 133.5 kJ/kg and - 116.6 kJ / kg at 100 kPa and 250 kPa respectively.

12.81 One kmole of an ideal gas is originally at 300 K and 1 bar. It is then heated at constant
pressure to a temperature of 400 K and compressed isothermally to a volume equal to
its initial volume. Assume that CP = 30 kJ/kmol K. Find At/, AH, Q and W .
464 Stoichiometry and Process Calculations

12.82 Argon gas at 300 K and 1.5 Pa is contained in a chamber of volume 2 x 10-3 m3. A
1000-ohm electric resistance heater is used to heat the gas. The mass of heater is 15 g
and its heat capacity is 0.35 kJ/kg K. The gas may be assumed ideal with CP = 5R/
2. The heater draws current at 40 V for 5 minutes. Calculate the final gas temperature
and pressure at equilibrium.
12.83 Hydrogenation of an edible oil is to be carried out in a reactor at a pressure of
136.8 kPa and a temperature of 453 K. The hydrogen gas at 293 K is heated to this
temperature by passing through a coil where it experiences a pressure drop of 300 kPa.
Hydrogen behaves like an ideal gas and its heat capacity at constant pressure is 29.4
kJ/kmol. Neglecting kinetic energy effects, determine the heat transfer rate in the coils
per 1000 kg of hydrogen.
Energy changes in ideal gas processes
12.84 The heat capacities of nitrogen gas which is assumed as an ideal gas are Cv = 20.8
and CP = 29.1 kJ/kmol K. The gas initially at 10 bar and 280 K is undergoing a change
of state to the final condition of 1 bar and 340 K. Determine the change in internal
energy and the change in enthalpy.
12.85 One cubic metre of an ideal gas is being compressed adiabatically from an initial
condition of 1 bar and 310 K to a pressure of 10 bar in an open system. If the efficiency
of the process is 80%, how much work is required? Take y = 1.4. Compare the result
with that if the operation is carried out in a closed system.
12.86 C02 is sold commercially in steel containers at 60 bar. The gas is leaking through the
outlet valve slowly so that the temperature may be assumed constant at the room
temperature of 300 K .
(a ) What is the work done in the expansion of 10 kg of this gas from 60 bar to 1 bar?
( b) If the temperature were constant at 290 K, would there be any difference in the
work done?
( c ) What are the changes in enthalpy in both the above cases?
12.87 An ideal gas is compressed adiabatically from 1.5 bar, 338 K to 9 bar. The process
is reversible, and y = 1.23 is constant over the entire range of conditions. Calculate the
following:
(a ) The temperature at the end of compression
( b) The work of compression
(c ) The heat transferred
(d ) The change in internal energy
(e ) The change in enthalpy
12.88 An ideal gas undergoes the following reversible processes:
(a ) From an initial state of 343 K and 1 bar, it is compressed adiabatically to 423 K.
( b) It is then cooled to 343 K at constant pressure.
(c ) Finally it is expanded to its original state isothermally.
Calculate AU AH , W and Q for each step as well as for the entire cycle. Assume
9

CV = ( 3 / 2 )R .
 Energy Balance: Thermophysics 465

12.89 Air initially at 389 K and 8 bar is expanded reversibly and isothermally to a pressure
such that when it is cooled to 278 K at constant volume, its pressure is 2 bar. Assume
air to be an ideal gas with CP = 29.3 J/mol K. Calculate the work, heat transferred,
changes in internal energy and change in enthalpy.
12.90 Assume that the P-V-T relationship for nitrogen gas can be approximated by the ideal
gas equation PV = nRT , where R = 8.314 kJ/kmol K . The heat capacities are Cv =
20.786 kJ/kmol K and CP = 29.1 kJ/kmol K. Nitrogen which was initially at 1 bar and
280 K is compressed to 5 bar and 280 K by two different reversible processes:
(a ) Cooling at constant pressure followed by heating at constant volume
( b) Heating at constant volume followed by cooling at constant pressure
For each of the above paths determine the conditions at the intermediate state and AU ,
AH , Q and W .
12.91 Methane is stored in a tank of capacity 5.7 x 10-2 m3 at a pressure of 15 bar and
294 K. The gas is allowed to flow from the tank through a partially opened valve to
a gas holder where the pressure is constant at 1.15 bar. When the pressure in the tank
dropped to 5 bar, what would be the mass of methane removed under the following
conditions:
( a ) If the process took place slowly so that the temperature was constant.
( b) If the process took place so rapidly that the heat transferred was negligible.
Methane behaves as an ideal gas with y = 1.4.
12.92 A rigid non-conducting tank with a volume of 4 m3 is divided into two equal parts by
a membrane. On one side of the membrane the tank contained gas A at 5 bar and 350 K
and on the other side a gas B at 10 bar and 450 K. A and B are ideal gases with Cv
values (5/2 )R and (7/2 )R respectively. The membrane is suddenly ruptured and the
gases get mixed . What are the final temperature and pressure?
12.93 One cubic metre of an ideal gas at 600 K and 20 bar expands to ten times its initial
volume as follows:
(a ) By a reversible, isothermal process
(b) By a reversible, adiabatic process
(c ) By an irreversible, adiabatic process in which the expansion is against a restraining
pressure of 1 bar
If CP = 21 J/mol K, calculate the final temperature, pressure and the work done by the
gas.

Energy balance for flow processes

12.94 In a test of water-jacketed air compressor, it was found that the shaft work required
to drive the compressor was 150 kJ per kg air compressed . The enthalpy of air leaving
the compressor was found to be greater than that of the air entering the compressor
by 80 kJ / kg and the heat removed by the cooling water was 100 kJ per kg of air.
Determine the amount of energy that must have been dissipated as heat to the atmosphere
from the bearings, cylinder walls, etc.
466 Stoichiometry and Process Calculations

12.95 A steam turbine using steam at 1368 kPa and 645 K and discharging saturated steam
at 137 kPa is used to generate power for a certain chemical plant . The turbine acts
adiabatically and the feed and discharge velocities may be considered equal. Determine
the theoretical horsepower developed by the turbine if it uses 1650 kg of steam per
hour. From steam tables, the enthalpy of superheated steam at 1368 kPa and 645 K
= 3200 kJ/ kg and the enthalpy of saturated steam at 137 kPa = 2690 kJ/kg.
12.96 3600 kg/h of superheated steam at 200 kPa and 673 K enters a turbine with a velocity
of 100 m/s. The inlet to the turbine is at an elevation of 10 m and the exit is at an
elevation of 3 m. The steam leaves the turbine at a velocity of 150 m /s and is 98% dry
at a pressure of 10 kPa . What is the power output of the turbine if the energy loss from
it is estimated to be 40000 kJ/h?
12.97 A trial run on a steam turbine power plant gave the following results
Entrance to boiler: Exit of turbine:
Mass flow rate = 3600 kg/h Velocity of steam = 25 m/s
Enthalpy of water = 850 kJ/kg Elevation above datum = 0
Elevation above datum = 4.3 m Enthalpy of steam = 2625 kJ/kg
Velocity of water = 5 m/s
Determine the power developed by the turbine if the heat added in the boiler is
2100 kJ / s.
12.98 In a small power plant steam at 573 K and 1800 kPa is expanded to 101.3 kPa with
85% quality at a rate of 0.1 kg/s. What is the horse power developed by the turbine?
12.99 A turbine is fed with steam at 78 bar and 698 K (enthalpy = 3213 kJ/kg ) at a rate of
1000 kg/ h. Saturated steam at 5 bar ( H = 2749 kJ /kg ) is withdrawn from one point in
the turbine at a rate of 250 kg/h. The remaining steam leaves the turbine saturated at
1 bar ( H =2676 kJ/kg). Determine the power output from the turbine if it operates
adiabatically.
12.100 A boiler receives water at 1800 kPa and 300 K where it is converted to superheated
steam at 1800 kPa and 673K. The superheated steam is expanded in an adiabatic
turbine and emerges at a pressure of 200 kPa and 98% quality. Per kg of steam calculate
the heat transferred, work done and the change in enthalpy for (a) the boiler and (b)
the turbine.
12.101 Superheated steam at 2000 kPa and 873 K is expanded in a turbine at a rate of 100 kg/
min. The feed line is 75 mm in diameter and the turbine exhausts through a 125 mm
diameter line after expanding adiabatically to 25 kPa. What is the horsepower rating of
the turbine?
12.102 The work required for compressing a gas from an initial condition of 100 kPa and
300 K to a final pressure of 300 kPa is found to be 280 kJ per kg of the gas. The
compressed gas is admitted to a nozzle where its velocity is increased to 700 m /s. If
the gas enters the compressor with negligible velocity and leaves the nozzle at 100 kPa
and 300 K, what is the heat removed during compression?
 Energy Balance: Thermophysics 467

12.103 Steam at 700 kPa and 553 K enters a nozzle with negligible velocity and discharges
at a pressure of 475 kPa. Determine the following:
( a ) The exit velocity
( b ) The cross-sectional area at the nozzle exit for a flow rate of 0.5 kg/s
12.104 Water at 368 K is pumped from a storage tank at the rate of 25 m3/h. The motor for
the pump supplies work at the rate of 2 hp. The water passes through a heat exchanger,
where it gives up heat at the rate of 42000 kJ/min and is delivered to a second storage
tank at an elevation of 20 m above the first tank. What is the temperature of the water
delivered to the second storage tank? Assume that the enthalpy of water is zero at
273 K and the specific heat of water is constant at 4.2 kJ/kg K.
12.105 Water is flowing in a straight horizontal insulated pipe 25 mm ID. There is no device
present for adding or removing energy as work . The upstream velocity is 10 m /s. The
water flows in a section where the diameter is suddenly increased.
(a ) What is the change in enthalpy if the downstream diameter is 50 mm?
( b ) What is the maximum enthalpy change for a sudden enlargement in pipe?
12.106 Water at 293 K is being pumped from a constant head tank open to atmosphere to a
second tank kept at a constant pressure of 1150 kPa through a 50 mm ID pipe at a rate
of 24 m 3/h. The level of water in the second tank is 10 m above that in the first tank.
The pump and motor have an overall efficiency of 70 %, and the energy loss in the
pipe line is estimated to be 50 J/ kg. Determine the horsepower rating of the pump.
12.107 Water at 200 kPa and 355 K ( H = 343.3 kJ/kg ) enters a straight horizontal pipe at a
velocity of 3 m/s, where it is heated by flue gases from the outside. Steam leaves the
system at 100 kPa and 423 K ( H = 2776.3 kJ/kg ) at a velocity of 200 m/s. How much
heat must have been supplied per kg of water flowing?
12.108 Calculate the horsepower rating of the pump required to pump 1000 kg/h of water
from 600 kPa and 300 K to 6000 kPa and 310 K. The discharge is 5 m above the
suction point.
12.109 Oil flows at a rate of 1000 kg/min from an open reservoir at the top of a hill, 400 m
in height to another reservoir at the bottom of the hill. Heat is supplied to the oil on
its way at the rate of 1800 kJ/min and work is supplied by a 1 -hp pump. Take the mean
specific heat of oil to be 3.35 kJ/kg K. Determine the temperature change of the oil.
12.110 A municipal water-supply system delivers water from a storage tank at a rate of
12 cubic metres per minute to consumers 15 m below the tank level utilizing pump
work at a rate of 1.5 hp. If the exit velocity of water is 0.5 m /s and its temperature
is the same as the temperature of water in the tank, estimate the heat loss from the
system . Assume that the water level in the tank is essentially constant.
12.111 A pump is used to transfer a solution of density 1200 kg/m 3 from a mixing vessel to
a storage tank through a pipe of diameter 0.08 m at a velocity of 1 m /s. The level
difference between the liquid in the mixing vessel and the storage tank is 20 m. Both
tanks are open to the atmosphere. Frictional loss is estimated to be 300 W. Determine
the pressure increase over the pump. What is the power input to the pump?
468 Stoichiometry and Process Calculations

12.112 A pump is used to transfer a solution of density 1250 kg/m3 at a rate of 12 m 3/h from
an open storage tank to the top of an absorption tower, which is operated at a pressure
of 500 kPa. The pump discharges into the tower through openings equivalent in area
to a 25 x 10-3 m pipe. The point of discharge is 30 m above the level of solution in
the tank. The pump intake is through a pipe of diameter 50 x 10-3 m which extends
to a depth of 2 m below the level of solution in the tank. The friction head in the suction
line is estimated to be 1.5 m of water and that in the discharge line is 10 m of water.
If the efficiency of the pump is 70%, what is the power input to the pump? What
pressures will be indicated by the pressure gauges at the inlet and exit of the pump?
12.113 Air, assumed to be an ideal gas with molar heat capacity CP = 30 kJ/kmol K, is flowing
through a pipe of diameter 0.15 m at a rate of 0.3 m 3/s at 100 kPa and 300 K before
entering a compressor. A cooler removes heat from the compressed gas at a rate of
75.0 kJ/s. The gas at 315 K and 550 kPa is then carried away through a pipe of diameter
0.03 m. What is the power input to the compressor?
12.114 A solution of 10% (weight) acetone in water is subjected to fractional distillation at a
rate of 1000 kg/h to produce a distillate containing 99% acetone and a bottom product
containing not more than 100 ppm acetone. The feed enters at 308 K, and the distillate
and residue leave the tower at 298 K and 373 K respectively. A reflux ratio (ratio of
the weight of reflux to the weight of distillate product) of 10 is employed. The rise
in temperature by 30 K is permitted for the cooling water circulated in the condenser
employed for condensing the vapours into the distillate product and the reflux. Saturated
steam at 276 kPa is available for supplying the heat of vaporization in the reboiler.
Heat losses from the column may be neglected . The heat capacity of acetone is
2.2 kJ / kg K and that of water is 4.2 kJ/ kg K . The boiling point of 99% acetone-water
solution is 330 K. The latent heat of acetone at 330 K is 620 kJ /kh and that of water
is 2500 kJ / kg. The laten heat of steam at 276 kPa is 2730 kJ / kg. Calculate the
following:
(a ) The cooling water circulation rate
( b ) The rate of circulation of steam
12.115 Air at a rate of 100 kg/h enters a compressor at 100 kPa and 260 K with an enthalpy
of 490 kJ/kg where it is compressed to 1000 kPa and 280 K. The air leaves the
compressor at 65 m/s with enthalpy 510 kJ/kg. Calculate the power required for the
compressor.
12.116 Water flowing upward through a vertical pipe enters a reducer with a velocity of 1 m/s.
The diameters at the entrance and exit of the reducer are 0.2 m and 0.1 m respectively.
If the pressure at the entrance to the section is 105 kPa, what is the pressure at the
exit given that the entrance and exit are 1.5 m apart?
12.117 1000 kg/ h of steam at 4500 kPa and 573 K enters the turbine through a 75 -mm
diameter main. In the turbine steam expands at constant entropy (reversible adiabatic)
to 10 kPa pressure. Determine (a) the power produced by the plant in kWh/day if the
conversion of mechanical to electrical work is 90% efficient and (b ) the size of exhaust
main if the steam were to have the same velocity as in the inlet main.
 Energy Balance: Thermophysics 469

12.118 The feed to a distillation column consists of 10000 kg/h of a mixture of benzene and
toluene containing 45% (mole) benzene at 300 K. On fractionation of this mixture a
distillate containing 99% (mole) benzene and a residue consisting of 1.5% (mole)
benzene are obtained. The distillate is condensed at 355 K and further cooled to 350 K
in the overhead condenser. The residue leaves at 383 K. A reflux ratio of 8 is employed.
Saturated steam at 412 K (k = 2148 kJ/kg) is supplied to the reboiler. The vapour
produced in the reboiler is 3.5 % (mole) benzene. The temperature rise for cooling
water is limited to 30 K. The latent heat of condensation of the distillate vapour is
32.05 kJ/mol. The heat capacity of all liquid streams in the column may be assumed to
be 160 kJ /kmol K. Calculate the rate of circulation of cooling water and the steam
supply rate in kg/ h .
12.119 A steam heated dryer evaporates 1000 kg/h of water from a wet solid material. The
dryer is operated at atmospheric pressure. Air enters the dryer at 303 K and 293 K wet
bulb and leaves at 365 K containing 0.3 mol water per mol dry air. The solid enters the
dryer at 290 K and the enthalpy change in the solid may be neglected. The heat loss
from the dryer is estimated to be 5 % of the total heat duty of the dryer. Calculate the
heat duty of the dryer.
12.120 A steam - jacketed vessel is charged with 200 kg of a feed material ( heat capacity
3.5 kJ /kg K ) at 295 K to heat it to 373 K . The heating is done by complete condensation
of saturated steam at 40 bar (k = 1714 kJ/kg) in the jacket. The rate of heat loss from
the vessel is estimated to be at a rate of 1.5 kJ/s. Determine the mass of steam needed
if the charge was heated for one hour.
12.121 10000 kg/ h of a wet solid containing 5% water on a wet basis is to be dried to 0.10%
in a counter-current rotary drier. The feed enters the drier at 300 K. Drying air enters
the drier at 422 K and leaves at 343 K. The solid leaves the drier at 366 K. The heat
capacity of solid may be taken as 1.5 kJ/kg K. The evaporation of the moisture occurs
at 307 K. The latent heat of vaporization of water at 307 K is 2420 kJ /kg and the
specific heat of water vapour is 1.884 kJ/kg K. Calculate the following:
(a ) The amount of heat required to bring the product to the discharge temperature
( b ) The amount of heat required to remove the moisture in the solid
12.122 Saturated steam at 500 K circulated at a rate of 100 kg/h is used as the heating medium
for preheating the feed to a reactor. Determine the amount of heat transferred to the
feed stream in one hour if the condensate leaving is at 425 K. If subcooling is not
allowed in the condenser, how much additional steam is to be supplied for the same
heat duty?
12.123 A liquid mixture consisting of 30% ( mole) ethane and the rest ^ -butane at 280 K and
a very high pressure is first heated by passing through a heat exchanger and then
throttled to a lower pressure of 1400 kPa. On throttling, partial vaporization of the
mixture takes place. The mixture is admitted into a flash chamber maintained at 1400 kPa.
The vapour and liquid products are separated here at 328 K. The vapour product
contains 60% ( mol) ethane and the liquid product contains 17% (mol) ethane. The
470 Stoichiometry and Process Calculations

enthalpy values are: feed at 280 K = - 8500 kJ /kmol, vapour at 328 K = 14 000 kJ/
kmol and liquid at 328 K = - 3500 kJ /kg. Find the quantity of heat required for the
flash vaporization of 100 kmol of the feed.
12.124 The discharge air from a drier has a dry-bulb temperature of 330 K and a wet-bulb
temperature of 317 K (humidity = 0.06 kg of water per kg of dry air, enthalpy 228 kJ/
kg dry air). To keep the drying rate within limits and to avoid undesirable effects, a
portion of this air is recycled and is mixed with fresh air before being sent to the heater
and then to the drier. Eighty percent of the dry air entering the heater is recycled. Fresh
air supplied is at 249 K with humidity 0.006 kg of water per kg of dry air (enthalpy
of fresh air is 49 kJ/ kg ). How much heat is required per kilogram of water evaporated?
12.125 Ammonium sulphate is dried from 3.5 % moisture to 0.2% moisture in a counter-
current rotary drier at a rate of 1000 kg/h of product. Atmospheric air at 298 K, 50%
humidity will be heated by passage over steam coils to 363 K before it is admitted into
the drier. The air leaves the drier at 305 K. The solids enter the drier at 298 K and is
expected to be discharged at 333 K. The heat loss from the drier is 40 x 103 kJ/h.
Determine the following:
(a ) The air circulation rate, kg/h
( b ) The heat duty of the drier, kJ/h
The heat capacity of ammonium sulphate is 1.5 kJ /kg K, the heat capacity of dry air
is 1.005 kJ/ kg K, the specific heat of water vapour is 1.884 kJ/kg k and the latent heat
of vaporization of water at 273 K is 2502 kJ/kg.
12.126 Air, with dry-bulb temperature 311 K and wet-bulb temperature 300 K, is scrubbed
with water to remove dust. The water is maintained at 298 K. The air leaving the
scrubber is in equilibrium with water. It is then heated to 366 K in an air pre-heater
and admitted to an adiabatic rotary drier. The air leaves the drier at 322 K. The material
to be dried enters and leaves the drier at 319 K. The material loses moisture at a rate
of 0.05 kg of water per kg of product The total product is 1000 kg/h. Using the
psychrometric chart, determine the heat supplied to the air pre-heater in kJ/h.
13 Energy Balance
Thermochemistry

Thermochemistry plays a very significant role in the design and analysis of chemical processes.
Energy balances in processes involving chemical reactions are important in the design of
process reactors for carrying out industrial reactions under specified conditions. A chemical
engineer should be able to make accurate estimates of energy requirements for carrying out
chemical processes and the energy changes involved in various stages of the process. The
enthalpy changes involved in chemical reactions, the influence of temperature on the enthalpy
changes of chemical reactions and the methods for the evaluation of the heat of reaction are
important for process calculations and these are discussed in the following sections.

13.1 HEAT EFFECTS ACCOMPANYING CHEMICAL REACTIONS

Energy changes are involved in the course of a chemical reaction; heat is either absorbed or
evolved during the reaction. The reactions in which heat is absorbed are called endothermic
reactions and those in which heat is evolved are called exothermic reactions. Knowledge of the
heat effects accompanying chemical reactions and the influence of the operating parameters on
these energy changes is essential for the proper design and operation of reaction vessels.

13.1.1 The Standard Heat of Reaction

By heat of reaction we mean the change in enthalpy of the system for the reaction proceeding
at constant temperature. It is the difference between the enthalpy of products and the enthalpy
of reactants and is denoted by AH . Thus, positive values of AH indicate increase in the enthalpy
and therefore represent endothermic reactions and, negative values of AH mean decrease in
enthalpy and therefore refer to exothermic reactions.
AHr = ZHP - ZHR ( 13.1 )
where AHr is the heat of reaction and HP and HR are the enthalpies of the products and

471
472 Stoichiometry and Process Calculations

reactants respectively. To complete the definition of the heat of reaction, it is necessary to

specify the conditions of every product and reactant involved in the reaction.
The standard heat of reaction is the enthalpy change accompanying a reaction when both
the reactants and products are at their standard states at constant temperature T . It is represented
by the symbol A H j , the superscript ‘0’ indicating that the heat of reaction refers to the
standard conditions. By convention, the standard heats of reaction are reported at a temperature
of 298 K and are represented by AH 298 . The standard state is specified by specifying the
pressure, composition and the state of aggregation, or the physical state of the species. By
convention, the standard state pressure is one standard atmosphere. The choice of one bar as
the standard state pressure is now widely accepted. The species are assumed to be pure
components in the standard state. The physical state of the components are: for gases, the pure
substances in the ideal gas state at 1 bar; for solids and liquids, the pure substances in the solid
or liquid state respectively at 1 bar.
For example, consider the following reaction:
CH4 (g) + 202 (g) -> C02 (g) + 2H20 (1) °
Atf 298 = - 890 kJ
This equation means 1 mole of methane in the form of pure methane gas at 1 bar reacts
completely with 2 moles of pure oxygen gas at 1 bar to produce one mole of pure C02 gas
and 2 moles of pure liquid water at 1 bar, all the substances being at 298 K. Since the heat
of reaction is negative, the above equation says that 890 kJ heat is liberated in the reaction. In
the reaction
2C (s) + 02 (g ) -4 2CO (g) AH % = - 221.2 kJ
2 mol solid carbon reacts with 1 mol gaseous oxygen both at their standard state of 1 bar giving
2 mol gaseous carbon monoxide also at the standard state of 1 bar, the temperature being kept
constant at 298 K. During this reaction 221.2 kJ of heat is liberated.
The heat evolved or absorbed in a chemical reaction corresponds to the stoichiometric
numbers of the reacting species as given in the chemical equation. For example, when the above
reaction is written as follows, the standard heat of reaction is just half of the value in the
previous equation:

C ( s) + — —
02 (g) » CO (g) AH °9 S = -110.6 kJ
In the absence of chemical equation, the reported values of heat of reaction should clearly
mention the basis as given below:
AH , = ~
110.6 kJ per mol CO
In the case of incomplete reactions, the heat of reaction is to be calculated considering only
the quantity of reactants actually consumed or the quantity of the products actually formed in
the reaction. Suppose that the heat liberated on the combustion of 12 kg of carbon is to be
calculated. We have seen that on complete combustion , the heat liberated is 110.6 x 103 kJ. If
only 50% carbon is reacted, the heat liberated will be 0.5 x (110.6 x 103) kJ.
 Energy Balance: Thermochemistry 473

EXAMPLE 13.1 A gas mixture analyzing 20% (mol) CO, 30% (mol) H 2 and 50% (mol) N2
is completely burned in air. The following heat of reaction data are available:

CO (g) + - 02 (g) -» C02 (g) AH ° = - 282.91 kJ/mol

H 2 (g ) + ~
02 (g) — > H 20 (g) AH° = - 241.83 kJ/mol
( a ) Determine the amount of heat liberated on the complete combustion of 100 mol of the
gas mixture.
(b) If only 90% of the CO and 80% of the H2 react, how much heat is liberated on the
combustion of 100 mol of the mixture?
Solution Basis: 100 mol gas mixture burned
(a) The heats of reactions are negative, indicating that heat is liberated during the reaction.
According to the stoichiometric equation, 1 mol CO on combustion liberates 282.91 kJ
of heat. The number of moles of CO present is 20 mol. Therefore, the amount of heat
liberated on combustion of CO = 20 x 282.91 kJ = 5658.2. Similarly, the amount of
heat liberated on combustion of 30 mol hydrogen = 30 x 241.83 kJ = 7254.9 kJ.
Therefore, the total amount of heat liberated is
5658.2 + 7254.9 = 12913.1 kJ
(b) The number of moles of CO reacted is
0.9 x 20 = 18 mol
The number of moles of hydrogen reacted is
0.8 x 30 = 24 mol
The total amount of heat liberated is
18 x 282.91 + 24 x 241.83 = 10,896.3 kJ

13.1.2 The Standard Heat of Combustion

When the reaction under consideration is a combustion reaction, the heat of reaction is known
as heat of combustion . The heat of combustion of a substance is the heat of reaction when a
substance is oxidized with molecular oxygen. The standard heat of combustion at temperature
T is the enthalpy change when the substance at its standard state and temperature T, undergoes
combustion, yielding products also at their standard state and temperature T. In the following
reaction, the standard heat of combustion of liquid acetaldehyde at 298 K, A/J ° 298 , is - 1168.12
kJ/kmol.
5
CH3CHO (1) + - 02 (g) -> 2C02 (g) + 2 H20 (1) °n
A//c 298 = - 1168.12 kJ
{ Note: The heat of combustion values are reported on the basis that water formed is in the
liquid state.)
474 Stoichiometry and Process Calculations

The heat of combustion is usually expressed per mole of the substance reacted. The
negative of the heat of combustion of a fuel is frequently referred to as its heating value. This
is the energy exchanged with the surroundings when the unit mass of fuel is burnt in oxygen.
The heat of combustion of a fuel is a negative quantity, whereas the heating value is positive.
When water formed during combustion is in the liquid state, the energy liberated will be more
than the energy liberated when the combustion products contain water in the vapour state. The
heating value in the former is known as higher heating value or gross heating value, and that
in the latter is known as lower heating value or net heating value. Unless otherwise stated , the
heating value reported along with the fuel analysis is the gross heating value since this is the
one that is usually determined using a calorimeter.
The gross heating value of coal can be calculated using the Diilong formula:
Heating value (kJ/ kg of coal) = 338.2wc + 1442.8wH ( net ) + 94.2 ws
where wc, ws, wH( net ) are, respectively, the weight percentage of carbon , sulphur and net
hydrogen. The net hydrogen

^H(net) = WH "
—w
0

where w0 is the weight percentage of oxygen and wH is the weight percentage of hydrogen.

13.1.3 The Standard Heat of Formation

The heat of formation is the heat evolved or absorbed in the formation of one mole of a
substance from its constituent elements or the change in enthalpy accompanying the formation
of one mole of a substance from the constituent elements is termed the heat of formation .
When the reactants and products are at their standard states, the heat of formation is called
standard heat of formation . The enthalpy of formation of the elements is taken as zero. The
standard heat of formation of carbon monoxide gas at 298 K, A// ° 298 > ?
ls - 110.6 kJ/mol. The
standard heat of formation at 298 K for methyl chloride is - 81.923 kJ /mol. These statements
are equivalent to the following equations:

C (s) +
\o 2(g) CO (g) AH °f 29S = - 110.6 kJ

C (s) + ~
|ci (g) -
H2 (g) + 2 4 CH3C1 (g) AH °f 29S = - 81.923 kJ

The standard heat of formation of sulphuric acid is given by the equation

H2 (g) + S (s ) + 202 (g ) -» H2S04 (1), AH °f 29g = - 811.86 kJ
which means that when one mole sulphuric acid is formed from its constituent elements all at
298 K and a pressure of one bar, 811.86 kJ heat is evolved.
Standard heats of formation and combustion data for certain compounds are given in Appendix
(Table A .2 ).
 Energy Balance: Thermochemistry 475

13.1.4 Hess’s Law of Constant Heat Summation

Heat of reaction represents the difference between the enthalpy of products and the enthalpy
of reactants. Enthalpy as we know, is a state function and the heat of reaction , therefore,
depends only on the initial and final states, no matter how this change is carried out. The net
heat evolved or absorbed in a chemical reaction is the same whether the reaction takes place
in a single step or in a series of steps. This is known as Hess s law. This law permits us to
treat all thermochemical equations as algebraic equations. Using this, we can calculate the heat
of formation of a compound from a series of reactions not involving the direct formation of
the compound from its elements. For example, the heat of formation of a compound can be
calculated if the heat of combustion data of all the species involved in the formation reaction
are known. Similarly, if the data on the heat of formation of all the substances taking part in
a chemical reaction are available, the heat of reaction may be readily calculated.
Hess’s law permits us to estimate accurately the heat of formation of compounds that are
difficult to determine experimentally. For example, the heat of formation of CaC03 (s) can be
estimated to be - 1207.8 kJ, given the following heat of reaction data:

Ca (s) +

CaO (s) +
^
C (s) +
02 (g) CaO (s)

02 (g) ^ C02 (g)

C02 (g) CaC03
A//0 =

AH 0 =
AH 0 =
-

-
-
635.8 kJ

393.8 kJ
178.2 kJ
Adding the above three equations together gives

Ca (s) + C (s) + —3 02 (g) CaC03 (s)

AH 0 = - 635.8 + (- 393.8) + (-178.2) = -1207.8 kJ

Heat of reaction from heat of combustion or heat of formation data : The heat of
reaction may be calculated as the difference between the algebraic sum of the heat of com-
bustion of the reactants and the algebraic sum of the heat of combustion of products.
AH ° = X AH °c - X A// ° (13.2)
Reactants Products

It can also be shown that the standard heat of reaction is the difference between the algebraic
sum of the standard heat of formation of products and that of the reactants.
AH ° = X A H °f - X A H °f (13.3 )
Products Reactants

EXAMPLE 13.2 The heat of combustion of methane, carbon and hydrogen are -890.4 kJ/mol,
kJ/mol and - 285.84 kJ/mol respectively. Calculate the heat of formation of methane.
- 393.51

Solution The desired reaction is

C (s) + 2 H2 (g) — > CH (g) 4 A H °f = ?
476 Stoichiometry and Process Calculations

The heat of reaction (in this case, the heat of formation) can be calculated either by using
the Hess’s law or by using Eq. ( 13.2) directly.
Using Hess’s law: Since the heat of combustion data are available, the following combus-
tion reactions may be written:
CH 4 (g) + 202 (g ) C02 (g ) + 2H20 (1) AH 0 = - 890.4 kJ (A)
C (s) + 02 (g) C02 (g ) AH 0 = - 393.51 kJ (B)

H 2 (g ) +

^ 02 (1) H20 (1) AH 0 = - 285.84

Multiply Eq. (C) by 2 and add the result to Eq. ( B ) and subtract Eq. (A ) from the sum.
The result is the desired reaction. That is, Eq. ( B ) + 2 x Eq. (C) - Eq. (A) gives
C (s) + 2H2 (g ) CH4 (g)
kJ (C )

The same algebraic operations are to be carried out on the respective heat of reactions. By
Hess’s law, the heat of desired reaction is
AH 0 ( B) + 2 AH (C ) ° - AH 0 ( A) = - 890.4) = - 74.79 kJ
393.51 + 2(- 285.84) - (-

Using Eq. (13.2): Heat of reaction can be calculated from heat of combustion data using
Eq. (13.2). The heat of reaction is the sum of the heat of combustion of all the reactants in
the desired reaction minus the sum of the heat of combustion of all the products of the desired
reaction. Here the reactants are one mole of carbon and two moles hydrogen, and the product
is one mole of methane. Therefore, the heat of reaction is
1 x (- 393.51 ) + 2 x (- 285.84) - (- 890.4) = - 74.79 kJ
Therefore, the heat of formation of methane is - 74.79 kJ .

EXAMPLE 13.3 Coal having the following analysis on a weight basis has a gross heating
value of 29000 kJ/kg: carbon, 70.0%; hydrogen, 5.5%; nitrogen, 1.5%; sulphur, 3.0%; oxygen:
13.0%; ash, 7.0%. Calculate the net heating value given that the latent heat of vaporization of
water is 2370 kJ/kg water.
Solution Basis: 1 kg of coal burned
The amount of hydrogen present in the coal is

—
100 x 2.016
= 27.28 x 10
" 3
kmol

The amount of water formed on combustion is

27.28 x 10 3 kmol = 0.492 kg
"

The amount of heat required for vaporization of 0.492 kg of water is

0.492 x 2370 = 1164.9 kJ
The net heating value of the coal is the heat given out when all the water formed is in the
vapour state. Therefore, the net heating value will be less than the gross heating value by the
quantity of heat required for vaporization of the water formed on combustion. Thus, the net
heating value is
29 000 - 1164.9 = 27 835.1 kJ/kg
 Energy Balance: Thermochemistry 477

EXAMPLE 13.4 Use the Diilong formula to calculate the gross and net heating values of coal
having the following composition:
C = 75%, H = 5%, N = 1 %, O = 9%, S = 1%, Moisture = 2.0%, Ash = 9.0%
Take the latent heat of vaporization of water to be 2370 kJ/kg of water.
Solution Basis: 1 kg of coal burned
Gross heating value is given by the Diilong formula:
Gross heating value (kJ/kg of coal) = 338.2wc + 1442.8wH( net ) + 94.2ws
where wc, ws, wH(net ) are, respectively, the weight percentages of carbon , sulphur and net
hydrogen.

"HO* = "H
) -

^ =5
Gross heating value = 338.2 wc + 1442.8wH( net ) + 94.2 ws
- 9/8 = 3.875

= 338.2 x 75 + 1442.8 x 3.875 + 94.2 x 1 = 31050 kJ/kg of coal

Water present in the combustion products = 0.05 x 18.016/2.016 + 0.02 = 0.4668 kg/kg
of coal
Heat liberated on condensation = 0.4668 x 2370 = 1106.4 kJ/kg of coal
Net heating value = 31050 - 1106 = 29944 kJ /kg

EXAMPLE 13.5 Calculate the heat of reaction for the esterification of ethyl alcohol with
acetic acid if the standard heats of combustion are: ethyl alcohol (1), - 1366.91 kJ/mol; acetic
acid (1), - 871.69 kJ/mol; ethyl acetate (1), -2274.48 kJ /mol.
Solution The esterification reaction may be represented as
C2H5OH (1) + CH3COOH (1) -> C2H5COOCH3 (1) + H20 (1) A// 2°98 = ?
Using Eq . (13.2): To calculate heat of reaction from the heat of combustion data
Eq. (13.2) may be directly used.
AH ° = X AH ° - X AH °c
Reactants Products

Here,
X A// ° = - 1366.91 - 871.69 = - 2238.6 kJ
Reactants

X
Products
°
AH c = - 2274.48 + 0 = - 2274.48 kJ

( Note that the heats of combustion of H20 and C02 are zero.)
Substituting these into Eq. (13.2 ), we get
AH 0 = - 2238.6 - (- 2274.48) = 35.88 kJ
478 Stoichiometry and Process Calculations

Using Hess’s law : The given data on heat of combustion may be used to write the
following chemical equations:
C2H5OH (1) + 302 (g) 2C02 (g ) + 3HzO (1) AH c° = - 1366.91 kJ (A)

CH3COOH (1) + 202 (g) -4 2C02 (g) + 2H20 (1) AH c° = - 871.691 kJ (B )

C2H 5COOCH3 (l) + 502 (g ) -4 4C02 (g ) + 4H20 (1) AH c° = - 2274.48 kJ (C)

Add Eqs. ( A ) and ( B) and subtract Eq. (C ) from the result. We get
C2H 5OH (1) + CH 3COOH (1) -> C2H 5COOCH3 (1) + H20 (1)
By Hess’s law the same algebraic operations may be performed on the heat of combustion data
as well, with the result that

° = Aff ° (A) + A// ° (B) + Aff ° (C)

A// 298 C = - 1366.91 - 871.69 - (- 2274.48) = 35.88 kJ

EXAMPLE 13.6 The vapour- phase hydration of ethylene to ethanol is represented by:
C 2 H4 (g) + H20 (g) C2H5OH (g)
Calculate the standard heat of reaction if the following data are available:
2C02 (g) + 3H20 (1) -> C2H5OH (l) + 302 (g) Atf 298 ° = 1366.91 kJ
The standard heat of combustion of ethylene at 298 K is -1410.99 kJ/mol and heats of
vaporization of water and ethanol are, respectively, 44.04 kJ/mol and 42.37 kJ/mol.
Solution The following equations may be formulated using the given data :

2C02 (g) + 3H20 (1) C 2H 5OH (l) + 302 (g) A// 2°98 = 1366.91 kJ (A)

C2 H4 (g ) + 302 (g) ^ 2C02 + 2H 20 (1) Ai/ 298 = - 1410.99 kJ ( B)

H20 (1) -4 H20 (g) A

^ v , 298 = 44.04 kJ (C )

C2H5OH (1) C 2H5OH (g) A

^ v , 298 = 42.37 kJ (D)

Perform the following arithmetic operations on the above equations:

Eq. (A ) + Eq. (B ) + Eq. (D) - Eq. (C )
The result is
C2H4 (g ) + H20 (g) C2H5OH (g )

A// °98 = A/7298 (A) + A/7°98 (B) + A// 298 ( D) - AH% { C ) = - 45.75 kJ
EXAMPLE 13.7 Calculate the standard heat of formation of acetylene (C2H 2) given that the
standard heat of combustion of acetylene is - 1299.61 kJ , the standard heat of combustion of
carbon is - 393.51 kJ and the standard heat of formation of liquid water is - 285.84 kJ.
 Energy Balance: Thermochemistry 479

Solution We have the following data:

|o (g) -> 2C02 (g) + H20 (1)

C2H 2(g ) + 2 AH °29 S = - 1299.61 kJ (A)

C (s) + 02 (g) -4 C02 (g) A// 2°98 = - 393.51 kJ (B )

H2 (g) +

^ 02 (g) -4 H20 (1) AH °29 S = - 285.84 kJ

We can apply Hess’s law to calculate the heat of the desired formation reaction.
2C (s) + H2 (g) -> C 2 H2 ( g ) A/f 298 =?
(C )

Multiply Eq. ( B) by 2, add Eq. (C ) to it and subtract Eq. (A) from the result. We get
2C (s) + H2 (g) C2 H5 (g)

A// 298 = 2 x (- 393.51) - 285.84 - (- 1299.61) = 226.75 kJ

EXAMPLE 13.8 In a sulphuric acid plant, sulphur dioxide is obtained by the roasting of iron
pyrites containing 80.0% FeS2 and 20% gangue. Iron sulphide reacts with oxygen according to
the reaction
4FeS2 + 1102 ^ 2Fe203 + 8S02
The cinder formed on the combustion analyzes 5.0% FeS2. Determine the standard heat of
reaction per kilogram of ore, given the following standard heat of formation values at 298 K :
FeS2 (s) = - 178.02 kJ/mol, Fe203 (s) = - 822.71 kJ /mol and S02 (g ) = - 296.9 kJ /mol.
Solution Basis: 100 kg of pyrites charged.
Let x kg of FeS2 be leaving with the cinder unbumed. Then the cinder has the following
composition:
Material Weight (kg )

FeS2 X

Fe203
(80 - x ) 1 _
x x 159 69 0 6655(80 Jc)
119.98 2
Gangue 20
Total 73.24 + 0.3345x

Since the cinder contains 5.0% FeS2, we have = 0.05 , which gives x =
73.24 + 0.3345 x
3.724 kg .
Therefore, the amount of FeS2 reacted is
76.276
80 - 3.724 = 76.276 kg = = 0.6357 kmol = 635.7 mol
119.98
480 Stoichiometry and Process Calculations

The heat of reaction for the following reaction can be calculated from the heat of formation data.

Using Eq. (13.3 )

4FeS2 + 1102 > — 2Fe203 + 8S02

A H° = X A H °f - X A H °f
Products Reactants

= 2 x (- 822.71) + 8 x (- 296.9) - 4 x (- 178.02) - 0 = - 3308.54 kJ

This is the heat of reaction when 4 mol FeS2 is completely consumed. Here 635.7 mol FeS2
is consumed. Therefore, the heat of reaction is
- 3308.54
x 635.7 = -5.258 x 10s kJ
4
The heat of reaction per 1 kg of pyrites burned is
- 5.258 x 105
= -5.258 x 10s kJ
100
EXAMPLE 13.9 Calculate the standard heat of formation of liquid methanol, given the standard
heat of combustion of liquid methanol is - 726.55 kJ/mol and the standard heat of formation
of gaseous C02 and liquid water are, respectively, - 393.51 and -285.84 kJ/mol.
Solution
Using Eq. (13.3): The combustion of liquid methanol is
3
CH3OH (l) + - 02 (g ) C02 (g) + 2H20 (1) AH % = - 726.55 kJ (A)

By Eq. ( 13.3), the heat of reaction is given as

AH ° = X AH °f - X AH °f
Products Reactants

Applying this equation to reaction (A), we can write

- 726.55 AH of ,Co2 + 2AH /o ,H 2O - AH /o ,CH 3OH

= - 393.51 + 2 x (- 285.84) - AH /0 ,CH 3OH

= - 965.19 - AH /0 ,CH3OH
or
Atf ° ,cH OH
3
= - 965.19 + 726.55 = - 238.64 kJ
Using Hess s law: The desired reaction is the formation of liquid methanol from the constituent
elements.

C ( s) + 2 H 2 ( g ) + — 02 (g) -> CH 3OH (l )

 Energy Balance: Thermochemistry 481

The available data may be put into the following forms:

|o (g) -> C02 (g) + 2H20 (1)

CH3OH (1) + 2 AH °298 = - 726.55 kJ (A)

C (s) + 02 (g) -> C02 (g) A// 2°98 = - 393.51 kJ (B )

H2 (g) +

^ 02 (g) -4 H20(1) AH % = - 285.84 kJ

The stoichiometric equation representing the formation of liquid methanol is obtained by
performing the following algebraic operations on these equations.
Eq. ( B) + 2 x Eq. (C) - Eq. (A )
(C )

Therefore, the heat of formation of methanol is

- 393.51 + 2 x (- 285.84) - (- 726.55) = - 238.64 kJ

EXAMPLE 13.10 Calculate the gross heating value and net heating value expressed in kJ/m 3
at STP of a fuel gas having the following analysis:
CO: 21.0%, H 2 = 15.6%, C02: 9.0%, CH4: 2.0%, C2H4: 0.4% and N2: 52.0%
Given that the standard heats of combustion are - 282.99 kJ/mol for CO, - 285.84 kJ/mol
for hydrogen, - 890.4 kJ/mol for methane and - 1410.99 kJ /mol for ethylene, and the heat of
vaporization of water at 298 K is 44.04 kJ/mol.
Solution Basis: 100 mol fuel gas
The total heat evolved on combustion of the fuel is
21 x (282.99) + 15.6 x (285.84) + 2.0 x (890.4) + 0.4 x (1410.99) = 12 747 kJ
Since 100 mol gas at STP occupies a volume of 100 x 22.4 x 10-3 = 2.24 m 3, the gross
heating value of the fuel is
12 747 kJ
2.240
= 5691 3
m
On combustion one mol hydrogen gives one mol water, one mol methane gives two mol
water and one mol ethylene gives two mol water. The number of moles of water formed on
combustion of 100 mol fuel gas = 15.6 + 4.0 + 0.8 = 20.4. The amount of heat required to
vaporize the water formed on combustion = 20.4 x 44.04 = 898.42 kJ.
Therefore, the net heating value is
5691 - 898.42 = 4792.58 kJ
EXAMPLE 13.11 Calculate the standard heat of the following reaction at 298 K:
C5 H 12 (g ) + 802 (g) -> 5 C02 (g) + 6 H20 (1)
The standard heats of formation are as follows:
C02 (g ) = - 393.51 kJ, H20 (g) = - 241.826 kJ , C5 H12 (g) = - 146.4 kJ
The latent heat of vaporization of water at 298 K is 43.967 kJ /mol.
482 Stoichiometry and Process Calculations

Solution The desired reaction can be obtained as the sum of the following two reactions:
C5H 12 (g) + 802 (g) -> 5 C02 (g) + 6H20 (g) AHx
6H20 (g) -> 6H20 (1) AH 2
The heat of reaction AH° = AHx + AH 2
A// ,= E
Products
AH °f - x
Reactants
AH °

= 5 x AH °f COi + 6 x AH 0f UiO ( g ) - AHf CsHi 2 (g )

= 5 x (- 393.51) + 6 x (- 241.826) - (- 146.4) = - 3272.106 kJ

AH2 = - 6 x 43.967 = - 263.802 kJ
AH 0 = AH\ + AH 2 = - 3272.106 - 263.802 = - 3535.908 kJ

13.1. 5 Heat of Reaction at Constant Pressure and Constant Volume

Heat of reaction can be experimentally determined in a constant volume calorimeter. However,
the standard heat of reaction requires that the pressure is maintained constant at 1 atm. Thus,
it becomes necessary that the heat of reaction obtained under constant volume conditions be
converted to the heat of reaction at constant pressure conditions. Since no work is done under
constant volume conditions, by the first law of thermodynamics, the heat transferred is equal to
the change in internal energy.
AUv = Qv ( 13.4 )
Assume that the reaction is now carried out under constant pressure conditions starting
from the same initial conditions as for the constant volume process and the final temperature
attained be the same as that attained in the constant volume process. By the first law of
thermodynamics for a constant pressure process,
AUp = QP - W = QP - PAV
QP = AUP + PAV (13.5 )
The difference between the heat of reaction at constant pressure and that at constant volume is
QP - Qv = AUp - AUv + PAV (13.6 )
For solid and liquid components, the change in internal energy is zero as internal energy
is mainly dependent on temperature and the effect of pressure is negligible. If the gases involved
in the reaction are assumed to behave ideally, the change in internal energy for the gaseous
constituents is zero. AUP = AUv. Therefore, Eq. (13.6 ) reduces to
Qp - Q v = PAV ( 13.7 )
Neglecting the change in volume of solids and liquids involved in the reaction, the volume
change accompanying the reaction is solely the change in volume of the gaseous constituents.
Assuming ideal behaviour of gases,
QP ~ Q v = ( An )RT (13.8 )
Here An is the change in the number of moles of gaseous constituents.
 Energy Balance: Thermochemistry 483

EXAMPLE 13.12 A fuel oil consisting of 10% (weight) hydrogen and 90% ( weight) carbon
is found to give a heat of combustion of 43 000 kJ/kg, when burned in a constant volume-bomb
calorimeter. Calculate the constant-pressure heat of combustion of the oil.
Solution Basis: 1 kg of oil burned
The amount of carbon burned:

0.9 kg = —0.9 = 0.075 kmol

C (s) + 02 (g) C02 (g)
The combustion of carbon produces no change in the volume of gaseous components.
The amount of hydrogen burned:
0.1
0.1 kg = = 0.0496 kmol
2.U 16
Change in the number of moles of gaseous components accompanying the combustion of
one mole of hydrogen in the liquid state is - !4 mol. Therefore, the total change in the volume
of gaseous components accompanying the combustion of 0.0496 kmol hydrogen is

Since
( An )RT = -

^ x 0.0496 x 8.314 x 298 = - 61.444 kJ

Q P - Q v = (A n )RT

QP = Qv + ( An )RT = - 43 000 - 61.44 = - 43 061.4 kJ

Therefore, the constant pressure heat of combustion of the fuel = - 43 061.4 kJ /kg.

13.2 EFFECT OF TEMPERATURE ON STANDARD HEAT OF REACTION

Chemical reaction can be represented as
S v, A = 0 (13.9)
i
where vz represents the stoichiometric number of the substance taking part in the reaction . The
stoichiometric number v, is positive for products and negative for the reactants. For example,
consider the reaction
aA + bB — > IL + mM
Here, a, b, / and m are called stoichiometric coefficients. This reaction may be written as
IL + mM - aA - bB = 0
in which - a, - b , l and m are called the stoichiometric numbers. If the standard heat of the
reaction at temperature Tx is known, the standard heat at any other temperature T can be
determined. Generally, the standard heat of reaction at temperature 298 K ( 7 ) will be available,
^
and it would be necessary to determine the standard heat at some other temperature ( 7). The
specific heat of the components constituting the reaction system should be known as function
484 Stoichiometry and Process Calculations

of temperature. The calculation makes use of the fact that enthalpy is a state property. The
change in enthalpy for a process occuring from a given initial state to a given final state is the
same whatever be the path along which the process is carried out . The actual reaction occurring
at temperature T, for which the standard heat of reaction is AHj , may be treated as occurring
along the three paths as shown in Figure 13.1.
Reaction at T ,
AH T
Reactants at T Products at T

O c/f o
W)
c C
c5 - GO O
CA

£3 §O 5
U
O
«
fl )
C
0)
OH
^
X

Reaction at T i
’
AH 2
Reactants at T Products at T

Figure 13.1 Effect of temperature on heat of reaction .

Step 1: From the initial state of temperature T the reactants are cooled to temperature Tx . The
enthalpy change for this step is
T T
AHx = Reactants *
f I Jf T VfCpjdT
X T ‘ n,CP’ i dT = Reactants
{
(13.10 )

Step 2 : The reaction is allowed to occur at temperature T { . The enthalpy change is

AH 2 = AH \ ( 13.11)
Step 3: The temperature of the products is raised from Tx to T in this step . The enthalpy
change is
T T
AH 3 = X
Products
[ niCPidT =
J Ti ’
X
Products *
[ Tx v,CPl dT (13.12)

Since the enthalpy change depends on the terminal conditions, the standard heat of reaction at
temperature T is obtained by adding the preceding three equations.
A H ° = A Hl + A H 2 + A H 3

AH X f VjCpj dT + AHj + X [ v, Cp , dT
° = Reactants ’ 1
Tx* Products Tx *

The above result can be written as

T
A Hj = A H j1 + !
T
X v, C dT ( 13.13 )
l

The summation in the above equation is over all species taking part in the reaction. Let the heat
capacity of the substances be represented by the following equation .
 Energy Balance: Thermochemistry 485

Cp = a + pr + yT2 (13.14)
Utilizing Eq. ( 13.14), Eq. (13.13 ) can be written as
T
AHj = AHj1 + f A dT
J Tx CP
(13.15)

where
A CP = Aa + A/5 T + A yT 2 (13.16 )
and
Aa = £ v, a, A/3 = Iv,/3, and Ay = £v, y ( 13.17 )
Equation (13.15) may be expanded as

AHj = AHjt + Aa ( T - Tx ) + - Afi ( T 2

2
-T ,2 ) + -3 Ay (I3 - T 2 )
The constants appearing in the above equation can be grouped together to a single constant
AH' , so that we have

AHj = AH' + AaT + —

2
- T 2 + -T 3
3 ^ ^ ( 13.18 )

The constant AH' in Eq . (13.18) can be evaluated if the heat of reaction at a single
temperature is known. Equation (13.18) can now be used for the evaluation of the standard
heat of reaction at any temperature T .

EXAMPLE 13.13 Ammonia is synthesized according to the following reaction:

- N 2 + -H 2
2 2 ^ N H3 ° = - 46.191 kJ
A // 298

The specific heats of the components are represented by

CP = a + pT + yT 2
where CP is in J/mol K and the constants a, /3 and y are:

Molecules a P 7
N2 27.31 5.2335 x 10 -3 - 4.1868 x 10 9
H2 29.09 - 8.374 x KT4 2.0139 x 10 6 -

NH3 25.48 36.89 x 10 3 -

- 6.305 x lO 6 ^

Determine the heat of reaction at 700 K.

Solution Equation (13.18) can be used to calculate the heat of reaction at any temperature.

AHj = AH' + AaT + MT

2
+ ELJ
2
3
3
486 Stoichiometry and Process Calculations

_ 1 3
Aa
A
- ANH 3 - ~ aN 2 ~ ~
an 2

= 25.48 - - x 27.31 - - x 29.09 = - 31.81

2 2
_ PN
^ P = PNH 3
~
2
~ ~
PH 2

= 36.89 xl 0 3 - —2 x 5.2335 xl 0 3 --2 x (- 8.374 xl 0 4 )

“ “ “

3
= 35.5294 x 10 “

a 7 = 7 NH _ 7N 2
_
3
2 ^ H2

= - 6.305 x 10 6 --2 x (- 4.1868 X 10 9 ) --2 x ( 2.0139 X 10-6 )

“ “

6
= - 9.3238 x 10 "

Substituting these values in Eq . (13.18), we get

35.5294 x 10v-3 _ 12 9.3238 x 10-6” 35
,
o ,
AHr = A/f ' - 31.8
^ ir
Ar 7
^+ 01

2
T
3
T

o
At 298 K, AHT = - 46 191 J. Substituting this in the above equation, we get AH' = - 38 207 J.
The heat of reaction can now be expressed as a function of temperature as
3 ®
35.5294 xl 0 “
„ 9.3238 x 10 “

AH £ = -38 207 - 31.817 + 2

2
7" -
3
T3

At T = 700 K,

AHj - -38 207 - 31.81 x 700 + -

35 5294 x 10
(7Q0) 2 - -
9 3238 xl
° (7QQ)3
2 3
= - 52 835 J
Therefore, the heat of reaction at 700 K is - 52.835 kJ.
EXAMPLE 13.14 Methanol is synthesized according to the following reaction:
CO (g) + 2 H2 (g) CH3OH ( g)
The standard heats of formation at 298 K are kJ/mol for CO and - 238.64 kJ/mol
- 110.6

for methanol ( l). The latent heat of vaporization of methanol at 298 K is 37.98 kJ/mol . The
specific heats (J/mol K ) are given by:

CP( CH 3OH ) = 18.382 + 101.564 x 10 - 3

r - 28.683 x 10 - 6
r2
Cp( CO) = 28.068 + 4.631 x 10 "

r - 2.5773 x 104 f 2
3 -

CP(H2) = 27.012 + 3.509 x 10 3 r + 6.9006 x 104 r 2

" "

Calculate the standard heat of reaction at 1073 K .

 Energy Balance: Thermochemistry 487

Solution Enthalpy of cooling the reactants consisting of 1 mol CO and 2 mol hydrogen
from 1073 K to 298 K:

A/7 , = l Jlf 298

073
( 28.068 + 4.631 xl 0 37 - 2.5773 xl 047
“
’ ’ 2)
“

rf 7’

r 298
(27.012 + 3.509 xlO 3 T + 6.9006 x \04 T 2
~ ~
+2 ) dT
Ji

•298
/

x 10-3 T + 11.2239 x 104 T ~ 2

= - 70 082.01 J
J1073 82.092 + 11.649
( ) dT

Enthalpy for heating the products from 298 to 1073 K:

•1073 _3 _
AH 2 = f
J 298
(18.382 + 101.564 xl 0 r - 28.683 x 10 6 r 2 ) dT = 56 644.78 J
The standard heat of reaction at 298 K is
A
^ £ ^ - X S H f = A// y methanol(g) - ( A//
= Products CO ( g) + 2A/fy H 2o(g) ) (A )
298
Reactants
?

^ >

The standard heat of formation of methanol (g) can be obtained from the standard heat of
formation of methanol (1) and the heat of vaporization.
o - 238.64 kJ
CO (g) + 2 H (g) - CH OH ( l) 2 + 3 AHJ =
CH3OH (1) -4 CH3OH (g) AH ® = + 37.98 kJ
Adding these two equations we get the desired reaction for the formation of methanol (g).

CO (g) + 2 H 2 (g) -» CH3OH (g) AH °f = - 200.66 kJ

Substituting the heat of formation values in Eq . (A ) we get
0 o
AH °2 9 S = AHlmethanoi( g ) - ( AH / ’CO(g) + ^
2AHV.H2 (g) )
T

= - 200.66 - (- 110.6 + 0) = - 90.06 kJ

The heat of reaction at 1073 K is now calculated:
AH “ = AHx + AH 29 S + AH 2
= - 70.082 - 90.06 + 56.645 = - 103.497 kJ/mol

EXAMPLE 13.15 Pure CO is mixed with 100 percent excess air and completely burned at
constant pressure. The reactants are originally at 400 K. Determine the heat added or removed
if the products leave at 600 K. The standard heat of reaction at 298 K is -282.99 kJ per mol
CO burned. The mean specific heats applicable in the temperature range of this problem are
29.10, 29.70, 29.10, and 41.45 J/mol K respectively for CO, 02, N 2 and C02.
488 Stoichiometry and Process Calculations

Solution Basis: 1 mol CO reacted

—
CO + O 2 — ^ CO 2

Oxygen theoretically required = 0.5 mol

Oxygen supplied = 1 mol (100 percent excess)
Nitrogen in the air supplied = 1 x 79/21 = 3.76 mol
Let AHx be the enthalpy of cooling the reactants from 400 K to 298 K. The reactants stream
contains 1 mol oxygen, 3.76 mol nitrogen, and 1 mol CO.

AHi = (1 x 29.70 + 3.76 x 29.10 + 1 x 29.10 )(298 - 400 )

= - 17.158 kJ
Let AH2 be the enthalpy of heating the products from 298 K to 600 K . The product stream
contains 1 mol C02, 0.5 mol oxygen, and 3.76 mol nitrogen.
AF2 = (1 X 41.45 + 3.76 x 29.10 + 0.5 x 29.70 )(600 - 298 )
= 50.046 kJ
AH = AHX + A// 298 + AH 2 = - 17.158 - 282.99 + 50.046
= - 250.102 kJ

EXAMPLE 13.16 Carbon monoxide reacts with water vapour to form carbon dioxide and
hydrogen .

CO (g) + H20 (g) C02 (g) + H2 (g) AH °29 S = - 41.190 kJ

The reactants are at 298 K. 75 percent of CO is converted in the reaction. The products leave
the reaction chamber at 800 K. The mean heat capacities in J/mol K are 30.35 for CO, 45.64
for C02, 36.00 for water vapour and 29.30 for hydrogen. Determine the quantity of heat to be
added or removed in the reaction chamber per 1000 kg of hydrogen produced.
Solution Assume a reactant mixture consisting of 1 mol CO (g) and 1 mol water vapour.
Since the reactants are at 298 K, AHx = 0.
The products consists of 0.75 mol C02, 0.75 mol H2, 0.25 mol CO and 0.25 mol water
vapour. The enthalpy of heating the products from 298 K to 800 K is
AH2 = [0.75(45.64 + 29.30 ) + 0.25(30.35 + 36.00)](800 - 298 )
= 36 541.8 J
The heat of reaction is

° = 0.75 x (- 41.190) = - 30.8925 kJ = - 30 892.5 J

Atf 298
 Energy Balance: Thermochemistry 489

The heat of reaction is

A // g00 = A// 298 + AH 2 = - 30 892.5 + 36 541.8 = 5649.3 kJ
This means 5.649 kJ of heat is to be added to the system. The amount of hydrogen produced
here is 0.75 mol or
0.75 x 2.016 x 10 3 = 1.512 x 10 3 kg
" "

Therefore, for 1000 kg of hydrogen produced, the amount of heat to be added is

—1.5125-6xl490 - x 1000 = 3.736 x 106 kJ

~3

EXAMPLE 13.17 A flue gas at 1298 K consisting of C 02, 02 and N 2 is passed through a
bed of carbon. The following reactions occur and both go to completion :

C02 (g) + C (s) -> 2CO (g), AH °r at 298 K = 170 kJ/mol

02 (g) + 2C (s) -> 2CO (g), AH °r at 298 K = - 221.2 kJ/mol

The combustion is adiabatic and the product gases exit at 1298 K. Calculate the required moles
of C02 per mole of 02 in the feed stream so that the net heat generated is zero and the bed
temperature remains constant at 1298 K. The mean molar heat capacities are 0.02, 0.03, 0.03,
and 0.05 kJ/mol K for carbon, oxygen, CO and C 02 respectively.
Solution Let the flue gas contain x mol C02 per mole of oxygen .
The products leaving the bed of carbon contains 2 ( 1 + x) mol CO. The amount of nitrogen
in the reactants and products being the same and both are at the same temperatures, enthalpy
of cooling and enthalpy of heating the nitrogen will numerically be the same and need not be
considered in the evaluation of net enthalpy change.
The enthalpy of cooling the reactants (x mol C02, 1 mol 02 and 2 + x mol carbon ) from
1298 K to 298 K:
AHX = [0.05x + 0.03 + (2 + x ) x 0.02](298 - 1298 )
= - 50x - 30 - 40 - 20x = - 70x - 70 kJ
The enthalpy of heating the products
AH2 = 2(1 + x ) x 0.03 x (1298 - 298) = 60 + 60x kJ
The heat of reaction at 298 K
Atf °98 = 170 x - 221.2
Since the net heat generated is zero,
AH \ + A // 298 + A H 2 =0
- 70* - 70 + 60 + 60* + 170* - 221.2 =0
Solving this equation, we get x = 1.445 mol.
The ratio of moles of C02 to oxygen in the feed stream should be 1.445:1 for the net heat
generation to be zero.
490 Stoichiometry and Process Calculations

EXAMPLE 13.18 Formaldehyde can be made by the partial oxidation of natural gas using
pure oxygen, natural gas being supplied in large excess.

CH 4 (g) + 02 (g) -> CH20 (g) + H 20 (g) AH °29 ,= - 282.926 kJ

The following side reaction also occurs.
CH 4 (g) + 202 (g) -4 C02 (g) + 2H20 (g) AH °29 S = - 802.372 kJ
Methane enters the reactor at 673 K and oxygen at 573 K, and the products leave at 873 K.
The Orsat analysis of the flue gas showed C02 1.9%, CH 20 11.7%, 02 3.8% and CH 4 82.6%.
How much heat is removed from the reaction chamber per 1000 kg of formaldehyde produced?
The mean heat capacities (J /mol K) for a temperature range from 298 K to T K are given
below :

T = 573 K T = 673 K T = 873 K

o2 30.5 31.9
CH4 45.9 51.4
co2 46.3
CH2O 47.1
H26 36.3

Solution Basis: 100 mol flue gas

Refer Figure 13.2.

Flue gas, 100 mol ,

Water, w mol

Methane, x mol

Oxygen, y mol

Figure 13.2 Sketch for Example 13.18 .

Carbon balance:
Carbon present in the flue gas = 96.2 mol
x = 96.2, or methane supplied = 96.2 mol
Hydrogen balance:
Hydrogen in the flue gas = 11.7 + 2 x 82.6 = 176.9 mol
2x = 176.9 + w
That is,
w = 2 x 96.2 - 176.9 = 15.5 mol
or the water formed on combustion is 15.5 mol.
 Energy Balance: Thermochemistry 491

Oxygen balance:
Oxygen present in the water = !4 (15.5) = 7.75 mol
Oxygen in the dry flue gas = 1.9 + !4 (11.7) + 3.8 = 11.55 mol
y = 7.75 + 11.55 = 19.3 mol
Thus, the amount of oxygen supplied is 19.3 mol.
The enthalpy change accompanying the cooling of the reactants:
19.3 mol oxygen is cooled from 573 K to 298 K and 96.2 mol methane is cooled from
673 K to 298 K . Therefore,
T
A//1 = Z f ' nfPldT
Reactants T
*

= 19.3 x 30.5 x (298 - 573) + 96.2 x 45.9 x (298 - 673)

= - 1.817721 x 106 J = - 1817.721 kJ
The heat of reaction is obtained as the sum of the heat liberated in the first reaction which
forms formaldehyde and the heat liberated in the combustion of methane to carbon dioxide.
A H 2 = 11.7 x (- 282.926) + 1.9 x (- 802.372) = - 4834.74 kJ
The products of combustion are C02 1.9 mol, CH 20 11.7 mol, 02 3.8 mol, CH4 82.6 mol and
water vapour 15.5 mol. Enthalpy change for heating the products to 873 K :

A H3 = Z [ Ti ^ C p^ d T
Products J

A H 3 = (1.9x 46.3 + 11.7 x 47.1 + 3.8 x 31.9 + 82.6 x 51.4 + 15.5 x 36.3)(873 - 298)
= 3.2019 x 106 J = 3201.9 kJ
Now the heat evolved or absorbed under the specified conditions is

A H ® = AHy + AH 2 + AH 3
= - 1817.721 - 4834.74 + 3201.9 = - 3450.56 kJ
The amount of formaldehyde produced is
11.7 mol = 11.7 x 30.016 = 351.19 g
The amount of heat to be removed per 1000 kg of formaldehyde produced is
3450 56
x 1000 = 9.8055 x 106 kJ
0.35119

13.2.1 Temperature of Reaction

If no heat is added to the system from the surroundings or no heat is removed from the system
during a reaction, the reaction can be termed an adiabatic reaction . Adiabatic conditions can
492 Stoichiometry and Process Calculations

be achieved by insulating the reaction vessel. In the case of combustion or explosions, the heat
is generated so rapidly that it is generally impossible to transfer the heat away, and as a
consequence, the adiabatic conditions are achieved naturally. The heat liberated during the
reaction will be utilized completely to increase the enthalpy of the products. In contrast, in an
isothermal reaction either heat is added to or heat is removed from the system to maintain the
temperature constant.
When the products get heated up utilizing the heat liberated during the reaction , the
temperature attained is termed the temperature of the reaction. In the case of adiabatic reactions,
this temperature is the adiabatic reaction temperature . When a fuel is burned in air or oxygen
under adiabatic conditions the heat of reaction is the heat of combustion and the temperature
attained by the system is known as the adiabatic flame temperature . The temperature attained
by the products of combustion when the unit quantity of a fuel is burned depends on the amount
of oxygen supplied as well as whether the oxygen is supplied as air or as pure oxygen . The
maximum adiabatic flame temperature is attained when the fuel is burned in theoretically
required amount of pure oxygen, and when there is no heat loss to the surroundings. This
maximum temperature is also known as the theoretical flame temperature . The adiabatic flame
temperature attained, when the fuel is burned in air or excess oxygen, is less than the theoretical
maximum flame temperature attained in oxygen.
Denoting as before, the enthalpy of cooling the reactants from temperature Tx to 298 K by
AHi and the enthalpy of heating the products from 298 to T, the adiabatic flame temperature
by A//2, we can write
AH = AHl + A// 29g + AH 2
Here AH is the difference between the enthalpy of products and the enthalpy of reactants, or
simply, the heat added or removed during the reaction. For an adiabatic reaction, this quantity
is zero, and therefore,
AH 2 = - AHX - Atf °98 ( 13.19)
Equation (13.19) may be used to evaluate the temperature attained in an adiabatic reaction.

EXAMPLE 13.19 Ammonia is produced by the following reaction

N2 + 3H 2 2NH3
In a commercial process for ammonia production, the feed to an adiabatic reactor contains
1 kmol/s of nitrogen and stoichiometric amounts of hydrogen at 700 K . What is the maximum
allowable conversion in the reactor, if the adiabatic temperature rise across the reactor should
not exceed 100 K.
Assume the feed and product streams to be ideal gas mixtures. The heat of reaction
at 700 K for the above reaction is calculated to be - 94.2 kJ/mol . The mean molar heat
capacities in the range of 700-800 K are 0.03, 0.0289, and 0.0492 kJ/mol K for nitrogen,
hydrogen and ammonia, respectively.
Solution Basis: Feed consisting of 1 kmol/s nitrogen and 3 kmol/s hydrogen
Let x be the fraction of nitrogen converted . Since the heat of reaction at 700 K is - 94.2
kJ/mol, the heat liberated by the reaction is - 94.2 x 103x kJ. The product stream consists of
 Energy Balance: Thermochemistry 493

2x kmol NH3, (1 - x ) kmol N2 and 3(1 - x) kmol hydrogen. When the temperature of the
product stream rises by 100 K, the heat utilized is
(1 - x ) x 0.03 x103 x 100 + 3(1 - JC) x 0.0289 x 103
x 100 + 2x x 0.0492 x 103 x 100 kJ
= 11.67 x 103 - 1.83 x 103;c kJ
Since the reaction is adiabatic, the only heat available for raising the temperature of the products
is the heat liberated by the reaction which is 94.2 x 103x kJ. Therefore,
11.67 x 103 - 1.83 x 103x = 94.2 x \ 03x
On solving this equation, we get x = 0.1215. It means that the maximum conversion for nitrogen
should be 13.15 % if the temperature rise permitted is 100 K.

EXAMPLE 13.20 Calculate the adiabatic flame temperature for CO when burned with 100
percent excess air when both the reactants are at 373 K. The heat capacities (J/mol K) may
be assumed constant at 29.23 for CO, 34.83 for 02, 33.03 for N2 and 53.59 for C02. The
standard heat of combustion at 298 K is - 282.99 kJ/mol CO.
Solution Basis: 1 mol CO .

CO H
2
02 ^ C02
Reactants: 02 = 1 mol; N2 = 3.76 mol; CO = 1 mol
Products: 02 = 0.5 mol; N2 = 3.76 mol; C02 = 1 mol

AHi = (1 x 34.83 + 3.76 x 33.03 + 1 x 29.23 )(298 - 373) = - 14 119 J

AH2 = (0.5 x 34.83 + 3.76 x 33.03 + 1 x 53.59)( T - 298) = 195.20 T - 58 169
where T is the adiabatic flame temperature.
Using Eq . ( 13.19),
195.20 T - 58 169 = 14 119 + 282 990
Solving this, we get the flame temperature as T = 1820.1 K.

EXAMPLE 13.21 Hydrogen gas is burned in an adiabatic reactor with two times the theo-
retical quantity of air, both air and hydrogen being at 298 K initially. What will be the tempera-
ture of the reaction products? The standard heat of formation of gaseous water is - 241.826
kJ/mol . The heat capacities (kJ/kmol K ) of the gases are given below:
Water vapour: CP = 30.475 + 9.652 x 10 3 T + 1.189 x 10 672
" "

Nitrogen: CP = 27.034 + 5.815 x 10-3 r - 0.2889 x 10 6 T 2 -

Oxygen: CP = 25.611 + 13.260 x 10 3 r - 4.2077 x 10 6 r 2

- -

Solution Basis: 1 kmol hydrogen burned. The theoretical requirement of oxygen is 0.5 kmol.
The amount of oxygen supplied = 2 x 0.5 = 1 mol
The amount of air supplied = lx = 4.762 kmol
21
494 Stoichiometry and Process Calculations

The amount of nitrogen in the air supplied = 4.762 - 1 = 3.762 kmol

Reactants: Hydrogen = 1 kmol, Air = 4.762 kmol
Products: Water vapour = 1 kmol, Oxygen = 1 - 0.5 = 0.5 kmol , Nitrogen = 3.762 kmol
Let T be the temperature attained.
Ix (30.475 + 9.652 xl 0 37’ + 1.189 xl 0 6 r 2 )
“ “

Then AH2 r
J 298
_3
+ 0.5 x ( 27.034 + 5.815 x 10 r - 0.2889 x 10 T )
+ 3.762 25.611 + 13.260 xl 0 r 4.2077 10 r
x ( 3
-
“

x
~6 2
6 2
)
dT
“

T
(140.34 + 62.444 x 10 3 T - 14.785 x 10 6 T 2 ) dT
“ ~

298

= 140.34(r - 298 ) +
62.444 xlO-3 , *2
(T
_ - 29802" )x -
14.785 xlO-6 3 -
(T 2983 )
2 3
= 140.34 T + 31.222 x 10-3 r2 - 4.928 x 10 "
6 r 2 - 44 463.54 kJ

The standard heat of reaction at 298 K, AH %9 S = - 241.826 xl 03 kJ .

Let us use Eq. (13.19), i.e.
AH 2 = - AHx - AH 298
Since AH { = 0, we have
140.34 T + 31.222 x 10 -3 r2 - 4.928
x 10-6 r3 - 44 463.54 = 241.826 x 103 kJ
On solving this equation, we get T = 1609.8 K.

EXERCISES
Standard heat of reaction and Hess's law
13.1 Using Hess’s law evaluate the heat of formation of solid CaC03. The following data
are available:

02 (g) — > CaO (s)

Ca (s) + —

C (s ) + 02(g) -4 C02 (g)

A77
^°
98

AH 2 gs
= -635.77 kJ

= - 393.51 kJ
CaO (s) + C02 (g ) -» CaC03(s) AH ?g 8 = -178.15 kJ
13.2 The heats of combustion of gaseous benzene, gaseous cyclohexane (C6H 12 ), and
hydrogen are respectively - 3287.4, - 3949.2 and - 285.58 kJ. Calculate the heat of
reaction for the hydrogenation of benzene to cyclohexane.
13.3 The standard heats of combustion of gaseous ethane and acetaldehyde are - 1559.9 kJ/
kmol and - 1192.36 kj/kmol respectively. The heat of vaporization of water at 298 K
is 44.014 kJ/mol. Calculate the heat of oxidation of gaseous ethane to acetaldehyde.
 Energy Balance: Thermochemistry 495

13.4 Find the standard heat of formation of methyl chloride from the following data:
3
C02 (g) + H20 (1) + HCl (aq) CH3Cl (g) + - 02 + aq AH 0 = 765.4 kJ
C (s ) + 02 (g) -4 C02 (g) AH 0 = -393.51 kJ

H2 (g) +

^ o2 (g) -4 H20 (1) AH 0 = - 285.84 kJ

^ H 2 (g) + ~
Cl 2 (g)
HCl (g) + aq -» HCl (aq)
-4 HCl (g) AH 0 =
AH 0 =
13.5 Using Hess’s law, calculate the heat of formation of chloroform ( CHC13) with the help
of the following data:
-

-
92.31 kJ
75.2 kJ

CHCl3 (g) +

^ ^ 02 (g)

H 2 (g ) +

C (s) +
+ H20 (1) -> C02 (g) + 3HCl (g)

02 (g) -> H20 (1)

02 (g) -» C02 (g)
AH

AH °9 S =

A // 298
°9S = - 281.67

- 285.84

= - 393.51
kJ

kJ
kJ

^ H 2 ( g) +

C(s) +
~
Cl 2 (g) -4 HCl (g)

02 (g) -» C02 (g) AH ,. =

Atf °98
13.6 Heats of reactions were measured experimentally for the following reactions as given
below :
-
= - 92.311

393.51 kJ/mol
kJ

CO (g) + —1 02(g) -» C02 (g) AHr = - 282.99 kJ/mol

Use the above data to calculate the heat of formation of CO, which is difficult to
measure experimentally.
13.7 Calculate the heat of formation of methane gas from the following heat of combustion
data :

CH4 (g) + 202 (g) -4 C02 (g) + 2H20 (1) AHn98 = - 890.4 kJ
C (s) + 02 (g) -4 C02 (g) A// 298 = - 393.51 kJ

H 2 (g) +

Heat of combustion ^ 02 (g) -4 H20 (1) A// 2°98 = - 285.84

13.8 The heats of combustion of solid carbon and gaseous CO are respectively - 393.51 kJ/mol
kJ

and - 282.99 kJ/mol. Determine the heat of formation of CO.

496 Stoichiometry and Process Calculations

13.9 Bituminous coal with a calorific value of 20000 kJ/kg is used for generating steam in
a boiler. The efficiency of combustion is 75%. Assume that coal contains 67% carbon
and 33% ash. (a ) How much coal has to be burned to generate 1 MW of energy?
(b) How much air is needed if 50% excess air is to be used?
13.10 Calculate the gross and net heating value (kJ/m3 at STP) of a fuel gas analyzing 80%
methane, 10% ethane, 6% propane and 4% butane. The standard heats of combustion
are -890.4, -1559.9, -2220, -2878.52 kJ/mol, respectively, for methane, ethane, propane,
and butane, and the latent heat of vaporization of water at 298 k is 44.014 kJ/mol.
13.11 Hydrocarbon fuels can be produced from methanol by reactions such as the following:
6CH 3OH (g) -> C6H 12 (g) + 6 H20 (g) AH % = - 142.216 kJ
Compare the standard heat of combustion at 298 K of CH 3OH (g ) with the standard
heat of combustion at 298 K of C6H12 (g), reaction products in both cases being
C02 (g) and H20 (g ).

Heat of formation
13.12 Calculate the standard heat of reaction at 298 K for the following reaction :
4HC1 (g) + 02 (g) 2 H20 (g ) + 2Cl 2 (g)
The standard heats of formation are - 92.311 kJ/mol for HCl (g) and - 241.826 kJ/mol
for H20 (g).
13.13 Calculate the heat of reaction for the following reaction:
4NH3 (g) + 502 (g) 4NO (g ) + 6H20 (g )
The heat of formation data are as follows:
NH3 = - 46.191 kJ/mol ; NO = 90.374 kJ/mol; H20 (g) = - 241.826 kJ/mol
13.14 Calculate the standard heat of reaction for the following:

2FeS2 (s) + y 02 (g) Fe203 (s) + 4S02 (g)

The standard heats of formation at 298 K are -178.02 kJ/mol for FeS2 ( s ), -822.71
kJ /mol for Fe203 (s) and - 296.9 kJ/mol for S02 (g).
13.15 If the standard heat of formation of H20 (1) is - 285.84 kJ/ mol and the heat of
vaporization of water is 44.01 kJ/mol, what is the standard heat of formation of
H20 (g)?
13.16 The heat of formation in kJ/ mol of C3H 8 ( g), C 02( g) and H20(g) are , respectively,
-103.85, - 393.51 and -241.826. Estimate the heat of reaction in the standard state for

the following:
C3H 8 (1) + 502 (g) 3C02 (g) + 4H20 (1)
The heats of vaporization at 298 K in kJ/mol are 16.00 and 44.04, respectively, for
C 3H8 and H20 .
 Energy Balance: Thermochemistry 497

13.17 The standard heat of combustion of benzene at 298 K is - 3267.6 kJ/mol when burned
completely to C 02 and liquid water. The standard heat of combustion of hydrogen to
liquid water is - 285.84 kJ/mol and that of carbon to carbon dioxide is - 393.51 kJ/mol.
Calculate the standard heat of formation of liquid benzene.
13.18 Calculate the standard heat of formation of 1-butene if the standard heat of combustion
is - 2720.4 kJ /mol and the heats of formation of gaseous C02 and liquid water are
- 393.51 kJ/mol and - 286.03 kJ/mol respectively.

13.19 In the production of ethylene from ethane and propane, the following yields were
found:
Reaction Percent of reactant
proceeding by the reaction
C2H6 -> C2H4 + H 2 100
C 3 H 8 -> C2H4 + CH4 60
C 3 H 8 -> C3 H6 + H 2 40
Calculate the standard heat of reaction for a mixture consisting of equimolar amounts
of ethane and propane, given the following heat of formation in kJ/mol:
C 2H6 (g): - 84.667, C 3H8: - 103.85, C2H4: 52.283, CH4: - 74.84, C 3H6 (g): 20.41
13.20 An iron pyrite ore containing 85.0% FeS2 and 15.0% gangue is roasted with 200%
excess air according to the reaction
4FeS2 + 1102 -> 2Fe203 + 8S02
in order to produce S02. The cinder analyzed 5.0% FeS2. Determine the standard heat
of reaction per kilogram of ore. The standard heat of formation data (kJ/mol ) are as
follows: FeS2 (s) = - 177.9, Fe203 (s) = - 822.156, S02 (g) = - 296.90.
13.21 Calculate the standard heat of reaction for the following:
NH 3 + HC1 (g) -> NH 4C1 ( S )
The standard heats of formation of ammonia, hydrogen chloride and ammonium chloride
are - 46.2 KJ, - 92.4 kJ and - 315.6 kJ respectively.
13.22 Calculate the standard heat of the following reaction:
1
2 FeO (s) + - 02 -> Fe203(s)

The standard heat of formation of FeO (s) and Fe203 (s) are - 268.1 kJ and - 822.7 kJ,
respectively.

Heat of reaction at constant pressure and constant volume

13.23 What would be the heat of reaction at constant pressure for the following reaction if
the heat evolved under constant volume conditions is 111.760 kJ/ mol at 298 K.

C+ Io 2 ^ CO (g)
498 Stoichiometry and Process Calculations

13.24 Calculate the heat of reaction at constant volume at 298 K for the following gas phase
reaction:
C2 H4 (g ) + 2 H 2 (g) -> 2CH4 (g)
The standard heat of formation at 298 K is 52.283 kJ/ mol for gaseous ethylene and
- 74.84 kJ/mol for gaseous methane .

13.25 The standard heat of combustion of liquid benzene at 298 K is - 3269.8 kJ/mol. 2.5 g
of liquid benzene is placed in a bomb calorimeter at 298 K. The water equivalent of
the bomb and surrounding water is 18.4 kJ /K. Determine the rise in temperature of
water assuming all water formed on the combustion of benzene is condensed.

Effect of temperature on standard heat of reaction

13.26 Calculate the heat of combustion of methane at 800 K given that the heat of combus-
tion at 298 K is - 890.4 kJ/mol and the mean heat capacity in the temperature range
of 298 to 800 K are 41.868 J/mol K, 30.563 J/mol K, 41.449 J/mol K and 34.332 J/mol K
for methane, oxygen, C02 and water vapour respectively.
13.27 Calculate the constant pressure and constant volume heat requirements of a catalytic
reactor oxidizing methanol to formaldehyde at 775 K using air according to the following
reaction:

CH3OH (g ) + -02 (g ) -» HCHO (g ) + H 20 (g ) AH ° gs = -156.67 kJ/mol

2
The reactants are admitted in stoichiometric proportions, and methanol is completely
converted to formaldehyde. The enthalpies of methanol and formaldehyde vapours at
775 K relative to 298 K are 29.84 kJ /mol and 21.44 kJ / mol, respectively. The mean
heat capacities of air, nitrogen and water vapour are, respectively, 30.3 kJ / kmol ,
30.0 kJ / kmol and 35.76 kJ /kmol.
13.28 CO at 1000 K is burned with 90 percent excess air at 800 K. The products of
combustion leave the reaction chamber at 1250 K. Calculate the heat evolved in the
reaction chamber per kmol of CO burned. The standard heat of reaction at 298 K is
- 282.99 kJ/mol CO. The mean specific heat applicable in the temperature range of this

problem are 29.38, 49.91, 33.13 and 31.43 J/mol K for CO, C02, 02 and N 2 respectively.
13.29 Carbon monoxide at 473 K is burned at a rate of 1 kmol/h in a furnace using 100%
excess air at 373 K. The combustion is complete and the gases leave at 1273 K.
Calculate the heat removed in the furnace . The mean heat capacity values in
kJ / kmol K in the temperature range of 298 to 1273 K are 49.91, 33.25, 31.43, 29.29,
and 29.38 for C02, 02, N2, air and CO, respectively. The standard heat of combustion
of CO at 298 K is - 282.99 kJ/mol.
13.30 Hydrochloric acid is produced from chlorine according to the following reaction:

Cl 2 + H20 -> 2 HC1 +

^ 02
The standard heats of formation at 298 K are - 241.826, - 92.311 kJ / mol for water
vapour and hydrochloric acid respectively. Determine the amount of heat to be added
 Energy Balance: Thermochemistry 499

or to be removed per kmol of acid obtained if the reactants enter at 500 K with a ratio
of 3 mol steam per mol chlorine, reaction goes to completion , and the products leave
at 500 K. The mean specific heats of chlorine gas, oxygen and HC1 may be taken as
35.0, 33.0, 40.0 J/ mol K respectively, and enthalpies of saturated water vapour at
298 K and 500 K are 2547 kJ/kg and 2801 kJ/kg respectively.
13.31 Ammonia oxidation occurs as per the reaction
4NH3 (g ) + 502 (g) -» 4NO (g) + 6H20 (g) AH °R = - 226 kJ/mol NO
The reactor is fed at a rate of 100 mol/h ammonia and 200 mol/h oxygen, both at
298 K. The product leaves the reactor at 575 K . Given the following heat capacity data
at 575 K , calculate the heat transferred from the reactor : 02 = 30.8 kJ /kmol
K , NO = 30.74 kJ/kmol K and H20 = 34.8 kJ /kmol K.
13.32 The standard heat of reaction at 298 K for the following reaction is -42.433 kJ.
C 2 H4 (g) + H20 (g) -> C2H5OH (g)
Calculate the heat of reaction at 400 K given that the constants in the heat capacity
equation CP = a + flT + yT 2 are as given below: (CP is in J/mol K and T in K ).

a P r
3 x 10 6
C2H4 11.85 119.75 x 10 -
- 36.53 -

H2O 30.38 9.62 x 10 3

“

+ 1.19 x 10
C2H5OH 29.27 166.39 x 103 - 49.93 x lO "6

13.33 For the following reaction the standard heat of reaction at 298 K is - 164.987 kJ.
C02 (g) + 4H 2 (g ) -> 2 H20 (g ) + CH4 (g )
The constants in the heat capacity (J/mol K) equation are given below:

a P r
C02 26.75 42.26 x 103 - 14.25 x 10 6
-

H2 26.88 4.35 x 103 - 0.33 x 10 6

-

H 2O 29.16 14.49 x 103 - 2.02 x 10 6

-

CH4 13.41 77.03 x 10 3 - 18.74 x 10 6

Calculate the standard heat of reaction at 773 K.

13.34 For the following gas-phase reaction, determine the heat of reaction if the reactants
enter and products leave at 800 K.
C02 + 4H2 -> 2 H20 + CH4
The standard heats of formation are - 393.51 kJ/mol for C02, - 241.826 kJ/mol for
H20 (g ) and - 74.84 kJ / mol for CH4. The constants in the heat capacity equation
CP = a + bT + cT 2
are given below where CP is in kJ/ kmol K and T in K.
500 Stoichiometry and Process Calculations

a bx 103 c x 106
Carbon dioxide 26.540 42.454 - 14.2979
Hydrogen 29.082 - 0.821 1.9917
Methane 13.415 77.079 - 18.7569

Water vapour 30.38 9.62 - 1.19

13.35 Methane is burned in a furnace with 100% excess air to generate steam in a boiler.
Methane and dry air enter the combustion chamber at 500 K and the product leaves the
furnace at 1200 K. If the effluent gases contain only C02, 02, H20 and N2, how much
heat is absorbed by water per kg of methane burned?
The standard heat of combustion of methane at 298 K is -890.4 kJ / mol. The latent
heat of vaporization of water at 298 K is 44.014 kJ/mol . The constants in the heat
capacity equation CP = a + bT + cT 2 where CP is in kJ /kmol and T in K are as follows:

a bx 103 c x 106
Water 30.38 9.62 1.19
Carbon dioxide 26.540 42.454 - 14.2979
Methane 13.415 77.079 - 18.7569
Nitrogen 27.034 5.815 - 0.2889

Oxygen 25.611 13.260 - 4.2077

13.36 The standard heat of combustion of graphite at 298 K is -393.51 kJ/mol. Determine
the heat of combustion at 800 K. The heat capacities in J/mol K are given as follows:

27 - 4 894 2
~ '
xlQ
Carbon: 11.19 + 1.096 xl 0
T

Oxygen: 34.62 + 1.08 xlO “ 3

r-
^p2L
2 8 185 x 105
Carbon dioxide: 43.29 + 1.147 x 10 T
rj-T Z

13.37 Calculate the heat of the following gas-phase reaction

2
—
H 2 + — 02 > H 20 Atf 298 = - 241.826 kJ

if the reactants are at 473 K and the product is at 993 K. The specific heats (J/mol K)
may be evaluated using the data given below:
CP = a + pT + yT 2

a P r
H2 29.09 - 8.374x 10^ 2.0139 x lO 6 "

02 25.74 12.987 x 10 3 “
- 3.864 x 10 6 “

H2O 30.38 9.621 x lO 3 "

- 1.185 x 10-6
 Energy Balance: Thermochemistry 501

13.38 A gaseous mixture at 600 K and 1 bar consisting of methane and steam in the ratio
1 : 2 by mole is sent to a catalytic reformer where the following reaction occurs.
CH4 (g ) + H20 (g) -> CO (g) + 3H2 (g) AH °29% = 206.284 kJ
The following side reaction may also occur:
CO (g) + H20 (g ) -4 C02 (g ) + H2 (g) A ° = - 41.20 kJ
298

Methane is completely converted during the reaction and the product stream contains
17.4% (mol) CO. Heat is supplied in the reactor so that the products reach a temperature
of 1300 K. The mean heat capacities in the temperature range of 298-600 K are 43.8
kJ/kmol K for methane and 34.8 kJ/kmol K for steam, and the mean heat capacities
in the temperature range of 298-1300 K are 31.8 kJ/kmol K for CO, 29.8 kJ/kmol K
for hydrogen, 50.1 kJ/kmol K for C02 and 38.9 kJ / kmol K for steam, respectively.
Calculate the heat requirement for the reactor per kmol methane.
13.39 0.5 mol hydrogen at 300 K, a mixture of 1.5 mol nitrogen and 0.5 mol oxygen at
400 K, and 0.3 mol CO at 500 K are mixed. 50 percent of CO present reacts. If the
final temperature of the system raises to 882 K under adiabatic conditions, calculate
the standard heat of formation of C02, if it is four times the standard heat of formation
of CO. The mean heat capacities in J/mol K are 32.5 for 02, 31.1 for N2, 29.0 for
H 2, 31.0 for CO, and 49.0 for C02.
13.40 A gas with the analysis 8.5% S02, 2.0% S03, 9.5% 02 and 80% N 2 is admitted to
a catalytic converter where S02 gets converted to S03. The outlet gases contain
82.47% N2. The reaction occurs at 700 K. Determine the heat evolved per 100 mol gas
entering the converter. The data given are: heat of formation of S03 at 298 K = - 395.72
kJ/mol, heat of formation of S02 at 298 K = - 296.9 kJ / mol, mean heat capacity of
S03 = 51.6 J /mol K, mean heat capacity of S02 = 45.7 J/mol K, mean heat capacity
of 02 = 32.5 J/mol K.
13.41 Calculate the standard heat of reaction at 800 K for the combustion of pentane gas
given that the mean heat capacities in J/mol K are 247 for C5 H 12, 33.62 for 02, 52.32
for C 02, and 38.49 for H20. The standard heat of combustion at 298 K is - 3271.67
kJ /mol .
13.42 Sulphur dioxide gas is oxidized in 100% excess air with 80% conversion to sulphur
trioxide. The gases enter the converter at 673 K and leave at 723 K . The mean heat
capacities are 45, 51, 32 and 31 J/mol K for S02, S03, 02, and N2 respectively, and
the standard heat of reaction is - 98.8 kJ/mol. How much heat is absorbed in the heat
exchanger of the converter per kilomole of S02 introduced?
13.43 In a fermentation process, sucrose (C12H22On ) is used as a nutrient and is oxidized
to C02 gas and H20 liquid . Calculate the heat of oxidation at 318 K in this fermentation.
The standard heat of combustion of sucrose at 298 K = - 5648.8 kJ/mol. Mean heat
capacities are 1.25 kJ/kg K for sucrose (s), 4.20 kJ/kg K for H20 (1), 29.38 J/mol K
for 02 and 37.55 J/mol K for C02.
502 Stoichiometry and Process Calculations

13.44 Pure CO is mixed with 100% excess air and burned . Only 80% of CO bums. The
reactants are at 373 K and the products at 573 K. Calculate the amount of heat to be
added or removed per kmol of CO fed to the reactor. Standard heats of formation in
kJ /mol at 298 K are - 110.6 for CO and - 393.51 for C02 . The mean molal heat
capacity between 298 K and T K in kJ/kmol K are

Gas T = 373 K T = 573 K

CD 29.22 30.61
C02 43.77
o2 29.84 30.99
N2 29.17 29.66

13.45 An internal combustion engine uses octane as fuel. The air and fuel vapour mixture
enter the engine at 298 K. 20 percent excess air is supplied . 75 percent of the carbon
present in the fuel is converted to C02 and the rest to CO, and the combustion
products leave the engine at 800 K. Calculate the energy transferred as heat to the
engine per kg of fuel burned . The mean heat capacities in J/mol K are 32.5 for 02,
31.1 for N 2, 31.0 for CO, 50.0 for H20 and 49.0 for C02. The heat of formation of
^-octane, C02, CO and H20 vapour at 298 K are - 208.75 kJ/mol, - 393.51 kJ/mol,
- 110.6 kJ/ mol and - 241.826 kJ/mol respectively.

13.46 A mixture of methane and steam at 600 K in the ratio 1 :2 is sent to the reactor where
the following reaction occurs:
CH 4 (g) + H20 (g) -4 CO (g) + 3H2 (g) AH % = 205.813 kJ
The following undesired side reaction also occurs:
CO (g) + H20 (g) -> C 02 (g) + H2 (g) A // 298 = - 41.198 kJ
Methane is completely converted and the products contain 15.0% (mole) CO. If the
products get heated to 1300 K, determine the quantity of heat supplied per mole of
methane. The following mean heat capacity values (J/mol K) are applicable— methane:
43.79, steam: 34.83, CO: 31.82, H2: 29.81 and C02: 50.12.
13.47 One hundred kilograms per hour of dry pyrites at 298 K containing 85% FeS2 and the
rest inert gangue is burned with dry air in a plant for the manufacture of sulphuric acid.
4FeS2 + 1102 — » 2Fe203 + 8S02
4FeS2 + 1502 — > 2Fe203 + 8S03
The cinder is at 800 K and contains 5% sulphur as FeS2. Burner gas at 800 K contains
10% S02, 7.0% 02 and 83% N2 on S03-free basis. Standard heats of reaction are
- 827.1 kJ for the first reaction and - 1023.7 kJ for the second reaction. The heat

capacity of the cinder is 0.75 kJ /kg K. The mean heat capacities in kJ / kmol K are 50.2
for S03, 46.9 for S02, 31.4 for 02 and 29.9 for N2. The pressure is 101.3 kPa.
Calculate the following:
 Energy Balance: Thermochemistry 503

( a ) The amount of FeS2 lost in the cinder, kg/h

( b ) The amount of burner gas, m3/h
(c) The amount of heat dissipated in the burner, kJ/h
13.48 Vinyl chloride is manufactured by the pyrolysis of l ,2,dichloroethane at 773 K.
C2H4C12 (g) -4 C2H3C1 (g ) + HC1 (g) AH °r = 70.224 kJ
The conversion is estimated to be 55%. How much heat is to be supplied to produce
500 kg/h of vinyl chloride from a feed of pure liquid dichloroethane at 290 K ? The
specific heat in kJ/kmol K is represented by the equation CP = a + bT + cT 2 + dT 3,
with the following values for the constants:

Component a b x 102 c x 105 dx 109

Vinyl chloride 5.94 20.16 - 15.34 47.65
HC1 30.28 - 0.761 1.325 - 4.305

Dichloroethane 20.45 23.07 - 14.36 33.83

Take the specific heat of liquid dichloroethane to be 116 kJ/kmol K, which is constant
and the latent heat of vaporization at 298 K is 34300 kJ/kmol .

Temperature of reaction
13.49 Calculate the maximum flame temperature attained when methane is burned with
theoretical air when both fuel and air are at 298 K initially. The mean heat
capacities in J / mol K are 62.75 for C02, 52.96 for H20, 38.67 for 02 and 37.13 for
N 2. The standard heat of combustion of methane at 298 K is - 890.4 kJ/mol .
13.50 A gas mixture consisting of 20% ethane and 80% oxygen at 298 K is burned com-
pletely after diluting it with double the volume of C02, also at 298 K. The mean heat
capacities in J/mol K are 54.56 for C 02, 43.02 for water vapour and 35.52 for oxygen.
The standard heat of reaction is - 1428 kJ/mol of ethane at 298 K. Determine the
theoretical flame temperature.
13.51 Calculate the theoretical flame temperature for a gas containing 25% CO and 75% N2
when burned with 100% excess air when both the reactants are at 298 K . The standard
heat of formation are - 393. 51 kJ/mol for C02 and - 110.6 kJ/mol for CO. The mean
molar specific heats in J/ mol K are

T (K ) noNJ o2 N2
800 45.43 31.59 30.31
1000 47.56 32.37 30.64
1200 49.35 33.02 31.22
1400 50.82 33.60 31.77
1600 51.99 34.05 32.25
1800 53.18 34.40 32.65
504 Stoichiometry and Process Calculations

13.52 Dry methane is burned with dry air. Both are at 298 K initially. The flame temperature
is 1573 K. If complete combustion is assumed, how much excess air is used?
CH4 + 202 -> C 02 + 2 H20
Standard heat of reaction is - 8.028 x 105 J/mole of methane reacted. Mean molal heat
capacities of gases between 298 K and 1573 K in J/mol K are: 51.88 for C02, 34.01
for 02, 40.45 for H20, and 32.21 for N2.
13.53 The dehydrogenation of butene is an endothermic reaction:
C4H8 (g) C4H6 (g) + H2 (g)
This reaction is to be carried out adiabatically and at atmospheric pressure, and in order
to minimize the temperature drop, the reactor feed will consist of 10 moles of steam
per mole of butene. The steam is unreactive. 20% of butene is converted. The feed
mixture enters the reactor at 900 K. Calculate the temperature of the products if mean
molar heat capacity in kJ/kmol K for the temperature range of 298 to 900 K are 148.7,
131.2, 36.6, and 29.4 for butene, butadiene, steam and hydrogen respectively. The standard
heats of formation are - 0.54 kJ/mol for butene and 109.24 kJ/mol for butadiene.
13.54 Calculate the theoretical flame temperature of a gas mixture consisting of 20% CO and
80% N 2 when burned with 100% excess air, both air and gas initially being at 298 K.
The standard heat of reaction at 298 K is - 282.99 kJ/mol CO. The heat capacities in
J /mol K are given by CP = a + [iT + yT 2 where the values of the constants are given
as follows:

a P r
co2 26.54 42.45 x 10 “ 3 - 14.298 x 10-6
02 25.61 13.26 x 10 3
“
- 4.208 x 10 6
“

N2 27.03 5.815 x 10 3 “
- 0.289 x 10 6 “

13.55 Calculate the adiabatic reaction temperature for complete combustion of ethyl alcohol
with 25% excess air. The alcohol and air are supplied at 298 K, and the water formed
is in the vapour state. The standard heat of combustion of alcohol is - 1366.91 kJ/mol,
the latent heat of vaporization of water is 44 kJ/mol, and heat capacities in kJ/kmol K
where T is in K are:
co2 24.55 + 0.0423 T
H2O 31.57 + 0.0069 T
02 25.90 + 0.01167
N2 28.40 + 0.00227
13.56 Aluminium metal powder is investigated as a fuel source for jet engines. Calculate the
theoretical flame temperature when aluminium metal is burned with 100% excess air.
Assume that the air and metal powder enter at 25°C and that combustion is complete.
Heat capacities in kJ/ kg are 140.26 for Al203 (s) and 142.35 for A1203 (1). The heat of
fusion of A1203 is 108.857 kJ /mol. The standard heat of formation of Al 203 (s ) is
- 1670.91 kJ/mol . The heat capacities of gases in J /mol K are as follows:
 Energy Balance: Thermochemistry 505

Cp ( 02) = 30.255 + 4.207 x 10 ~

r - 1.8873 x 105 r2
3

Cp ( N 2) = 27.270 + 4.930 x 10 3 r - 3.3256 x 104 r2

"

13.57 The catalytic converter in a sulphuric acid plant is supplied with a gas mixture analyzing
7.8% S02, 11.0% 02 and 81.2% N2, which enters the converter at a temperature of
675 K where 80% of S02 is oxidized to S03 by combination with the oxygen present
in the gases. Assume that there is no heat losses from the reactor. Calculate the
temperature of the gas leaving the converter.
Standard heats of formation at 298 K in kJ /mol are: S02 = -296.9 and S03 =
-395.72. The heat capacities in kJ /kmol K and T in K are as follows:

Gas a b x 103 c x 106

Nitrogen 27.034 5.815 - 0.2889
Oxygen 25.611 13.260 - 4.2077
Sulphur dioxide 29.077 41.910 - 15.8847

Sulphur trioxide 31.208 80.093 - 27.7501

13.58 Methane is burned with 20 percent excess air, both methane and air being at 298 K.
The standard heat of combustion of methane at 298 K is - 890.4 kJ. The heat capacities
in J/mol K are as follows:
CP(CH4) = 14.150 + 75.499 x 10 3 r - 17.9915 x lO 6
" "

^
CP( 02) = 30.255 + 4.207 x 10-3 r - 1.8873 x 105 r2
>
C ( N2) = 27.270 + 4.930 x 10 3 T
~

-104 r2
3.3256 x
Cp( C 02) = 45.369 + 8.688 x 10 3 T - 9.6193 x 105 r2
"

Cp{ H20) = 28.850 + 12.055 x 10 Z T - 1.006 x 105 r2

~

Calculate the adiabatic flame temperature attained .

Appendix Tables of Properties

Table A. l Atomic weights of elements, 2001

Atomic number Symbol Name Atomic weight

89 Ac Actinium [227]
13 A1 Aluminium 26.981538(2)
95 Am Americium [243]
51 Sb Antimony 121.760( 1)
18 Ar Argon 39.948( 1)
33 As Arsenic 74.92160(2)
85 At Astatine [210]
56 Ba Barium 137.327(7)
97 Bk Berkelium [247]
4 Be Beryllium 9.012182(3)
83 Bi Bismuth 208.98038(2)
107 Bh Bohrium [264]
5 B Boron 10.811(7)
35 Br Bromine 79.904( 1)
48 Cd Cadmium 112.411(8)
55 Cs Caesium 132.90545(2)
20 Ca Calcium 40.078(4)
98 Cf Californium [251]
6 c Carbon 12.0107(8)
58 Ce Cerium 140.116( 1 )
17 Cl Chlorine 35.453(2)
24 Cr Chromium 51.9961(6)
27 Co Cobalt 58.933200(9 )
29 Cu Copper 63.546(3)
96 Cm Curium [247]
110 Ds Darmstadtium [281]
105 Db Dubnium [262]
(C
< ontd. )

507
508 Appendix: Tables of Properties

Table A. l Atomic weights of elements, 2001 (Contd .)

Atomic number Symbol Name Atomic weight

66 Dy Dysprosium 162.500( 1 )
99 Es Einsteinium [252]
68 Er Erbium 167.259(3)
63 Eu Europium 151.964( 1 )
100 Fm Fermium [257]
9 F Fluorine 18.9984032(5)
87 Fr Francium [223]
64 Gd Gadolinium 157.25( 3)
31 Ga Gallium 69.723( 1)
32 Ge Germanium 72.64( 1 )
79 Au Gold 196.96655(2)
72 Hf Hafnium 178.49(2)
108 Hs Hassium [277]
2 He Helium 4.002602(2)
67 Ho Holmium 164.93032(2 )
1 H Hydrogen 1.00794(7)
49 In Indium 114.818(3 )
53 I Iodine 126.90447(3)
77 Ir Iridium 192.217(3)
26 Fe Iron 55.845( 2)
36 Kr Krypton 83.798(2)
57 La Lanthanum 138.9055(2)
103 Lr Lawrencium [262]
82 Pb Lead 207.2( 1)
3 Li Lithium [6.941( 2)]
71 Lu Lutetium 174.967( 1)
12 Mg Magnesium 24.3050(6)
25 Mn Manganese 54.938049(9)
109 Mt Meitnerium [268]
101 Md Mendelevium [258]
80 Hg Mercury 200.59(2)
42 Mo Molybdenum 95.94(2)
60 Nd Neodymium 144.24(3)
10 Ne Neon 20.1797(6)
93 Np Neptunium [237]
28 Ni Nickel 58.6934(2)
41 Nb Niobium 92.90638(2 )
7 N Nitrogen 14.0067(2)
102 No Nobelium [259]
76 Os Osmium 190.23(3)
8 O Oxygen 15.9994(3)
46 Pd Palladium 106.42( 1)
15 P Phosphorus 30.973761(2)
78 Pt Platinum 195.078(2)
94 Pu Plutonium [244]
84 Po Polonium [209]

(C
< ontd. )
 Appendix: Tables of Properties 509
Table A. l Atomic weights of elements, 2001 (Contd .)

Atomic number Symbol Name Atomic weight

19 K Potassium 39.0983( 1 )
59 Pr Praseodymium 140.90765(2)
61 Pm Promethium [145 ]
91 Pa Protactinium 231.03588( 2 )
88 Ra Radium [226]
86 Rn Radon [222]
75 Re Rhenium 186.207( 1)
45 Rh Rhodium 102.90550( 2)
37 Rb Rubidium 85.4678(3)
44 Ru Ruthenium 101.07(2)
104 Rf Rutherfordium [261]
62 Sm Samarium 150.36(3)
21 Sc Scandium 44.955910(8)
106 Sg Seaborgium [266]
34 Se Selenium 78.96(3)
14 Si Silicon 28.0855(3)
47 Ag Silver 107.8682(2)
11 Na Sodium 22.989770(2)
38 Sr Strontium 87.62( 1 )
16 S Sulfur 32.065(5)
73 Ta Tantalum 180.9479( 1)
43 Tc Technetium [98]
52 Te Tellurium 127.60(3)
65 Tb Terbium 158.92534(2)
81 T1 Thallium 204.3833(2)
90 Th Thorium 232.0381( 1)
69 Tm Thulium 168.93421(2)
50 Sn Tin 118.710(7 )
22 Ti Titanium 47.867( 1)
74 W Tungsten 183.84( 1)
112 Uub Ununbium [285]
116 Uuh Ununhexium
118 Uuo Ununoctium
114 Uuq Ununquadium [289]
111 Uuu Unununium [272]
92 U Uranium 238.02891(3)
23 V Vanadium 50.9415( 1)
54 Xe Xenon 131.293(6)
70 Yb Ytterbium 173.04(3)
39 Y Yttrium 88.90585(2)
30 Zn Zinc 65.409(4)
40 Zr Zirconium 91.224(2)

Note: The value enclosed in brackets, e .g. [289], indicates the mass number of the
longest -lived isotope of the element that has no stable nuclides. A number in parentheses
for, e.g. 91.224( 2 ) indicates the uncertainty in the last digit of the atomic weight .
Reference: Values from the 2001 table of atomic weights, Pure Appl. Chem . , 75,
1107-1122 (2003).
510 Appendix: Tables of Properties

Table A.2 Standard heat of formation and combustion

Compound AH ° (kJ/mol) AH ° (kJ/mol)

Acetic acid (1) 486.2

- - 871.69
Acetaldehyde (g ) 166.4
- - 1192.36
Acetylene (g) 226.75 - 1299.61
Ammonia (g ) - 46.191 - 382.58
Benzene (1) 48.66 - 3267.6
n-Butane (1) - 147.6 - 2855.6
Isobutane (1) - 158.5 - 2849.0
1-Butene ( g) - 0.54 - 2718.58
1,3-Butadiene (g) 109.24 - 2540.8
Calcium oxide (s) - 635.77
Carbon (s, graphite ) 0 - 393.51
Carbon dioxide (g) - 393.51
Carbon disulphide (1) 87.86 - 1075.2
Carbon monoxide ( g) - 110.6 - 282.99
Carbon tetrachloride (1) - 139.5 - 352.2
Ethane ( g) - 84.667 - 1559.9
Ethyl acetate (1) - 442.92 - 2274.48
Ethyl alcohol (1) - 277.63 - 1366.91
Ethylene (g ) 52.283 - 1410.99
Ferric oxide (s) - 822.71
Ferrous sulphide (s) - 178.02
Formaldehyde (g) - 115.89 - 563.46
n-Heptane (1) - 224.4 - 4816.91
n-Hexane (1) - 198.8 - 4163.1
Hydrogen (g) 0 - 285.84
Hydrogen Chloride (g) - 92.311
Hydrogen sulphide (g) - 20.15 - 562.589
Methane (g) - 74.79 - 890.4
Methyl alcohol (1) - 238.64 - 726.55
Methyl chloride (g) - 81.923 - 766.63
Nitric acid (1) - 173.23
Nitric oxide (g) 90.374
Nitrogen dioxide (g) 33.85
n-Pentane ( g) - 146.4 - 3536.15
Phosphorous pentoxide (c) - 1506.0
Propane ( g ) - 103.85 - 2220.0
n-Propyl alcohol (1) - 255.0 - 2068.6
Sodium carbonate (c) - 1130
Sodium chloride (c) - 411.0
Sodium nitrate (s) - 466.68
Sodium sulphate (s) - 1384.5
Sucrose (s) -5648.8
Sulphur dioxide (g) - 296.9
Sulphur trioxide (g ) - 395.18
Sulphuric acid (1) - 811.32
Tolune (1) 11.99 - 3909.9
Water (1) - 285.84
Water (g) - 241.826
 Appendix: Tables of Properties 511
Table A.3 Thermodynamic properties of saturated steam

Specific volume Internal energy Enthalpy Entropy

(
xlO3 (kJ/kg) (kJ/kg) (kJ/kg K)
kg
Pressure Temp. Sat. Sat. Sat. Sat. Sat. Sat. Sat. Sat.
(kPa) (K) liquid vapour liquid vapour liquid vapour liquid vapour

0.6113 273.16 1.000 206140 0.00 2375.30 0.01 2501.40 0.0000 9.1562
1.00 280.13 1.000 129210 29.30 2385.00 29.30 2514.20 0.1059 8.9756
1.50 286.18 1.001 87980 54.71 2393.30 54.71 2525.30 0.1957 8.8279
2.00 290.65 1.001 67000 73.48 2399.50 73.48 2533.50 0.2607 8.7237
2.50 294.23 1.002 54250 88.48 2404.40 88.49 2540.00 0.3120 8.6432
3.00 297.23 1.003 45670 101.04 2408.50 101.05 2545.50 0.3545 8.5776
4.00 302.11 1.004 34800 121.45 2415.20 121.46 2554.40 0.4226 8.4746
5.00 306.03 1.005 28190 137.81 2420.50 137.82 2561.50 0.4764 8.3951
7.50 313.44 1.008 19240 168.78 2430.50 168.79 2574.80 0.5764 8.2515
10.00 318.96 1.010 14670 191.82 2437.90 191.83 2584.70 0.6493 8.1502
15.00 327.12 1.014 10020 225.92 2448.70 225.94 2599.10 0.7549 8.0085
20.00 333.21 1.017 7649 251.38 2456.70 251.40 2609.70 0.8320 7.9085
25.00 338.12 1.020 6204 271.90 2463.10 271.93 2618.20 0.8931 7.8314
30.00 342.25 1.022 5229 289.20 2468.40 289.23 2625.30 0.9439 7.7686
40.00 349.02 1.027 3993 317.53 2477.00 317.58 2636.80 1.0259 7.6700
50.00 354.48 1.030 3240 340.44 2483.90 340.49 2645.90 1.0910 7.5939
75.00 364.93 1.037 2217 384.31 2496.70 384.39 2663.00 1.2130 7.4564
100.00 372.78 1.043 1694.0 417.36 2506.10 417.46 2675.50 1.3026 7.3594
125.00 379.14 1.048 1374.9 444.19 2513.50 444.32 2685.40 1.3740 7.2844
150.00 384.52 1.053 1159.3 466.94 2519.70 467.11 2693.60 1.4336 7.2233
175.00 389.21 1.057 1003.6 486.80 2524.90 486.99 2700.60 1.4849 7.1717
200.00 393.38 1.061 885.7 504.49 2529.50 504.70 2706.70 1.5301 7.1271
225.00 397.15 1.064 793.3 520.47 2533.60 520.72 2712.10 1.5706 7.0878
250.00 400.59 1.067 718.7 535.10 2537.20 535.37 2716.90 1.6072 7.0527
275.00 403.75 1.070 657.3 548.59 2540.50 548.89 2721.30 1.6408 7.0209
300.00 406.70 1.073 605.8 561.15 2543.60 561.47 2725.30 1.6718 6.9919
325.00 409.45 1.076 562.0 572.90 2546.40 573.25 2729.00 1.7006 6.9652
350.00 412.03 1.079 524.3 583.95 2548.90 584.33 2732.40 1.7275 6.9405
375.00 414.47 1.081 491.4 594.40 2551.30 594.81 2735.60 1.7528 6.9175
400.00 416.78 1.084 462.5 604.31 2553.60 604.74 2738.60 1.7766 6.8959
450.00 421.08 1.088 414.0 622.77 2557.60 623.25 2743.90 1.8207 6.8565
500.00 425.01 1.093 374.9 639.68 2561.20 640.23 2748.70 1.8607 6.8213
550.00 428.63 1.097 342.7 655.32 2564.50 655.93 2753.00 1.8973 6.7893
600.00 432.00 1.101 315.7 669.90 2567.40 670.56 2756.80 1.9312 6.7600
650.00 435.16 1.104 292.7 683.56 2570.10 684.28 2760.30 1.9627 6.7331
700.00 438.12 1.108 272.9 696.44 2572.50 697.22 2763.50 1.9922 6.7080
750.00 440.93 1.112 255.6 708.64 2574.70 709.47 2766.40 2.0200 6.6847
800.00 443.58 1.115 240.4 720.22 2576.80 721.11 2769.10 2.0462 6.6628
850.00 446.11 1.118 227.0 731.27 2578.70 732.22 2771.60 2.0710 6.6421
900.00 448.53 1.121 215.0 741.83 2580.50 742.83 2773.90 2.0940 6.6226
950.00 450.84 1.124 204.2 751.95 2582.10 753.02 2776.10 2.1172 6.6041
(Contd. )
512 Appendix: Tables of Properties

.
Table A 3 Thermodynamic properties of saturated steam (Contd.)

Specific volume Internal energy Enthalpy Entropy

(
xlO3 (kJ/kg) (kJ/kg) (kJ/kg K)
kg
Pressure Temp. Sat. Sat. Sat. Sat. Sat. Sat. Sat. Sat.
(kPa) (K) liquid vapour liquid vapour liquid vapour liquid vapour

1000 453.06 1.127 194.4 761.68 2583.60 762.81 2778.10 2.1387 6.5865
1100 457.24 1.133 177.53 780.09 2586.40 781.34 2781.70 2.1792 6.5536
1200 461.14 1.139 163.33 797.29 2588.80 798.65 2784.80 2.2166 6.5233
1300 464.79 1.144 151.25 813.44 2591.00 814.93 2787.60 2.2515 6.4953
1400 468.22 1.149 140.84 828.70 2592.80 830.30 2790.00 2.2842 6.4693
1500 471.47 1.154 131.77 843.16 2594.50 844.89 2792.2 2.3150 6.4448
1750 478.91 1.166 113.49 876.46 2597.80 878.50 2796.40 2.3851 6.3896
2000 485.57 1.177 99.63 906.44 2600.30 908.79 2799.50 2.4474 6.3409
2250 491.60 1.187 88.75 933.83 2602.00 936.49 2801.70 2.5035 6.2972
2500 497.14 1.197 79.98 959.11 2603.10 962.11 2803.10 2.5547 6.2575
3000 507.05 1.217 66.68 1004.78 2604.10 1008.42 2804.20 2.6457 6.1869
3500 515.75 1.235 57.07 1045.43 2603.70 1049.75 2803.40 2.7253 6.1253
4000 523.55 1.252 49.78 1082.31 2602.30 1087.31 2801.40 2.7964 6.0701
5000 537.14 1.286 39.44 1147.81 2597.10 1154.23 2794.30 2.9202 5.9734
6000 548.79 1.319 32.44 1205.44 2589.70 1213.35 2784.30 3.0267 5.8892
7000 559.03 1.351 27.37 1257.55 2580.50 1267.00 2772.10 3.1211 5.8133
8000 568.21 1.384 23.52 1305.57 2569.80 1316.64 2758.00 3.2068 5.7432
9000 576.55 1.418 20.48 1350.51 2557.80 1363.26 2742.10 3.2858 5.6772
10000 584.21 1.452 18.026 1393.04 2544.40 1407.56 2724.70 3.3596 5.6141
11000 591.30 1.489 15.987 1433.70 2529.80 1450.10 2705.60 3.4295 5.5527
12000 597.90 1.527 14.263 1473.00 2513.70 1491.30 2684.90 3.4962 5.4924
13000 604.08 1.567 12.780 1511.10 2496.10 1531.50 2662.20 3.5606 5.4323

14000 609.90 1.611 11.485 1548.60 2476.80 1571.10 2637.60 3.6232 5.3717
15000 615.39 1.658 10.337 1585.60 2455.50 1610.50 2610.50 3.6848 5.3098
16000 620.59 1.711 9.306 1622.70 2431.70 1650.10 2580.60 3.7461 5.2455
17000 625.52 1.770 8.364 1660.20 2405.00 1690.30 2547.20 3.8079 5.1777
18000 630.21 1.840 7.489 1698.90 2374.30 1732.00 2509.10 3.8715 5.1044
19000 634.69 1.924 6.657 1739.90 2338.10 1776.50 2464.50 3.9388 5.0228
20000 638.96 2.036 5.834 1785.60 2293.00 1826.30 2409.70 4.0139 4.9269
21000 643.04 2.207 4.952 1842.10 2230.60 1888.40 2334.60 4.1075 4.8013
22000 646.95 2.742 3.568 1961.90 2087.10 2022.20 2165.60 4.3110 4.5327
22090 647.29 3.155 3.155 2029.60 2029.60 2099.30 2099.30 4.4298 4.4298
 Appendix: Tables of Properties 513
Table A.4 Thermodynamic properties of superheated steam

V U H S' V U H 5
r, K P = 10 kPa (Sat. Temp = 318.96 K ) P = 50 kPa (Sat . Temp = 354.48 K )
Sat. 14.674 2437.9 2584.7 8.1502 3.240 2483.9 2645.9 7.5939
323.15 14.869 2443.9 2592.6 8.1749
373.15 17.196 2515.5 2687.5 8.4479 3.418 2511.6 2682.5 7.6947
423.15 19.512 2587.9 2783.0 8.6882 3.889 2585.6 2780.1 7.9401
473.15 21.825 2661.3 2879.5 8.9038 4.356 2659.9 2877.7 8.1580
523.15 24.136 2736.0 2977.3 9.1002 4.820 2735.0 2976.0 8.3556
573.15 26.445 2812.1 3076.5 9.2813 5.284 2811.3 3075.5 8.5373
673.15 31.063 2968.9 3279.6 9.6077 6.209 2968.5 3278.9 8.8642
773.15 35.679 3132.3 3489.1 9.8978 7.134 3132.0 3488.7 9.1546
873.15 40.295 3302.5 3705.4 10.1608 8.057 3302.2 3705.1 9.4178
973.15 44.911 3479.6 3928.7 10.4028 8.981 3479.4 3928.5 9.6599
1073.15 49.526 3663.8 4159.0 10.6281 9.904 3663.6 4158.9 9.8852
1173.15 54.141 3855.0 4396.4 10.8396 10.828 3854.9 4396.3 10.0967
1273.15 58.757 4053.0 4640.6 11.0393 11.751 4052.9 4640.5 10.2964
1373.15 63.372 4257.5 4891.2 11.2287 12.674 4257.4 4891.1 10.4859
1473.15 67.987 4467.9 5147.8 11.4091 13.597 4467.8 5147.7 10.6662
1573.15 72.602 4683.7 5409.7 11.5811 14.521 4683.6 5409.6 10.8382

P = 100 kPa (Sat. Temp = 372.96 K) P = 200 kPa (Sat. Temp = 393.38 K )
Sat. 1.6940 2506.1 2675.5 7.3594 0.8857 2529.5 2706.7 7.1272
373.15 1.6958 2506.7 2676.2 7.3614
423.15 1.9364 2582.8 2776.4 7.6134 0.9596 2576.9 2768.8 7.2795
473.15 2.1720 2658.1 2875.3 7.8343 1.0803 2654.4 2870.5 7.5066
523.15 2.4060 2733.7 2974.3 8.0333 1.1988 2731.2 2971.0 7.7086
573.15 2.6390 2810.4 3074.3 8.2158 1.3162 2808.6 3071.8 7.8926
673.15 3.1030 2967.9 3278.2 8.5435 1.5493 2966.7 3276.6 8.2218
773.15 3.5650 3131.6 3488.1 8.8342 1.7814 3130.8 3487.1 8.5133
873.15 4.0280 3301.9 3704.7 9.0976 2.0130 3301.4 3704.0 8.7770
973.15 4.4900 3479.2 3928.2 9.3398 2.2440 3478.8 3927.6 9.0194
1073.15 4.9520 3663.5 4158.6 9.5652 2.4750 3663.1 4158.2 9.2449
1173.15 5.4140 3854.8 4396.1 9.7767 2.7060 3854.5 4395.8 9.4566
1273.15 5.8750 4052.8 4640.3 9.9764 2.9370 4052.5 4640.0 9.6563
1373.15 6.3370 4257.3 4891.0 10.1659 3.1680 4257.0 4890.7 9.8458
1473.15 6.7990 4467.7 5147.6 10.3463 3.3990 4467.5 5147.3 10.0262
1573.15 7.2600 4683.5 5409.5 10.5183 3.6300 4683.2 5409.3 10.1982
( Contd. )
514 Appendix: Tables of Properties

Table A.4 Thermodynamic properties of superheated steam (Contd .)

V U H S' V U H 5
P = 300 kPa (Sat. Temp = 406.7 K ) P = 400 kPa (Sat. Temp = 416.78 K )
Sat. 0.6058 2543.6 2725.3 6.9919 0.4625 2553.6 2738.6 6.8959
423.15 0.6339 2570.8 2761.0 7.0778 0.4708 2564.5 2752.8 6.9299
473.15 0.7163 2650.7 2865.6 7.3115 0.5342 2646.8 2860.5 7.1706
523.15 0.7964 2728.7 2967.6 7.5166 0.5951 2726 A 2964.2 7.3789
573.15 0.8753 2806.7 3069.3 7.7022 0.6548 2804.8 3066.8 7.5662
673.15 1.0315 2965.6 3275.0 8.0330 0.7726 2964.4 3273.4 7.8985
773.15 1.1867 3130.0 3486.0 8.3251 0.8893 3129.2 3484.9 8.1913
873.15 1.3414 3300.8 3703.2 8.5892 1.0055 3300.2 3702.4 8.4558
973.15 1.4957 3478.4 3927.1 8.8319 1.1215 3477.9 3926.5 8.6987
1073.15 1.6499 3662.9 4157.8 9.0576 1.2372 3662.4 4157.3 8.9244
1173.15 1.8041 3854.2 4395.4 9.2692 1.3529 3853.9 4395.1 9.1362
1273.15 1.9581 4052.3 4639.7 9.4690 1.4685 4052.0 4639.4 9.3360
1373.15 2.1121 4256.8 4890.4 9.6585 1.5840 4256.5 4890.2 9.5256
1473.15 2.2661 4467.2 5147.1 9.8389 1.6996 4467.0 5146.8 9.7060
1573.15 2.4201 4683.0 5409.0 10.0110 1.8151 4682.8 5408.8 9.8780
P = 500 kPa (Sat. Temp := 425.01 K ) P = 600 kPa (Sat . Temp = 432 K )
Sat. 0.3749 2561.2 2748.7 6.8213 0.3157 2567.4 2756.8 6.7600
473.15 0.4249 2642.9 2855.4 7.0592 0.3520 2638.9 2850.1 6.9665
523.15 0.4744 2723.5 2960.7 7.2709 0.3938 2720.9 2957.2 7.1816
573.15 0.5226 2802.9 3064.2 7.4599 0.4344 2801.0 3061.6 7.3724
623.15 0.5701 2882.6 3167.7 7.6329 0.4742 2881.2 3165.7 7.5464
673.15 0.6173 2963.2 3271.9 7.7938 0.5137 2962.1 3270.3 7.7079
773.15 0.7109 3128.4 3483.9 8.0873 0.5920 3127.6 3482.8 8.0021
873.15 0.8041 3299.6 3701.7 7.3522 0.6697 3299.1 3700.9 8.2674
973.15 0.8969 3477.5 3925.9 8.5952 0.7472 3477.0 3925.3 8.5107
1073.15 0.9896 3662.1 4156.9 8.8211 0.8245 3661.8 4156.5 8.7367
1173.15 1.0822 3853.6 4394.7 9.0329 0.9017 3853.4 4394.4 8.9486
1273.15 1.1747 4051.8 4639.1 9.2328 0.9788 4051.5 4638.8 9.1485
1373.15 1.2672 4256.3 4889.9 9.4224 1.0559 4256.1 4889.6 9.3381
1473.15 1.3596 4466.8 5146.6 9.6029 1.1330 4466.5 5146.3 9.5185
1573.15 1.4521 4682.5 5408.6 9.7749 1.2101 4682.3 5408.3 9.6906
( Contd. )
 Appendix: Tables of Properties 515
Table A.4 Thermodynamic properties of superheated steam (Contd .)

V U H S' V U H 5

P = 800 kPa (Sat. Temp = 443.58 K ) P = 1000 kPa (Sat. Temp = •453.06 K )
Sat. 0.2404 2576.8 2769.1 6.6628 0.19444 2583.6 2778.1 6.5865
473.15 0.2608 2630.6 2839.3 6.8158 0.2060 2621.9 2827.9 6.6940
523.15 0.2931 2715.5 2950.0 7.0384 0.2327 2709.9 2942.6 6.9247
573.15 0.3241 2797.2 3056.5 7.2328 0.2579 2793.2 3051.2 7.1229
623.15 0.3544 2878.2 3161.7 7.4089 0.2825 2875.2 3157.7 7.3011
673.15 0.3843 2959.7 3267.1 7.5716 0.3066 2957.3 3263.9 7.4651
773.15 0.4433 3126.0 3480.6 7.8673 0.3541 3124.4 3478.5 7.7622
873.15 0.5018 3297.7 3699.4 8.1333 0.4011 3296.8 3697.9 8.0290
973.15 0.5601 3476.2 3924.2 8.3770 0.4478 3475.3 3923.1 8.2731
1073.15 0.6181 3661.1 4155.6 8.6033 0.4943 3660.4 4154.7 8.4996
1173.15 0.6761 3852.8 4393.7 8.8153 0.5407 3852.2 4392.9 8.7118
1273.15 0.7340 4051.0 4638.2 9.0153 0.5871 4050.5 4637.6 8.9119
1373.15 0.7919 4255.6 4889.1 9.2050 0.6335 4255.1 4888.6 9.1017
1473.15 0.8497 4466.1 5145.9 9.3855 0.6798 4465.6 5145.4 9.2822
1573.15 0.9076 4681.8 5407.9 9.5575 0.7261 4681.3 5407.4 9.4543

P = 1200 kPa (Sat. Temp = 461.14 K ) P = 1400 kPa (Sat. Temp = 468.22 K )
Sat. 0.16333 2588.8 2784.8 6.5233 0.14084 2592.8 2790.0 6.4693
473.15 0.16930 2612.8 2815.9 6.5898 0.14302 2603.1 2803.3 6.4975
523.15 0.19234 2704.2 2935.0 6.8294 0.16350 2698.3 2927.2 6.7467
573.15 0.2138 2789.2 3045.8 7.0317 0.18228 2785.2 3040.4 6.9534
623.15 0.2345 2872.2 3153.6 7.2121 0.2003 2869.2 3149.5 7.1360
673.15 0.2548 2954.9 3260.7 7.3774 0.2178 2952.5 3257.5 7.3026
773.15 0.2946 3122.8 3476.3 7.6759 0.2521 3121.1 3474.1 7.6027
873.15 0.3339 3295.6 3696.3 7.9435 0.2860 3294.4 3694.8 7.8710
973.15 0.3729 3474.4 3922.0 8.1881 0.3195 3473.6 3920.8 8.1160
1073.15 0.4118 3659.7 4153.8 8.4148 0.3528 3659.0 4153.0 8.3431
1173.15 0.4505 3851.6 4392.2 8.6272 0.3861 3851.1 4391.5 8.5556
1273.15 0.4892 4050.0 4637.0 8.8274 0.4192 4049.5 4636.4 8.7559
1373.15 0.5278 4254.6 4888.0 9.0172 0.4524 4254.1 4887.5 8.9457
1473.15 0.5665 4465.1 5144.9 9.1977 0.4855 4464.7 5144.4 9.1262
1573.15 0.6051 4680.9 5407.0 9.3698 0.5186 4680.4 5406.5 9.2984

( Contd. )
516 Appendix: Tables of Properties

Table A.4 Thermodynamic properties of superheated steam (Contd .)

V U H S' V U H 5

P = 1600 kPa (Sat. Temp = 474.56 K ) P = 1800 kPa (Sat. Temp = 480.3 K )
Sat. 0.12380 2596.0 2794.0 6.4218 0.11042 2598.4 2797.1 6.3794
498.15 0.13287 2644.7 2857.3 6.5518 0.11673 2636.6 2846.7 6.4808
523.15 0.14184 2692.3 2919.2 6.6732 0.12497 2686.0 2911.0 6.6066
573.15 0.15862 2781.1 3034.8 6.8844 0.14021 2776.9 3029.2 6.8226
623.15 0.17456 2866.1 3145.4 7.0694 0.15457 2863.0 3141.2 7.0100
673.15 0.19005 2950.1 3254.2 7.2374 0.16847 2947.7 3250.9 7.1794
773.15 0.2203 3119.5 3472.0 7.5390 0.19550 3117.9 3469.8 7.4825
873.15 0.2500 3293.3 3693.2 7.8080 0.2220 3292.1 3691.7 7.7523
973.15 0.2794 3472.7 3919.7 8.0535 0.2482 3471.8 3918.5 7.9983
1073.15 0.3086 3658.3 4152.1 8.2808 0.2742 3657.6 4151.2 8.2258
1173.15 0.3377 3850.5 4390.8 8.4935 0.3001 3849.9 4390.1 8.4386
1273.15 0.3668 4049.0 4635.8 8.6938 0.3260 4048.5 4635.2 8.6391
1373.15 0.3958 4253.7 4887.0 8.8837 0.3518 4253.2 4886.4 8.8290
1473.15 0.4248 4464.2 5143.9 9.0643 0.3776 4463.7 5143.4 9.0096
1573.15 0.4538 4679.9 5406.0 9.2364 0.4034 4679.5 5405.6 9.1818

P = 2000 kPa (Sat. Temp = 487.57 K ) P = 2500 kPa (Sat . Temp = 497.14 K )
Sat. 0.09963 2600.3 2799.5 6.3409 0.07998 2603.1 2803.1 6.2575
498.15 0.10377 2628.3 2835.8 6.4147 0.08027 2605.6 2806.3 6.2639
523.15 0.11144 2679.6 2902.5 6.5453 0.08700 2662.6 2880.1 6.4085
573.15 0.12547 2772.6 3023.5 6.7664 0.09890 2761.6 3008.8 6.6438
623.15 0.13857 2859.8 3137.0 6.9563 0.10976 2851.9 3126.3 6.8403
673.15 0.15120 2945.2 3247.6 7.1271 0.12010 2939.1 3239.3 7.0148
723.15 0.16342 3031.0 3357.8 7.2859 0.13014 3025.5 3350.8 7.1746
773.15 0.17568 3116.2 3467.6 7.4317 0.13998 3112.1 3462.1 7.3234
873.15 0.19960 3290.9 3690.1 7.7024 0.15930 3288.0 3686.3 7.5960
973.15 0.22320 3470.9 3917.4 7.9487 0.17832 3468.7 3914.5 7.8435
1073.15 0.24670 3657.0 4150.3 8.1765 0.19716 3655.3 4148.2 8.0720
1173.15 0.27000 3849.3 4389.4 8.3895 0.21590 3847.9 4387.6 8.2853
1273.15 0.29330 4048.0 4634.6 8.5901 0.2346 4046.7 4633.1 8.4861
1373.15 0.31660 4252.7 4885.9 8.7800 0.2532 4251.5 4884.6 8.6762
1473.15 0.33980 4463.3 5142.9 8.9607 0.2718 4462.1 5141.7 8.8569
1573.15 0.36310 4679.0 5405.1 9.1329 0.2905 4677.8 5404.0 9.0291
(Contd. )
 Appendix: Tables of Properties 517
Table A.4 Thermodynamic properties of superheated steam (Contd .)

V U H S' V U H 5

P = 3000 kPa (Sat. Temp = 507.05 K ) P = 3500 kPa (Sat. Temp = .515.75 K )
Sat. 0.06668 2604.1 2804.2 6.1869 0.05707 2603.7 2803.4 6.1253
523.15 0.07058 2644.0 2855.8 6.2872 0.05872 2623.7 2829.2 6.1749
573.15 0.08114 2750.1 2993.5 6.5390 0.06842 2738.0 2977.5 6.4461
623.15 0.09053 2843.7 3115.3 6.7428 0.07678 2835.3 3104.0 6.6579
673.15 0.09936 2932.8 3230.9 6.9212 0.08453 2928.4 3222.3 6.8405
723.15 0.10787 3020.4 3344.0 7.0834 0.09196 3015.3 3337.2 7.0052
773.15 0.11619 3108.0 3456.5 7.2338 0.09918 3103.0 3450.9 7.1572
873.15 0.13243 3285.0 3682.3 7.5085 0.11324 3282.1 3678.4 7.4339
973.15 0.14838 3466.5 3911.7 7.7571 0.12699 3464.3 3908.8 7.6837
1073.15 0.16414 3653.5 4145.9 7.9862 0.14056 3651.8 4143.7 7.9134
1173.15 0.17980 3846.5 4385.9 8.1999 0.15402 3845.0 4384.1 8.1276
1273.15 0.19541 4045.4 4631.6 8.4009 0.16743 4044.1 4630.1 8.3288
1373.15 0.21098 4250.3 4883.3 8.5912 0.18080 4249.2 4881.9 8.5192
1473.15 0.22652 4460.9 5140.5 8.7720 0.19415 4459.8 5139.3 8.7000
1573.15 0.24206 4676.6 5402.8 8.9442 0.20749 4675.5 5401.7 8.8723
P = 4000 kPa (Sat. Temp = 523.55 K ) P = 4500 kPa (Sat. Temp = 530.64 K )
Sat. 0.04978 2602.3 2801.4 6.0701 0.04406 2600.1 2798.3 6.0198
548.15 0.05457 2667.9 2886.2 6.2285 0.04730 2650.3 2863.2 6.1401
573.15 0.05884 2725.3 2960.7 6.3615 0.05135 2712.0 2943.1 6.2828
623.15 0.06645 2826.7 3092.5 6.5821 0.05840 2817.8 3080.6 6.5131
673.15 0.07341 2919.9 3213.6 6.7690 0.06475 2913.3 3204.7 6.7047
723.15 0.08002 3010.2 3330.3 6.9363 0.07074 3005.0 3323.3 6.8746
773.15 0.08643 3099.5 3445.3 7.0900 0.07651 3095.3 3439.6 7.0301
873.15 0.09885 3279.1 3674.4 7.3688 0.08765 3276.0 3670.5 7.3110
973.15 0.11095 3462.1 3905.9 7.6198 0.09847 3459.9 3903.0 7.5631
1073.15 0.12287 3650.0 4141.5 7.8502 0.10911 3648.3 4139.3 7.7942
1173.15 0.13469 3843.6 4382.3 8.0647 0.11965 3842.2 4380.6 8.0091
1273.15 0.14645 4042.9 4628.7 8.2662 0.13013 4041.6 4627.2 8.2108
1373.15 0.15817 4248.0 4880.6 8.4567 0.14056 4246.8 4879.3 8.4015
1473.15 0.16987 4458.6 5138.1 8.6376 0.15098 4457.5 5136.9 8.5825
1573.15 0.18156 4674.3 5400.5 8.8100 0.16139 4673.1 5399.4 8.7549
( Contd. )
518 Appendix: Tables of Properties

Table A.4 Thermodynamic properties of superheated steam (Contd .)

V U H S' V U H 5

P = 5000 kPa (Sat. Temp = 537.14 K ) P = 6000 kPa (Sat . Temp = .548.79 K )
Sat. 0.03944 2597.1 2794.3 5.9734 0.03244 2589.7 2784.3 5.8892
548.15 0.04141 2631.3 2838.3 6.0544
573.15 0.04532 2698.0 2924.5 6.2084 0.03616 2667.2 2884.2 6.0674
623.15 0.05194 2808.7 3068.4 6.4493 0.04223 2789.6 3043.0 6.3335
673.15 0.05781 2906.6 3195.7 6.6459 0.04739 2892.9 3177.2 6.5408
723.15 0.06330 2999.7 3316.2 6.8186 0.05214 2988.9 3301.8 6.7193
773.15 0.06857 3091.0 3433.8 6.9759 0.05665 3082.2 3422.2 6.8803
823.15 0.07360 3181.0 3549.0 7.1215 0.06101 3174.6 3540.6 7.0288
873.15 0.07869 3273.0 3666.5 7.2589 0.06525 3266.9 3658.4 7.1677
973.15 0.08849 3457.6 3900.1 7.5122 0.07352 3453.1 3894.2 7.4234
1073.15 0.09811 3646.6 4137.1 7.7440 0.08160 3643.1 4132.7 7.6566
1173.15 0.10762 3840.7 4378.8 7.9593 0.08958 3837.8 4375.3 7.8727
1273.15 0.11707 4040.4 4625.7 8.1612 0.09749 4037.8 4622.7 8.0751
1373.15 0.12648 4245.6 4878.0 8.3520 0.10536 4243.3 4875.4 8.2661
1473.15 0.13587 4456.3 5135.7 8.5331 0.11321 4454.0 5133.3 8.4474
1573.15 0.14526 4672.0 5398.2 8.7055 0.12106 4669.6 5396.0 8.6199

P = 7000 kPa (Sat. Temp = 559.03 K ) P = 8000 kPa (Sat . Temp = 568.21 K )
Sat. 0.02737 2580.5 2772.1 5.8133 0.02352 2569.8 2758.0 5.7432
573.15 0.02947 2632.2 2838.4 5.9305 0.02426 2590.9 2785.0 5.7906
623.15 0.03524 2769.4 3016.0 6.2283 0.02995 2747.7 2987.3 6.1301
673.15 0.03993 2878.6 3158.1 6.4478 0.03432 2863.8 3138.3 6.3634
723.15 0.04416 2978.0 3287.1 6.6327 0.03817 2966.7 3272.0 6.5551
773.15 0.04814 3073.4 3410.3 6.7975 0.04175 3064.3 3398.3 6.7240
823.15 0.05195 3167.2 3530.9 6.9486 0.04516 3159.8 3521.0 6.8778
873.15 0.05565 3260.7 3650.3 7.0894 0.04845 3254.4 3642.0 7.0206
973.15 0.06283 3448.5 3888.3 7.3476 0.05481 3443.9 3882.4 7.2812
1073.15 0.06981 3639.5 4128.2 7.5822 0.06097 3636.0 4123.8 7.5173
1173.15 0.07669 3835.0 4371.8 7.7991 0.06702 3832.1 4368.3 7.7351
1273.15 0.08350 4035.3 4619.8 8.0020 0.07301 4032.8 4616.9 7.9384
1373.15 0.09027 4240.9 4872.8 8.1933 0.07896 4238.6 4870.3 8.1300

P = 10000 kPa (Sat. Temp = 584.11 K ) P = 12000 kPa (Sat. Temp =: 597.8 K )
Sat. 0.01803 2544.4 2724.7 5.6141 0.01428 2517.8 2689.2 5.5002
623.15 0.02242 2699.2 2923.4 5.9443 0.01715 2640.6 2846.4 5.7578
673.15 0.02641 2832.4 3096.5 6.2120 0.02108 2801.8 3054.8 6.0810
723.15 0.02975 2943.4 3240.9 6.4190 0.02411 2921.7 3211.0 6.2944
773.15 0.03279 3045.8 3373.7 6.5966 0.02679 3028.2 3349.6 6.4906
823.15 0.03564 3144.6 3500.9 6.7561 0.02925 3128.5 3479.5 6.6532
873.15 0.03837 3241.7 3625.3 6.9029 0.03160 3226.4 3605.7 6.8022
923.15 0.04101 3338.2 3748.2 7.0398 0.03387 3323.8 3730.2 6.9409
< ontd. )
(C
 Appendix: Tables of Properties 519
Table A.4 Thermodynamic properties of superheated steam (Contd .)

V U H S' V U H 5

P = 14000 kPa (Sat. Temp = 609.79 K ) P = 15000 kPa (Sat . Temp = 615.28 K )
Sat. 0.01150 2481.4 2642.4 5.3803 0.01034 2455.5 2610.5 5.3098
623.15 0.01311 2563.4 2746.9 5.5492 0.01147 2520.4 2692.4 5.4421
673.15 0.01723 2764.4 3005.6 5.9513 0.01565 2740.7 2975.5 5.8811
723.15 0.02007 2896.0 3177.0 6.1969 0.01845 2879.5 3156.2 6.1404
773.15 0.02251 3008.7 3323.8 6.3937 0.02080 2996.6 3308.6 6.3443
823.15 0.02472 3112.7 3458.8 6.5627 0.02293 3104.7 3448.6 6.5199
873.15 0.02680 3213.2 3588.5 6.7159 0.02491 3208.6 3582.3 6.6776
923.15 0.02880 3312.5 3715.6 6.8575 0.02680 3310.3 3712.3 6.8224

Specific volume in m 3/kg

Internal energy in kJ/ kg
Enthalpy in kJ/ kg
Entropy in kJ/kg K
 Objective Type
Questions

.
1 Which of the following is not equivalent to 1 standard atmosphere pressure?
(a) 1.01325 bar (b) 1.01325 Pa
(c) 760 mm Hg (d) 1.01325 x 105 N /m2
.
2 Pa s is a unit of
(a) Pressure (b) Power
(c) Thermal conductivity (d) Viscosity
3. Pressure head is defined as
(a) Absolute pressure/density
(b) Gauge pressure + atmospheric pressure
(c) Absolute pressure x density
(d) acceleration due to gravity x density x height of liquid column
4. Thermal conductivity of material A is 40 W/m K, that of material B is 40 kcal/(m h °C )
and that of material C is 40 Btu/(ft h °F). Which material is a better conductor of heat
in comparison with others?
(a) Material A (b) Material B
(c) Material C (d) Both materials A and B
.
5 Only one of the following statements is correct regarding gc, the Newton’s law conversion
factor. Spot the correct statement.
(a) It is a dimensionless constant.
(b) It is numerically equal to g, the local acceleration due to gravity.
(c) Weight of a body is equal to the product of mass and gc .
(d) Numerical values of gc are different for different system of units.
6. One Btu of heat is supplied to one kilogram of water. What will be the temperature rise
for water?
(a) 0.252°C (b) 1°C
(c) 3.97°C (d) 4.186°C
521
522 Objective Type Questions

.
7 If the temperature of water rises by 2°C when one kJ heat is supplied to it, how much
water is being heated?
(a) 0.153 kg (b) 0.263 lb
(c) 200 g (d) 4.186 kg
8. The SI system uses bar as a unit of pressure. Which one of the following is equivalent
to 1 bar?
(a) 1.01325 atm (b) 1.01325 x 105 N /m2
(c) 100 kPa (d) 101.325 kPa
9. If the velocity v of a fluid is related to the pressure drop AP and density p of the fluid
[ AP
by v = k I— , where A: is a constant, what are the units of k in SI system?
P
(a) m s 1 ( b) s 1
(c) kg0 - 5 Pa 05 m 15 (d) None of the above
.
10 The dependence of thermal conductivity of a material on temperature is given by an
empirical equation k = aeb/T where a and b are constants, and k is in W /m K and T is
in K. Spot the true statement from the following set.
(a) a and b have the same dimension as k.
(b) a has the dimension of k and b is dimensionless.
(c) a and b are dimensionless.
(d) a has the dimension of k and b has the dimension of T.
11. How many moles are there in 500 g of oxygen?
(a) 31.25 (b) 15.625
(c) 9.41 x 1024 (d) 22.4 x 103
12. Two bottles A and B are filled with 100 g each of HN03 and H 2S04 respectively. Which
one of the following statements is true?
(a) Bottle A contains more molecules.
(b) Bottle B contains more molecules.
(c) Bottles A and B contain the same number of molecules.
(d) Bottles A and B contain the same number of moles of the liquids.
.
13 How many kilogram of CS2 will contain 42 kg of carbon ?
(a) 3.5 x 103 (b) 266.45
(c) 76.13 (d) None of the above
.
14 The molecular formula of an organic compound is C 10H7 Br ( molecular weight 206.96 ).
The weight percentages of carbon, hydrogen and bromine in the compound are:
(a) 55.56% C , 38.89% H and 5.55% Br
(b) 71.43% C, 25.00% H and 3.57% Br
(c) 58.00% C, 3.40% H and 38.60% Br
(d) 40.83% C, 4.80% H and 54.37% Br
15. A mole of a compound contains
(a) One molecule of the substance (b) One atom of the substance
(c) 6.023 x 1023 molecules (d) 22.4 x 103 molecules
 Objective Type Questions 523

16. Molecular weight of an ideal gas is 44. Which of the following statements is not true
about the gas?
(a) 44 g of the gas contains 6.023 x 1023 molecules.
(b) The mass of one molecule is 44 g .
(c) The molar volume of the gas is 22.4 x 10-3 m 3/mol at STP.
(d) The number of molecules in 44 g of the gas is the same as number of atoms in 12 g C.
17. The molar composition of a gas is 10% H2, 10% 02, 30% C02 and balance H20. If 50%
H20 condenses, the final mole percent of H 2 in the gas on a dry basis will be
(a) 10% ( b) 5%
( c ) 18.18% (d) 20%
18. Six kg of NaCl is mixed with 2 kg of KC1. The atomic weights of Na, K and Cl are
respectively, 23, 39.1 and 35.5. What is the mole percent of NaCl in the mixture?
(a) 75 (b) 70.2
(c) 79.3 (d) 81.5
19. A solution of KOH in water has a molarity of 7.0 and a KOH content of 30.21%
(weight). What is the density of the solution?
(a) 900 kg/m 3 (b) 1200 kg/m 3
(c) 1300 kg/m 3 (d) 1288 kg/m 3
20. Two effluent streams are mixed. One stream contains 10% salt and the other none. The
combined stream contains 2% salt. The ratio of the two streams are
(a) 1 : 4 (b) 1 : 5
(c) 1 : 2 (d) 1 : 8
21. One hundred kilomoles of ammonia-air mixture containing 10% (volume ) ammonia is
scrubbed with water to recover 80% of ammonia in the entering gas. Air is assumed
insoluble in water. What is the mole percent of ammonia in the gas leaving the scrubber?
(a) 0.2 (b) 20
(c) 1.9 (d) 2.2
22. An evaporator while concentrating an aqueous solution from 10% to 40% solids evaporates
30 000 kg of water. The amount of solids handled by the system in kg is
(a) 4000 (b) 9000
(c) 4600 (d) 3000
23. 1000 kg of wet solids are to be dried from 60% to 20% moisture. The mass of water
removed in kilograms is
(a) 520 (b) 200
(c) 400 (d) 500
24. Pure oxygen is mixed with air to produce an enriched air containing 50 volume % of
02. The ratio of moles of air to oxygen is
(a) 1.72 (b) 0.58
(c) 0.5 (d) 0.2
524 Objective Type Questions

25. One thousand kilograms of a salt solution containing 50% salt is cooled. 400 kg of
anhydrous salt is separated out. The solubility of the salt at the lower temperature in
kg/100 kg of water is
(a) 80 (b) 50
(c) 40 (d) 20
26. The weight fraction of methanol in an aqueous solution is 0.64. The mole fraction of
methanol (xM) satisfies
(a) xM < 0.5 (b) xM = 0.5
(c) 0.5 < xM < 0.64 (d) xM > 0.5
27. Pure A in the gas phase enters a reactor. 50% of this A is converted to B through the
—
reaction A > 3 B . The mole fraction of A in the exit stream is
(a) 1 /2 (b ) 1 / 3
(c) 1 /4 ( d ) 1 /5
28. Assume that 50% of water present in a wet material is removed by drying. Which one
of the following statements is true?
(a) The mass fraction of water in the solids leaving is half the mass fraction of water
in the entering solid .
(b ) The mass ratio of water in the solids leaving is half the mass ratio of water in the
entering solid.
( c ) The mass fraction and the mass ratio of water in the solid leaving the dryer are half
of the respective values in the feed.
( d ) The weight percent of water in the solids leaving the dryer is 25%.
29. Two solids of same volume, one of steel and the other of stone, are immersed in water.
Which one will suffer a greater loss of weight?
(a) Steel (b) Stone
(c) Equal for both (d) Depends on their mass
30. A body floats in water with three-fourths of it submerged. What is the specific gravity
of the body?
(a) 0.25 (b) 0.33
(c) 0.75 (d) 1.25
31. A test tube carrying some lead balls sinks to a depth of 0.15 m when placed in water.
The same tube sinks only to a depth of 0.10 m when placed in a liquid. What is the
specific gravity of the liquid?
(a) 1.5 (b) 0.75
(c) 2.0 (d) 1.33
32. A metallic spherical ball of radius 0.05 m weighs 0.850 kg. What is its density?
(a) 1800.27 kg/m 3 (b) 1623.4 kg/m3
(c) 1700 kg/m 3 (d) 850.00 kg/m3
33. A body weighs 1 kg in air and 0.85 kg in water. What would be the weight of the object
in a liquid of specific gravity 0.8?
(a) 0.8 kg (b) 1.15 kg
(c) 0.88 kg (d) 0.78 kg
 Objective Type Questions 525

34. Which of the following statements is not true for a mixture of ideal gases?
(a) Total pressure is equal to the sum of the partial pressures.
(b) Partial pressure is equal to the product of mole fraction and the total pressure.
(c) Molar volume is equal to 22.4 m 3/kmol.
(d) Mole % of the components equal the volume %.
35. The specific gravity of a hydrocarbon oil is 0.903 at 288.8 K. What is the corresponding
value on the Baume scale?
(a) 30°Be (b) 29°Be
(c) 25°Be (d) - 16°Be
36. An aqueous solution of 2.45% by weight H 2S04 has a specific gravity of 1.011. The
composition expressed in normality is
(a) 0.2500 (b) 0.2528
(c) 0.5000 (d) 0.5055
37. A hydrocarbon oil is rated at 30°API. What is its specific gravity at 288.8 K?
(a) 1.235 (b) 0.876
(c) 0.300 (d) 0.675
38. What is the porosity of a solid if its bulk density is 1125 kg/m 3 and the true density is
1500 kg/m 3?
(a) 0.25 (b) 0.75
(c) 1.33 (d) 0.33
39. The molarity of water in pure water is
(a ) 1 (b) 18
(c ) 55.55 (d) Infinity
40. An aqueous solution of NaCl contains 20% NaCl. The density of the solution is
1160 kg/m 3. 500 mL of water of density 1000 kg/m3 is added to one litre of the solution.
What is the molality of the resulting solution?
(a) 2.779 mol/kg (b) 2.644 mol/L
(c) 2.779 mol/L (d) 2.644 mol/kg
41. A 10% solution of an organic compound in benzene has a molality of 0.62. The
molecular weight of the compound is
(a) 62 (b) 179.2
(c) 111.1 (d) 620
42. A sample of well water contains 140 g/m3 of Ca2+ ions and 345 g/m 3 of Na+ ions. The
hardness of the sample of water expressed in terms of equivalent CaC03 in g/m 3
(assume atomic masses of Ca: 40, Na: 23, C: 12, and O: 16 ) is
(a) 350 (b) 485
(c) 140 (d) 345
43. The concentration of S02 in the flue gases from a boiler is found to be 0.2 kg/m 3 at
STP. The concentration of SCL in parts per million (by volume) is
(a) 70 000 (b) 20 000
(c) 200 (d) 45 000
526 Objective Type Questions

.
44 A body when immersed in liquid A experiences a greater loss in weight compared to that
in liquid B . Which one of the following is true?
(a) Liquid A is lighter than liquid B .
(b) Liquid B is lighter than liquid A .
(c) Body is lighter than liquids A and B.
(d) Body is lighter than A , heavier than B .
.
45 A solution of specific gravity 1.0 consists of 35% A by weight and the remaining B. If
the specific gravity of A is 0.7, the specific gravity of B is
(a) 1.25 (b) 1.3
(c) 1.35 (d) 1.2
46. The loss of weight of a body in a liquid depends on
(a) The volume of the body and the specific gravity of the liquid
(b) The mass of the body and the specific gravity of the liquid
(c) The volume and specific gravity of the body
(d) The volume of the body only
.
47 The analysis of a gas entering the secondary converter of a contact sulphuric acid plant
is 4% S02, 13% 02 and 83% N2 (volume %). In the converter, S02 is oxidized to S03.
The gases leaving the converter contain 0.45% S02 in an S03-free basis. The percent
conversion of S02 to S03 is
(a) 88.75% (b) 13.75%
(c) 45.00% (d) 89.35 %
48. How much potassium chlorate ( KC103) must be taken to produce the same amount of
oxygen that will be produced by 25 kg of mercuric oxide ( HgO )? (Atomic weight:
Hg = 200.59, K = 39.10)
(a) 5.236 kg (b) 14.145 kg
(c) 4.715 kg (d) 44.186 kg
.
49 If 90 g of iron react with sulphuric acid, how many litres of hydrogen are liberated at
STP? ( Atomic weight of Fe: 55.85)
(a) 36.12 L (b) 0.0361 L
(c) 90 L (d) 1.62 L
.
50 A wet paper pulp contains 75% water. After 100 kg of water is removed in a dryer, it
is found that the pulp is now containing 30% water. The weight of the original pulp is
(a) 200.36 kg (b) 150.00 kg
(c) 222.20 kg (d) 155.56 kg
51. It is required to make 100 kg of a solution containing 40% salt by mixing solution A
containing 25% salt and solution B containing 50% salt. The mass in kilograms of
solution A required is
(a) 40 kg (b) 60 kg
(c) 75 kg (d) 25 kg
 Objective Type Questions 527

52. Pure carbon is completely burnt in oxygen. The flue gas analysis is 70% C02, 20% CO
and 10% 02. The percent excess oxygen used is
(a) 20 (b) 12.5
(c) 0 (d) 10
—
53. The gaseous reaction A > 2B + C takes place in a constant volume reactor starting with
a mixture of 75% A and the rest inert materials. What would be the conversion of A
when the pressure is double the original pressure?
(a) 50% (b) 66.7%
(c) 75% (d) 100%
54. The fraction of the total pressure exerted by oxygen in a mixture containing equal
weights of methane and oxygen is
(a) 1 /3 (b) 1 /2
(c) 1 /4 ( d) 3 / 4
55. Assuming that C02 obeys perfect gas law, calculate the density of C02 at 540 K and
202 kPa, and express it as kilograms per cubic metre.
(a) 1 (b ) 2
(c) 3 (d ) 4
56. 1.2 g -atom of carbon and 1.5 moles of oxygen are reacted to give one mole of carbon
dioxide. The limiting reactant is
(a) Carbon (b) Oxygen
(c) Both (d) None
57. Forty five moles of oxygen is supplied for the combustion of 36 g-atom of carbon. The
percent excess reactant supplied is
(a) 80% (b) 33.3%
(c) 30% (d) 25%
—
58. A gaseous reaction A > 2 B + C takes place isothermally in a constant pressure reactor.
Starting with a gaseous mixture containing 50% A and the rest inert materials, the ratio
of final to initial volume is found to be 1.8. The percent conversion of A is
(a) 80 (b) 50
(c) 60 (d) 74
59. Methane is completely burnt with air. The maximum possible volume percent of carbon
dioxide (on a dry basis) in the flue gas is
(a) 11.7 (b) 21.0
(c) 44.0 (d) 28.0
60. H2S is produced from the following reaction:
FeS + 2 HC1 FeCl 2 + H 2S
120 kg of FeS react with 150 kg of HC1 and 0.5 kmol of H 2S has been produced.
( Atomic weight, Fe = 55.85). The degree of completion of the reaction is
(a) 12.2% (b) 14.2%
(c ) 36.6% (d) None of the above
528 Objective Type Questions

61. Iron pyrites contains 75% FeS2 by weight. What is the iron content in the ore?
(a) 46.55% (b) 35%
(c) 75% (d) 53.45%
62. The molecular weight of an ideal gas is 40. What will be the volume occupied by 0.20 kg
of this gas at STP?
(a) 22.4 L (b) 22.4 m3
(c) 112 L (d) 4.48 m3
63. C02 is contained in a closed rigid container. If it is heated to a temperature twice its
original value what will be the pressure of the gas?
(a) Twice the original pressure (b) Half the original pressure
(c) Same as the initial pressure (d) Cannot be predicted
64. How many molecules of nitrogen will be present in 28 g of nitrogen at standard
temperature and pressure?
(a) 1 molecule (b) 2 molecules
(c) 6.023 x 1023 molecules (d) 12.046 x 1023 molecules
65. What is the volume of oxygen at STP required for the combustion of 5 L carbon
monoxide at STP?
(a) 56 L (b) 0.223 L
(c) 2.5 L (d ) 5 L
.
66 If on combustion, 4 kg of organic compound gives 11 kg of C02, the percentage of
carbon in the compound will be
(a) 50 (b) 25
(c) 60 (d) 75
67. Forty litres of a mixture of methane and nitrogen requires 24 L of pure oxygen for
complete combustion. The percentage of methane in the mixture is
(a) 40 (b) 25
(c) 30 (d) 60
.
68 15 kg of oxygen and 15 kg of hydrogen are mixed together. Which one will have greater
partial pressure in the resulting mixture?
(a) Hydrogen
(b) Oxygen
(c) Both have same partial pressure
(d) Partial pressure depends on their vapour pressure.
69. 100 m3 of a gas mixture containing 20% C02 is sent to an absorber in which 90% of
C02 is absorbed. The temperature and pressure of the gas entering are the same as those
of the gas leaving. What will be the pure-component volume of C02 in the gas leaving?
(a ) 2 m 3 (b) 80 m 3
3
(c) 82 m (d) 100 m 3
70. Six grams of carbon is burnt with an amount of air containing 18 g of oxygen. The
product contains 16.5 g of C02 and 2.8 g of CO besides other constituents. What is
the degree of conversion on the basis of the disappearance of the limiting reactant?
 Objective Type Questions 529

(a) 100% (b) 95%

(c) 75% (d) 20%
71 . Nitrogen dioxide associates and forms nitrogen tetroxide:
2N02 -> N204
One cubic metre of nitrogen dioxide at 100 kPa and 300 K is taken in a rigid closed
container. If 29.5% of the gas associates to form N204, what will be the final pressure
of the gas in the vessel at constant temperature?
(a) 70.5 kPa (b) 736 kPa
(c) 120 kPa (d) 85 kPa
72. How many kilograms of hydrogen can be stored at 325 K and 100 bar in a compressed
gas cylinder that normally holds 0.5 kg of hydrogen at 300 K and 130 bar?
(a) 0.665 (b) 0.207
(c) 0.335 (d) 0.5
.
73 A tank contains oxygen gas at 1.40 x 107 N/m2. On withdrawal of 140 L of oxygen
measured at 1.01 x 105 N /m2, the pressure in the tank is observed to fall to 1.30 x 105
N/m2. Assume that there is no change in the temperature of the gas. What is the volume
of the tank in m 3?
(a) 1.0 (b) 0.88 x 10 3 “

(c) 1.02 x 10 3
"

(d) 0.860 m3
74. A mixture of oxygen and sulphur dioxide is at 200 kPa. The average molecular weight
of the mixture is 44.8. The partial pressure of oxygen in the mixture is
(a) 89.6 kPa (b) 120 kPa
(c) 101.3 kPa (d) 80 kPa
75. In an air-naphthalene ( C10H8) mixture at 100 kPa and 300 K, the partial pressure of
naphthalene is found to be 10 kPa. What volume of this mixture will contain 1 kg of
naphthalene?
(a) 1.95 m3 (b) 0.0195 m 3
(c) 3.25 m 3
(d) 249.6 m3
76. N204 decomposes to N02 at high temperatures. A sample of N204 weighing 27.6 g,
when heated to 300 K at 100 kPa, is found to occupy a volume of 0.012 m3. Assuming
the applicability of the ideal gas law, calculate the percent dissociation of N204 to N02.
(a) 78% (b) 75%
(c) 60% ( d) 50%
77. A closed container of volume 0.02 m 3 contains a mixture of neon (atomic weight, 20 )
and argon ( atomic weight , 40 ) gases, at a temperature of 300 K and a pressure
of 1 x 105 N /m 2. The total mass of the mixture is 28 g . The gases may be assumed
to be ideal. How many grams of argon are there in the container?
(a) 14 g (b) 24 g
(c) 4 g (d) 10 g
78. A mixture of ethane (C2H6) and ethylene (C2H4) occupies 6.5 x 10 2 m 3 at 1.0233 bar
“

and 400 K. The mixture reacts completely with 0.2112 kg of 02 to produce C02 and
530 Objective Type Questions

H20. Assume the ideal gas behaviour. What is the volume percent of ethane in the
mixture?
(a) 40% (b) 60%
(c) 50% (d) 75%
.
79 The weight ratio of carbon to hydrogen in a paraffinic hydrocarbon fuel is found to be
5.25. What is the chemical formula for the fuel?
(a) C7H16 (b) C6H14
(c) C5H 12 (d) C8Hlg
80. The pressure of a real gas is less than the pressure of an ideal gas because in a real gas,
(a) The molecules have finite size.
(b) The number of molecular collisions is greater.
(c) The kinetic energy of molecules is greater.
(d) Intermolecular forces exist.
.
81 In the van der Waals equation of state, the term that accounts for intermolecular forces
is
(a) V - b (b) a / V 2
(c ) RT (d) ( RT ) l
~

.
82 A gas above its critical temperature can be condensed to the liquid state by
( a) Reducing the temperature at constant pressure
( b ) Increasing the pressure at constant temperature
( c ) By reducing the temperature at constant pressure or by increasing the pressure at
constant temperature
( d ) Can not be condensed
83. Which one of the following statements regarding critical point of a substance is not true?
(a) It represents the condition of the highest temperature and pressure at which a gas
and a liquid can exist in vapour-liquid equilibrium .
(b ) It is an idealized concept and can never be attained in practice.
( c ) The PF-isotherm at critical point exhibits a point of inflection.
(d ) Liquid and vapour phases at the critical point have identical properties.
.
84 One of the following statements regarding compressibility factor Z is incorrect. Identify
it.
(a) For real gases Z is greater than 1.
( b ) For ideal gases Z is equal to 1.
( c ) For real gases the value of Z depends on pressure and temperature of the gas.
( d ) All gases have approximately the same Z when compared at the same reduced
temperature and reduced pressure.
85. At 286 K and 139.2 bar, the compressibility factor of methane is found to be 0.8. At
approximately what temperature and pressure, nitrogen gas will have the compressibility
factor of 0.8? (The critical constants are Tc = 190.7 K, Pc = 45.8 bar for methane and
Tc = 126.2 K, Pc = 33.5 bar for nitrogen.)
(a) 189 K, 100 bar (b) 229 K, 111 bar
(c) 286 K, 33.5 bar (d) 84 K, 11.1 bar
 Objective Type Questions 531

.
86 Which one of the following statements is not true?
(a) Vapour pressure of a liquid is independent of the size of the liquid surface.
(b) Vapour pressure is independent of the size and nature of the molecules.
(c) Vapour pressure increases with temperature.
(d) Surrounding pressure has only a negligible effect on the vapour pressure.
.
87 A pure gas is above its critical temperature.
(a) It cannot be condensed by cooling at constant pressure.
(b) It cannot be condensed by compressing isothermally.
(c) It cannot be condensed by cooling or by compression .
(d) It can be liquefied either by cooling or by compression .
88. The process occurring by heating a pure substance at a pressure below that correspond-
ing to the triple point is known as
(a) Evaporation (b) Condensation
(c) Sublimation (d) Fusion
.
89 The saturation temperature of a pure substance is generally known as
(a) The critical temperature (b) The three-phase temperature
(c) The triple point (d) The boiling point
.
90 The logarithm of the vapour pressure of the substance is plotted as the ordinate against
the logarithm of the vapour pressure of the reference at the same temperature as the
abscissa in
(a) Hausbrandt chart (b) Diihring plot
(c) Cox chart (d) Psychrometric chart
91. If the Diihring lines are straight parallel lines, what does that indicate?
(a ) Boiling point elevation is independent of concentration of solute.
(b) Boiling point elevation is independent of pressure for a given solution .
(c) Boiling point of solution is the same as that of the solvent .
(d) Boiling point of the solution is independent of the pressure.
.
92 The vapour pressure of an organic liquid is given by the Antoine equation
2940.46
In Ps = 14.5463 -
T - 49.19
where Ps is in kPa and T is in K. What is the normal boiling point of the substance?
(a) 373.2 K (b) 1022.8 K
(c) 345.4 K (d) 283.7 K
93. A vessel of volume 1000 m 3 contains air which is saturated with water vapour. The total
pressure and temperature are 100 kPa and 293 K respectively. Assuming that the vapour
pressure of water at 293 K is 2.34 kPa, the amount of water vapour in kilograms in the
vessel is approximately
(a) 17 (b) 20
(c) 25 (d) 34
532 Objective Type Questions

.
94 The vapour pressure of water is given by In Psat = A , where A is constant, Psat
is vapour pressure in atm and temperature in K . The vapour pressure of water in atm
at 323 K is approximately
(a) 0.07 (b) 0.11
(c) 0.09 (d) 0.13
95. The saturation temperature of a liquid at 101.3 kPa is 350 K. Which one of the following
statements about this liquid is wrong?
( a) The vapour pressure of the liquid at 350 K is 101.3 kPa.
( b ) At a temperature of 350 K and pressure of 80 kPa the substance is a superheated
vapour.
( c ) At a temperature of 300 K and a pressure of 101.3 kPa the substance is a cold
liquid.
(d ) The vapour and liquid cannot exist in equilibrium at 350 K and 101.3 kPa.
.
96 Vaporization equilibrium constant of ideal solutions depends on
(a) Temperature alone
(b) Temperature and pressure
(c) Temperature, pressure and composition
(d) Temperature and composition
97. Which one of the following statements is not true in the case of ideal solutions?
(a) There is no volume change on mixing the constituents.
( b ) There is no temperature change on mixing .
( c ) The total pressure over the solution varies linearly with x , the liquid composition at
constant temperature.
(d ) The total pressure varies linearly with y the vapour concentration at constant
9

temperature.
98. The temperature at which a binary solution exists as a heterogeneous mixture consisting
of finite quantities of liquid and vapour phases
(a) Is known as its dew-point
(b) Is known as its bubble point
(c) Lies between the bubble point and the dew-point of the mixture
(d) Will be below the boiling points of pure constituents
.
99 A liquid solution is in equilibrium with its vapour. The concentration of the more volatile
component in the vapour is maximum
(a) At the bubble point temperature
(b) At the dew-point temperature
(c) Between the bubble point and the dew-point temperatures
(d) At the normal boiling point of the mixture.
100. An air-water vapour mixture has a dry-bulb temperature of 333 K and a dew-point
temperature of 313 K. The total pressure is 101.3 kPa and the vapour pressure of water
 Objective Type Questions 533

at 313 K is 7.3 kPa and that at 333 K is 19.91 kPa. The wet bulb temperature Tw for
the above mixture would be
(a) less than 313 K (b) 313 K
(c) 313 < Tw < 333 (d) 333 K
101. The slope of the P-x diagram of an ideal binary solution at constant temperature is
/
(a) Equal to P - P
^ (b) Equal to P /
(c) Independent of the vapour pressures (d) Equal to the Henry’s law constant.
102. An ideal solution containing 40% A and 60% B is in equilibrium with its vapour. The
vapour pressures of pure liquids at the equilibrium temperature are 80 kPa for A and
40 kPa for B . The vapour composition is
(a) 80% A (b) 67% A
(c) 57% A (d) 40% A
103. In a real solution the partial pressure is
(a) Greater than that in an ideal solution
(b) Less than that in an ideal solution
(c) Greater than or less than that in an ideal solution
(d) Equal to that in an ideal solution
104. An air-water vapour mixture has a dry-bulb temperature of 333 K and a dew-point
temperature of 313 K. The total pressure is 101.3 kPa and the vapour pressure of water
at 313 K is 7.3 kPa and that at 333 K is 19.91 kPa. The humidity of air expressed as
kg of water vapour per kg of dry air is
(a) 0.048 (b) 0.079
(c) 0.122 (d) 0.152
105. In a dilute solution
(a) The solvent obeys Henry’s law
(b) The solute obeys Henry’s law
(c) The solvent and solute obey Henry’s law
(d) The solute obeys Raoult’s law
106. Which one of the following statements is incorrect with regard to a solution?
(a) The partial pressure approaches the vapour pressure as mole fraction tends to unity.
( b ) The partial pressure is directly proportional to concentration as mole fraction tends
to zero.
( c ) The volume of the solution is greater than the sum of the volumes of the constituents.
( d ) The total pressure over the solution is equal to the sum of the partial pressures.
107. Air, initially at 101.3 kPa and 313 K and with a relative humidity of 50%, is cooled at
constant pressure to 303 K. The cooled air has
(a) A higher dew point (b) A higher absolute humidity
(c) A higher relative humidity (d) A higher wet bulb temperature
108. The solubility of gases in liquid at a given partial pressure is
(a) Directly proportional to the Henry’s law constant
(b) Inversely proportional to the Henry’s law constant
534 Objective Type Questions

(c) Increases with increasing temperature

(d) Not related to the Henry’s law constant
109. The boiling point of a mixture of two immiscible liquids
(a) Is greater than the boiling points of both pure liquids
(b) Lies between the boiling points of the pure liquids
(c) Is less than the boiling point of the more volatile liquid
(d) May be greater or less than the boiling point of the low volatile liquid.
110. The partial pressure over an immiscible solution is
(a) Equal to the product of mole fraction and vapour pressure of pure components
(b) Equal to the vapour pressure of components
(c) Is not related to vapour pressure
(d) Is equal to the product of weight fraction and vapour pressure
111. The three-phase temperature of a system made up of two immiscible liquids
(a) Depends only on the pressure
(b) Depends on the amounts of both liquids constituting the system
(c) Depends on the pressure as well as the amounts of liquids
(d) Is independent of both pressure as well as the amounts present
112. A mixture of two immiscible liquids is in equilibrium with its vapour. The composition
of the vapour
(a) Will not change by changing the pressure
(b) Will change by changing the pressure
(c) Will change only if the amounts of the constituent liquids are altered.
(d) Will change by changing the pressure as well as the amounts of liquids
113. Two immiscible liquids A and B are taken in the mole ratio 1: 3 and heated. At the three-
phase equilibrium temperature, the vapour pressures are 32 kPa for A and 68 kPa for
B. The mole percent of A in the vapour is
(a) 13.6% (b) 32%
(c) 68% (d) 47.1%
114. A mixture of two immiscible liquids A and B is in equilibrium with its vapour at
101.3 kPa. The normal boiling points are: 373 K for A and 473 K for B . Which one of
the following statements can be true regarding the boiling point ( 7) of the two-phase
mixture?
(a) T = 373 K (b) 373 K < T < 473 K
(c) T = 363 K (d) T = 473 K
115. The presence of a non-volatile solute decreases
(a) The boiling point of the solvent
(b) The boiling point and vapour pressure of the solvent
(c) The boiling point and increase the vapour pressure
(d) The vapour pressure
116. If Raoult’s law is applicable, the predicted boiling point of the solution will be independent of
(a) The mole fraction of the solvent (b) The mole fraction of the solute
(c) The solute (d) The surrounding pressure
 Objective Type Questions 535

117. The boiling point elevation of an aqueous 1 molal solution of sodium chloride will be
greater than that of a 1 -molal solution of sucrose in water. This is because of
(a) Ionisation of sodium chloride
(b) The increase in the effective mole fraction of sucrose in the solution
(c) The higher solubility of sucrose in water
(d) The low vapour pressure of sodium chloride
118. Components A and B form ideal solution. At 350 K, a liquid mixture containing 40%
( mole) A is in equilibrium with a vapour containing 70% (mole) A . If the vapour pressure
of A at 350 K is 70 kPa, what is the vapour pressure of B1
(a) 25 kPa (b) 20 kPa
(c) 40 kPa (d) 12 kPa
119. A vapour containing 70% A and 30% B is compressed at a constant temperature of
350 K. It is known that A and B form ideal solutions and at 350 K, the vapour pressures
of A and B are respectively 70 kPa and 30 kPa. At what pressure does condensation
begin?
(a) 70 kPa (b) 30 kPa
(c) 58 kPa (d) 50 kPa
120. A vapour containing 70% A and 30% B is compressed at a constant temperature of
350 K. It is known that A and B form ideal solutions and at 350 K the vapour pressures
of A and B are respectively 70 kPa and 30 kPa. What is the composition of the first
drop of condensate?
(a) 50% A , 50% B (b) 30% A , 70% B
(c) 70% A, 30% B (d) None of the above
121. A liquid mixture of benzene and toluene is in equilibrium with its vapour at 101 kPa and
373 K. The vapour pressures of benzene and toluene are 156 and 63 kPa respectively.
Assuming that the system obeys Raoult’s law, the mole fraction of benzene in the liquid
phase is
(a) 0.65 (b) 0.41
(c) 0.065 (d) 0.04
122. The solubility of oxygen in water at 298 K is found to be 10 ppm for a partial pressure
of oxygen of 25 kPa. What is the Henry’s law constant for oxygen in water at 298 K?
(a) 2.5 kPa (b) 2.5 x 106 kPa
(c) 4.4 x 106 kPa (d) 1.4 x 106 kPa
123. At a specified temperature the molal humidity at saturation
(a) Depends on pressure but is independent of the properties of the gas
(b) Independent of pressure and properties of the gas
(c) Depends on the properties of the gas but is independent of the pressure
(d) Depends on properties of the gas and the total pressure.
124. At what temperature, the saturation humidity value is infinity?
(a) At the triple point temperature of the liquid
(b) At the critical temperature of the liquid
536 Objective Type Questions

(c) At the boiling point of the liquid

(d) At the dew-point of the system
125. Assume that benzene is insoluble in water. The normal boiling points of benzene and
water are 353.3 K and 373.2 K respectively. At a pressure of 101.3 kPa, the boiling point
of a mixture of benzene and water is
(a) 353.3 K
(b) 373.2 K
(c) greater than 353.3 K, less than 373.2 K
(d) less than 353.3 K
126. The vapour pressures of benzene and toluene are 3 atm and 4/3 atm respectively. A
liquid feed of 0.4 mol benzene and 0.6 mol toluene is vaporized . Assuming that the
products are in equilibrium, the vapour phase mole fraction of benzene is
(a) 0.4 (b) 0.6
(c) 0.8 (d) 0.2
127. Which one of the following statements is true with regards to the percent saturation ( PS)
and relative saturation ( RS)?
(a) PS = RS (b) PS > RS
(c) PS < RS (d) PS and RS are not interrelated .
128. Which of the following statements is true with respect to the dew point of a vapour-
gas mixture?
( a) The dew point is independent of the humidity of the gas-vapour system.
( b ) The vapour pressure at the dew point is equal to the partial pressure of the vapour
in the gas.
( c ) When the given gas-vapour mixture is subjected to saturation, the temperature
attained is the dew point.
(d ) The saturation humidity of the gas vapour system is equal to the saturation humidity
at the dew point.
129. What will happen if an air-water vapour sample is cooled below the dew point?
(a) Its humidity will increase. (b) Its percent saturation will increase.
(c) Its percent saturation will decrease , (d) Its humidity will decrease.
130. The wet-bulb temperature of an unsaturated gas-vapour system
(a) Is the same as its dew point (b) Is always greater than the dew point
(c) Is always less than the dew point (d) None of the above.
131. Choose the right statement.
( a) The vapour pressure at the wet-bulb temperature is equal to the existing partial
pressure of the vapour in the vapour-gas mixture.
( b ) The existing partial pressure of the vapour is less than the vapour pressure at the
wet-bulb temperature.
( c ) Wet-bulb and dry-bulb temperatures can never be equal .
(d ) The lower the wet bulb depression the higher the percent saturation of the vapour-
gas mixture.
 Objective Type Questions 537

132. The enthalpy of a gas-vapour mixture can be increased by

(a) Increasing the humidity and decreasing the temperature
(b) Increasing the humidity and temperature
(c) Decreasing the humidity and increasing the temperature
(d) Decreasing both temperature and humidity.
133. Adiabatic saturation temperature of a vapour-gas mixture is
( a) The steady-state temperature attained by the liquid evaporating into the gas
( b ) The temperature to which the gas can be cooled at constant pressure without
condensation
( c ) The temperature attained by the gas when it is humidified to saturation in contact
with the liquid at constant temperature
(d ) The temperature at which the existing vapour content is sufficient to saturate the
gas.
134. An air-water vapour mixture has a dry bulb temperature of 303 K and wet bulb
temperature of 293 K. The mixture is heated at constant pressure to 333 K. The wet-
bulb temperature will be
(a) Constant at 293 K (b) Less than 293 K
(c) Greater than 293 K (d) Equal to 303 K.
135. At certain temperature, the saturation humidity of air-water vapour system is found to
be 0.065 kg of water vapour/kg of dry air at 101.3 kPa. What is the vapour pressure
of water at this temperature?
(a) 3.9 kPa (b) 9.6 kPa
(c) 6.2 kPa (d) 13.1 kPa
136. Air at 318.15 K and 101.3 kPa has a dew point of 298.15 K . What is the partial pressure
of water vapour in the air if the vapour pressure of water in kPa is given by the Antoine
equation
3799.887
In P s = 16.26205 -
T - 46.854
(a) 6.2 kPa (b) 9.72 kPa
(c) 3.13 kPa (d) 4.52 kPa
.
137 The enthalpy of dry air and saturated air are respectively 60 kJ / kg of dry air and
470 kJ / kg of dry air at 333 K. What is the enthalpy of air if the dry bulb temperature
is 333 K and dew point is 310 K? The vapour pressure of water is given by
3799.887
In P s = 16.26205 -
T - 46.854
(a) 265 kJ/kg (b) 442 kJ/kg
(c) 345 kJ/ kg (d) 170 kJ/kg
138. The adiabatic saturation temperature of air-benzene system at 300 K is found to be
285 K at 101.3 kPa. The vapour pressure of benzene at 285 K is 6.7 kPa. The humid
heat of the system may be taken to be constant at 1.155 kJ/kg K and the latent heat
538 Objective Type Questions

of vaporization of benzene at 285 K is 435.4 kJ /kg. The benzene content in the air at
300 K is kg of benzene vapour per kg of dry air.
(a) 0.15 (b) 0.20
(c) 0.30 (d) 0.25
139. It is desired to produce air at 308 K and 30% saturated with water vapour from an air
supply of 30% saturated air at 298 K. Pressure is constant at 101.3 kPa. Suggest a
suitable method for achieving this.
( a) Heating at constant pressure from 298 K to 308 K.
( b ) Heating at constant pressure from 298 K to 308 K followed by adiabatic humidification.
( c ) Adiabatic humidification followed by heating at constant pressure.
(d ) Adiabatic dehumidification.
140. It is required that the air leaving an adiabatic spray chamber contains 0.02 kg of water/
kg of dry air and is 30% saturated with water vapour. If the ambient air at 308 K with
30% saturation is preheated before sending into the spray chamber, to what temperature
this air need be preheated?
(a) 321 K (b) 342 K
(c) 368 K (d) No preheating is required .
141. The absolute humidity of air at 101.3 kPa is measured to be 0.02 kg of water per kg
of dry air. Determine the partial pressure of water vapour in the air?
(a) 1.99 kPa (b) 2.55 kPa
(c) 3.16 kPa (d) 3.87 kPa
142. If the specific heats of air and vapour are 0.2 kJ /kg K and 1.5 kJ /kg K respectively and
the humidity is 0.01, the humid heat in kJ/kg K is
(a) 0.31 ( b) 0.107
(c) 0.017 (d) 0.215
143. A process flow sheet analysis results in the degrees of freedom having a value - 2.
Which one of the following steps must be next carried out?
(a) Identify and add two independent new equations from the process model .
(b ) Remove two equations that have been wrongly assumed to be independent .
( c ) Assign values of two variables in the process.
(d ) Assign value to one variable and remove one equation that was wrongly assumed
to be independent.
144. A butane isomerisation process produces 70 kmol/h of pure isobutane. A purge stream,
removed continuously, contains 85% // -butane and 15% impurity (mole% ). The feed
stream is /2-butane containing 1% impurity. The flow rate of the purge stream will be:
(a) 3 kmol/h (b) 4 kmol/h
(c) 5 kmol/h (d) 6 kmol/h
145. 5.85 g of NaCl is dissolved in one kilogram of water.
(a ) The molarity of the solution is 0.1. (b) The molarity of the solution is 1.0.
(c) The molality of the solution is 0.1. (d) The normality of the solution is 0.1 .
 Objective Type Questions 539

146. The average molecular weight of a mixture of oxygen and other gases is calculated to
be 23.2 using an incorrect value of 16 for the molecular weight of oxygen whereas the
correct value is 29.6. What is the volume percent of oxygen in the mixture?
(a) 40% (b) 60%
(c) 50% ( d) 28%
147. A flow sheet is depicted below:
Fresh feed,
100 mol/h ,
( pure A ) Reactor
WA Separator
A B Product , P
( pure B )

r
R ( pure A )

If the single pass (once through) conversion of A to B is 20%, then the rate of recycle
R (mol/h) is
(a) 300 (b) 400
(c) 500 (d) 600
148. Ideal solution obeys
(a) Boyle’s law (b) Amagats’s law
(c) Raoult’s law (d) All the above laws
149. With increase in the molecular weight, the vapour pressure of chemically similar liquids
at any given temperature
(a) Increases ( b) Decreases
(c) Remains unchanged (d) May increase or decrease
150. Assuming that C02 obeys the perfect gas law, calculate the density of C02 in kilograms
per cubic metre at 540 K and 202 kPa.
(a) 1 (b ) 2
(c) 3 (d ) 4
151. A mixture of ethyl acetate vapour and air has a relative saturation of 50% at 303 K and
a total pressure of 100 kPa. If the vapour pressure of ethyl acetate at 303 K is 16 kPa,
the percent of air is
( a) 92% (b) 45.7%
(c) 50% ( d ) 8%
152. A mixture of ethyl acetate vapour and air has a relative saturation of 50% at 303 K and
a total pressure of 100 kPa. If the vapour pressure of ethyl acetate at 303 K is 16 kPa,
the molal saturation is
(a) 0.080 (b) 0.087
(c) 0.264 (d) 0.029
540 Objective Type Questions

153. Air at 293 K and 750 mm Hg pressure has a relative humidity of 80% . What is its
percent humidity? The vapour pressure of water at 293 K is 17.5 mm Hg .
(a) 80.38 (b) 80
(c) 79.62 ( d) 78.51
154. Na 2SO4 - 10H 2O crystals are formed by cooling 100 kg of 30% by weight aqueous
solution of Na2S04. The final concentration of the solute in the solution is 10%. The
weight of crystals is
(a) 22.33 (b) 32.2
(c) 45.35 (d) 58.65
155. A distillation column separates 10,000 kg/h of a benzene-toluene mixture as shown in
the figure below. xF , xD and xw
represent the weight fractions of benzene in the feed,
distillate and residue respectively.

8000 kg/h

D
TQ XQ 0.95

Feed ,
10000 kg /h
-
xF = 0.50

% = 0.05
(firay -

The reflux ratio is

(a) 0.5 (b) 0.6
(c) 1.0 ( d) 2.0
156. Purging operation is performed on recycle streams for
(a) Increasing yield (b) Reducing the accumulation of inerts.
(c) Conserving heat (d) Improving efficiency
157. A substance which is at a pressure smaller than the saturation pressure at the tempera-
ture in question is in the state.
(a) Superheated vapour (b) Subcooled liquid
(c) Saturated vapour (d) Saturated liquid
 Objective Type Questions 541

158. The weather bureau reports a dry-bulb temperature of ambient air as 302 K and a relative
humidity of 80%. The barometer reads 100 kPa. The vapour pressure of water at 302 K
is 30 mm Hg. The percent humidity of the ambient air is
(a) 80% (b) 30%
(c) 74% ( d) 84%
159. Which of the following gives specific gravity on the Baume scale for liquids heavier than
water ?
, , 141.5
(a )
spgr
,(cv) 145
101

145
,
131.5 (b) i
^
spgr
-130
1 lc
/
(d) 200(sp gr - 1.00)
sp gr
160. If 50 kg of dry solid containing 6% water is obtained by drying 65 kg of wet material,
what was the initial moisture content?
(a) 27.7% (b) 77%
(c) 23% (d) 21%
161. There exists a unique solution for a set of material balance equations if
(a) The number of degrees of freedom is positive
(b) The number of degrees of freedom is negative
(c) The number of degrees of freedom is zero
(d) The number of degrees of freedom is non-zero value
162. With increase in pressure, the heat of vaporization of liquids
( a) Decreases (b) Increases
(c) Remain unchanged (d) May increase or decrease
163. The pH value of a solution increases by one unit. The hydrogen ion concentration
(a) Decreases by one unit
(b) Increases by one unit
(c) Becomes 10 times the original value
(d) Decreases to one-tenth of the original value
164. A multiple effect evaporator has a capacity to process 4000 kg of solid caustic soda per
day when it is concentrating from 10% to 25% solids. The water evaporated in kilo-
grams per day is
(a) 800 (b) 24 000
(c) 60 000 (d) 48 000
165. An evaporator is fed with 100 kg/h of a solution which contains 10% NaCl, 10% NaOH
and the rest water. During evaporation water is removed as vapour and NaCl crystallizes
and is settled and removed. The mother liquor contains 50% NaOH and 2% NaCl. How
many kilograms of salt are precipitated per hour?
(a ) 9.6 (b) 8.0
(c ) 9.0 (d) None of the above
166. An evaporator is fed with 100 kg/h of a solution which contains 10% NaCl, 10% NaOH
and the rest water. During evaporation, water is removed as vapour and NaCl crystallizes
542 Objective Type Questions

and is settled and removed . The mother liquor contains 50% NaOH and 2% NaCl . What
is the weight of concentrated liquor leaving per hour?
(a) 50 kg (b) 25 kg
(c) 20 kg (d) 75 kg
167. A metal recovery unit (MRU) of intake capacity 5000 kg/h treats a liquid product from
a plant and recovers 90% of the metal in the pure form. The unrecovered metal and its
associated liquid are sent to a disposal unit along with the untreated product from the plant
(see figure). Find the flow rate m6 and the weight fraction of the metal (w6). The liquid
product flow rate is 7500 kg/h of composition 0.1 (weight fraction ). Assume steady state.

Pure metal
m4 , w 4 = 1.0

m2 = 5000 kg /h,
w 2 = 0.1
— . MRU
Liquid product ,
m ] = 7500 kg/h ,
vv 1 = 0.1

m 5’ w5 To disposal
unit , m6, w6
*Bypass,
m 3 = 2500 kg /h,
w 3 = 0.1

(a ) m6 = 7500 kg/h , xv6 = 0.0 (b) m 6 = 7050 kg/h , w6 = 0.04255

(c) m6 = 4500 kg/h , w6 = 0.1712 (d) m6 = 5600 kg/h , w6 = 0.0314
168. A feed stream (SI ) at 100 kg/h and containing only A mixes with recycle stream 55
before entering the reactor (see figure), where the reaction A > B takes place. The —
operation is at steady state. The stream S3 leaving the reactor is separated, without either
phase change or composition change, into two streams S4 and S5. If the mass fraction
of B in S4 is 0.95 and the total flow rate of S5 is 10 kg/h , then the ratio of flow rates
of streams S3/S5 and the flow rate of A in S3 are, respectively,

5> 4
Separator
SI S2 S3
^
1 w Reactor

S5 1r
k —
(a) 11 and 110 kg/h (b) 24 and 240 kg/h
(c) 11 and 5.5 kg/h (d) 70 and 330 kg/h
 Objective Type Questions 543

169. Which of the following conditions are to be satisfied for using the Clausius-Clapeyron
equation to estimate the vapour pressure?
(a) The vapour behaves as an ideal gas.
(b) The latent heat of vaporisation is constant.
(c ) The molar volume of liquid is negligibly small.
(d) All the above.
170. A rigid vessel, containing three moles of nitrogen gas at 303 K is heated to 523 K.
Assume the average heat capacity of nitrogen to be C p = 29.1 J/mol K and C y = 20.8
J/mol K. The heat required, neglecting the heat capacity of the vessel, is
(a) 13 728 J (b) 19 206 J
(c ) 4576 J (d) 12 712 J
171. One cubic metre of an ideal gas at 500 K and 1000 kPa expands reversibly to 5 times
its initial volume in an insulated container. If the specific heat capacity at constant
pressure of the gas is 21 J/mol K, the final temperature will be
(a) 35 K (b) 174 K
(c) 274 K (d) 154 K
172. At 373 K, water and methyl cyclohexane both have a vapour pressure of 1.0 atm. The
latent heats of vaporization are 40.63 kJ/kmol for water and 31.55 kJ/kmol for cyclohexane.
The vapour pressure of water at 423 K is 4.69 atm . The vapour pressure of
methylcyclohexane at 423 K is expected to be
(a) Significantly less than 4.69 atm (b) Nearly equal to 4.69 atm
(c ) Significantly more than 4.69 atm (d) Indeterminate due to lack of data
173. For the estimation of heat capacity of a solid compound, one can use
(a) Clapeyron equation (b) Gibb’s equation
(c ) Kopp’s rule (d) Trouton’s rule
174. An insulated container holds 20 kg of water initially at 298 K. It is stirred by an agitator,
which is made to turn by a body weighing 40 kg slowly falling through a height of 4 m.
The process is repeated 500 times. The acceleration due to gravity is 9.8 m/s2. Neglect-
ing the heat capacity of the agitator, the temperature attained by the water is
(a) 313.5 K (b) 307.4 K
(c) 299.8 K (d) 298 K
.
175 One mole of nitrogen at 8 bar and 600 K is contained in a piston-cylinder assembly. It
is brought to 1 bar isothermally against a resisting pressure of 1 bar. The work done
in kJ by the gas is
(a) 30.554 (b) 10.373
( c) 4.9884 (d) 4.3649
176. Heat capacity of gas can be approximately expressed as C p = 26.693 + 7.365 x 10-3 r
where C p is in J/ mol K and T is in K . The heat given off by one mole of air when cooled
at atmospheric pressure from 773 Kto 173 Kis
(a) 10.73 kJ (b) 16.15 kJ
(c ) 18.11 kJ (d) 18.33 kJ
544 Objective Type Questions

.
177 One kilogram of saturated steam at 373 K and 1.01325 bar is contained in a rigid walled
vessel. It has a volume of 1.673 m 3. It is cooled to a temperature at which the specific
volume of water vapour is 1.789 m 3. The amount of water vapour condensed in
kilograms is
(a) 0.0 (b) 0.065
( c) 0.1 (d) 1.0
178. One kilogram of saturated steam at 373 K and 1.01325 bar is contained in a rigid walled
vessel. It has a volume of 1.673 m 3. It is cooled to a temperature at which the specific
volume of water vapour is 1.789 m3. If the heat liberated is 147 kJ, the latent heat of
condensation in kJ/ kg under these conditions is
(a) 40 732 (b) 2676
( c) 2263 (d) 540
179. The heat capacity at constant pressure of a single-component system consisting of liquid
and vapour phases in equilibrium is
(a) infinite (b) zero
(c) positive (d) negative

.
180 For ideal gases, AH
(a )
= JcP dT is valid
For a constant volume process
( b) For a constant pressure process
(c ) Irrespective of the nature of the process
(d ) The statement is never true.
181. The difference between the heat supplied and the work extracted in a steady-flow
process, in which the kinetic and potential energy changes are negligible, is equal to
(a) The change in internal energy (b) The change in enthalpy
(c ) The change in the work function (d) The change in the Gibbs free energy
.
182 To obtain the integrated form of the Clausius-Clapeyron equation
r1 1
In —R =
I R Tl 7T2
/

from the exact Clapeyron equation, it is assumed that

(a) The volume of the liquid phase is negligible compared to that of the vapour phase
(b) The vapour phase behaves as an ideal gas
(c ) The heat of vaporization is independent of temperature
(d) All the above are applicable
183. Which one of the following is not true?
(a) Internal energy is a thermodynamic property of a system.
(b) Internal energy is a state function.
(c ) Internal energy of a system does not change in a cyclic process.
(d) Internal energy is independent of temperature and pressure of the system.
 Objective Type Questions 545

184. The heat supplied to a system under constant pressure is equal to

(a) The work done by the system (b) The change in internal energy
(c ) The change in enthalpy (d) The change in kinetic and potential energy
185. Which one of the following is true?
(a) Generally Cp > Cv for all substances, (b) For solids and liquids, Cv > Cp.
(c ) For all substances, Cp - Cv = R. (d) Cp = Cv for compressible substances.
186. If the heat capacity is given by Cp = a + bT where Cp is in kJ/kmol K and T is in K
(a) The constants a and b are dimensionless constants
(b) Both a and b have the dimensions kJ/kmol K
(c ) The dimension of a is kJ/ kmol K and that of b is kJ/kmol
(d) The dimensions of a is kJ/kmol K and that of b is kJ/kmol K2
187. The Kistyakowsky equation is
(a) Used to estimate the heat capacity of non-polar liquids
(b) Used to estimate the heat capacity of organic compounds
(c) Used to estimate the heat of vaporization of non-polar liquids
(d) Used to estimate the heat of vaporization of polar liquids
188. Trouton’s ratio is
(a) The ratio of heat of vaporization to heat of vaporization at normal boiling point
(b) The ratio of heat of vaporization to the normal boiling point
(c ) The ratio of heat of vaporization to heat of vaporization at critical temperature
(d) The ratio of heat capacity to the heat capacity at normal boiling point
189. The heat capacity of potassium permanganate is equal to the heat capacity of potassium
+ the heat capacity of manganese + 4 x ( the heat capacity of oxygen). This is a
consequence of
(a) Trouton’s rule (b) Kopp’s rule
(c ) Kistayakowsky equation (d) Dulong and Petit rule
190. If the heat capacity of a substance varies linearly with temperature the mean heat
capacity of the substance is equal to
(a) The average of the heat capacity at Tx and heat capacity at T2
(b) The heat capacity at ( Tx + T2 )l2
(c ) The ratio of the heat required to raise the temperature from T { to T2 to ( Tx - T2 )
(d) All the above
191. Which of the following is valid if dH is the enthalpy change for an ideal gas?
(a) dH = Cv dT only for constant volume process
(b) dH = Cp dT only for constant pressure process
(c ) dH = dQ = Cp dT for all processes
(d) dH = Cp dT for all processes
192. For processes involving ideal gases only one of the following is true.
(a) dH = Cv dT (b) dU = Cv dT
(c) dU = Q = Cv dJ ( d ) dH = Q = Cp dT
546 Objective Type Questions

193. In a cyclic process involving ideal gases, the work extracted is equal to the heat supplied
for
( a) Isobaric process (b) Isothermal process
(c ) Adiabatic process (d) Isochoric process
194. The absolute temperature of an ideal gas gets doubled in an adiabatic process. If Cp =
1.4 Cv, the initial volume Vl and final volume V2 are related as
(a) V 2 = 5.66 Vl (b) V2 = 1.22 Vl
(c ) V2 = 0.82 Vl (d) V2 = 0.18 V {
195. Calculate the change in internal energy when one kilomole water is vaporized at a
constant temperature of 373 K and a constant pressure of 101.3 kPa. The specific
volumes of liquid and vapour under these conditions are 1.04 x 10 3 m 3/kmol and 1.675
“

m 3/kmol respectively. 1030 kJ heat is added for this change.

(a) 169.6 kJ (b) 1030 kJ
(c) 860.4 kJ (d) 1199.6 kJ
196. Determine the heat capacity of Na2SO4 10H2O at room temperature using Kopp ’s rule.
*

The atomic heat capacities of elements (J/g-atom K) are 26.04 for Na, 22.6 for S, 16.8
for O, and 9.6 for H .
(a) 325.4 (b) 501.9
( c) 65.44 (d) 177.90
197. The higher heating value is obtained when water formed on combustion of a fuel is
(a) In the liquid state (b) In the vapour state
(c ) Negligible (d) In the liquid or in the vapour state
198. The calorific value of a fuel is equal to
(a ) Heat of formation of the fuel
(b) Heat of combustion of the fuel
(c ) Negative of the heat of combustion
(d) Heat of combustion - Heat of vaporization of water
199. The standard state for heat combustion data assumes water in the liquid state at 298 K.
The standard heat of combustion is thus numerically equal to
(a) Net heating value (b) Gross heating value
(c ) Heat of formation of water (d) None of the above
200. The heats of combustion of yellow phosphorus and red phosphorus are -9.91 kJ and
- 8.78 kJ respectively. The heat of transition of yellow phosphorus to red phosphorus is

(a) - 18.69 kJ (b) 1.13 kJ

(c ) 18.69 kJ (d) - 1.13 kJ
201. In an adiabatic humidification
(a) The temperature and humidity of air increase
(b) Humid heat remains constant
(c ) Enthalpy of air remains constant
(d) Humidity increases and temperature remains constant.
 Objective Type Questions 547

.
202 The difference between heats of reaction at constant pressure and constant volume for
the reaction
2QH, (1) + 150, (g ) -> 12CO, (g) + 6H,0 (1)
at 298 K in kJ is
(a) - 7.43 (b) 3.72
( c) - 3.72 (d) 7.43
203. The standard heats of combustion of ethylene, ethane and butane in kJ/mol are -
1410.99, - 1559.9 and - 2855.6 respectively. The heat absorbed for the isothermal
reaction
C4H 10 (g) -> C2H4 (g ) + C2H6 (g )
at 298 K and 1 atmosphere pressure is
(a) 2706.7 kJ (b) - 2706.7 kJ
(c) 115.3 kJ (d) - 115.3 kJ
.
204 Given that
2C (s) + 202 -> 2CO?2 (g) AH = - 789 kJ
1
H 2 (g) + - 02 (g) -> H20 (1) AH = - 286 kJ

5
C 2H5 (g) + - 092 (g ) -> 2CO?2 (g) + H,20 (1) AH = - 1310 kJ
2
the heat of formation of acetylene is
(a) 1802 kJ (b) - 1802 KJ
(c ) - 800 kJ (d) 235 kJ
205. The actual flame temperature is less than adiabatic flame temperature. This is due to
( a) Loss of heat
( b ) Incomplete combustion
( c ) Energy expended for performing mechanical work and increasing external kinetic
and potential energy
( d ) All the above
206. The maximum flame temperature is attained
(a) When the fuel and air are in stoichiometric quantities
(b) When fuel is burned with an excess of pure oxygen
(c ) When stoichiometric amount of oxygen is used
(d) When excess of air supply is provided
207. An exothermic reaction takes place in an adiabatic reactor. The product temperature
the reactor feed temperature.
(a) Is always equal to (b) Is always greater than
(c ) Is always less than (d) May be greater or less than
208. A batch adiabatic reactor at an initial temperature of 373 K is being used for the reaction
A B. Assume that the heat of reaction is - 1 kJ/mol at 373 K and the heat capacity
548 Objective Type Questions

of both A and B to be constant and equal to 50 J/mol K. The temperature rise after a
conversion of 0.5 will be
(a ) 5 K (b) 10 K
(c) 20 K (d) 100 K
209. In the hydrodealkylation of toluene to benzene, the following reactions occur.
C7H 8 + H 2 -> C6H6 + CH 4

^^ 6 6 ^ ^12^10 + ^2
Toluene and hydrogen are fed to a reactor in a molar ratio of 1 :5. 80% of the toluene
gets converted and the selectivity of benzene ( defined as moles of benzene formed per
mole of toluene converted) is 90%. The fractional conversion of hydrogen is
(a) 0.16 (b) 0.144
( c) 0.152 (d) 0.136
210. Determine Qp - Qv for the following reaction at 298 K

C (s) + ~
02 (g) CO (g) AH = - 110.5 kJ

where Qp is the heat of reaction at constant pressure and Qv is the heat of reaction at
constant volume.
(a) 1239 J/mol (b) 2178 J/mol
(c ) - 1239 J/mol (d) 4956 J/mol
211. One mole of methane undergoes complete combustion in a stoichiometric amount of air.
Both the reactants and products are in the gas phase. The mole fraction of water vapour
in the product gas is about
(a) 0.19 (b) 0.33
( c) 0.40 (d) 0.67
212. One mole of methane at 298 K undergoes complete combustion in a stoichiometric
amount of air also at 298 K. Both the reactants and products are in the gas phase.
CH4 + 202 CO., + 2 H20 A// 298 = - 730 kJ/mol
If the average specific heat of all the gases/vapours is 40 J/mol K, the maximum
temperature rise ( K) of the exhaust gases would be approximately
(a) 1225 (b) 1335
(c) 1525 (d) 1735
213. The heat of reaction is
(a) Independent of temperature and pressure
(b) Independent of temperature but changes with pressure
(c ) Independent of the number of intermediate steps involved
(d) Independent of the state of aggregation of the reactants and products
214. The adiabatic flame temperature of a fuel in air is that in pure oxygen.
(a) Greater than (b) Less than
(c) Equal to (d) Greater than or equal to
 Objective Type Questions 549

215. Steam at 1500 kPa is throttled (i.e., expanded at constant enthalpy ) to 100 kPa. If the
temperature rises to 423 K on expansion, what was the quality of original steam?
(a) 0.844 (b) 0.992
( c) 0.112 (d) 1.115
216. In the absence of experimental values, may be used to calculate the heat capacity
of solids
(a) Dulong and Petit law (b) Kopp’s rule
(c ) the Kistyakowsky equation (d) Trouton’s rule
217. At standard conditions,
N2 + 202 -> 2N02 AH 0 = - 90 kJ/ mol

NO + ~
02 — > N02 AH 0 = - 11 kJ/mol

The standard heat of formation of NO in kJ/mol is

(a) - 78 (b) 78
(c) - 34 (d) - 101
218. Enthalpy change in a chemical reaction is independent of the steps through which the
reaction proceeded. This is a consequence of
(a) Boyle’s law (b) Van’ t Hoff ’s law
(c ) Hess’s law (d) LeChatlier’s principle
219. When methane is burnt in a stoichiometric quantity of air, the Orsat analysis of flue gas
will be
(a) 9.5% C02, 19.0% H20, 71.5% N2 (b) 33.3% C02, 66.7% H20
(c ) 21.0% C02, 79.0% N 2 (d) 11.7% C02, 88.3% N2
220. Which one of the following represents the Orsat analysis of the flue gas when methane
is completely burnt in a theoretical supply of air?
(a) C02 5.7%, CO 5.7%, 02 2.9%, N2 85.7%
(b) C02 9.5%, H20 19.0%, N2 71.5%
(c) 33.3% C02, 66.7% N 2
(d) None of the above
221. The proximate analysis of coal gives
(a) Carbon, hydrogen and ash
(b) Volatile matter, moisture, ash and fixed carbon
(c ) Carbon, hydrogen, sulphur and nitrogen
(d) Volatile matter, moisture, nitrogen and carbon
222. Trouton’s ratio is the ratio of
(a) Latent heat of vaporization to the normal boiling point
(b) The heat supplied to the absolute temperature
(c ) The heat capacity of a substance to the heat capacity of water
(d) None of the above
550 Objective Type Questions

.
223 Trouton’s ratio in SI units is
(a) 21 (b) 87.9
( c) 5 (d) 79.8
224. A sample of natural gas containing 80% methane and the rest nitrogen is burnt with 20%
excess air. With 80% of the combustibles producing C02 and the remainder going to CO
the Orsat analysis in volume percent is
(a) C02: 6.26, CO: 1.56, 02: 3.91, H20: 15.66, N2: 72.60
(b) C02: 7.42, CO: 1.86, 02: 4.64, N2: 86.02
(c ) C02: 6.39, CO: 1.60, 02: 3.99, H20: 15.96, N2: 72.06
(d) C02: 7.60, CO: 1.90, 02: 4.75, N2: 85.74
225. The heat capacity of air can be approximately expressed as
Cp = 26.693 + 7.365 x 10 3 T
"

where Cp is in J/mol K and T is in K. The heat given off by one mole of air when cooled
at 1 atmospheric pressure from 500-100°C is
(a) 10.73 kJ (b) 16.15 kJ
(c) 18.11 kJ (d) 18.33 kJ
226. One mole methane undergoes complete combustion in a stoichiometric amount of air.
The reaction proceeds as
CH4 + 202 -> C02 + 2H20
Both the reactants and the products are in gas phase.
AH0 = - 730 kJ/mol of methane
The mole fraction of water vapour in the product gases is about
(a ) 0.19 (b) 0.33
( c) 0.40 (d) 0.67
227. One mole methane undergoes complete combustion in a stoichiometric amount of air.
The reaction proceeds as
CH4 + 202 C02 + 2H20
Both the reactants and the products are in gas phase.
AH0 = - 730 kJ/mol of methane. If the average specific heat of all gases and vapours
is 40 J/ mol K, the maximum temperature rise of the exhaust gases in K would be
approximately equal to
(a) 1225 (b) 1335
(c) 1525 (d) 1735
228. By increasing the air/fuel ratio, the adiabatic flame temperature
(a) increases (b) decreases
(c ) remains unchanged (d) change is unpredictable
 Objective Type Questions 551

.
229 The reaction A( l ) + B(g) — > C( l ) + D(g) is carried out in a reactor followed by
separator as shown below:

FRG PG

FF FB c
->
Reactor Separator
F

Notation: Molar flow rate of fresh B = Ffb ; Molar flow rate of A = F4 ; Molar flow rate
of recycle gas = FRG ; Mole fraction of B in recycle gas = YRB ; Molar flow rate of purge
gas = FpG ; Molar flow rate of C = Fc; FfB = 2 mol/s, FA = 1 mol/s, FB/ FA = 5, A is
completely converted. If YRB = 0.3, the ratio of recycle gas to purge gas { FRG!FpG ) is
(a ) 2 (b) 5
( c) 7 (d) 10
. —
230 The reaction A( l ) + B(g) » C( l ) + D(g) is carried out in a reactor followed by
separator as shown below:

YRB> FRG PG

FF FB C
> Reactor Separator
F

Notation: Molar flow rate of fresh B = Ffb\ Molar flow rate of A = FA; Molar flow rate
of recycle gas = FRG\ Mole fraction of B in recycle gas = YRB\ Molar flow rate of purge
gas = FpG; Molar flow rate of C = Fc; FFB = 2 mol/s, FA = 1 mol/s, FB/FA = 5, A is
completely converted. If the ratio of recycle gas to purge gas ( FRG/FpG ) is 4, then FRB
is
( a) 3 / 8 ( b ) 2 /5
(c ) 1/ 2 ( d ) 3 /4
231. One mole of methane is contained in a leak-proof piston cylinder assembly at 8 bar and
1000 K. The gas undergoes isothermal expansion to 4 bar under reversible condition.
Methane can be considered as an ideal gas under these conditions. The value of universal
gas constant is 8.314 J/mol K. The heat transferred (in kJ) during the process is
( a) 11.52 (b) 5.76
( c ) 4.15 (d) 2.38
232. Ammonia is synthesized at 200 bar and 773 K by the reaction N2 + 3 H 2 <-> 2NH3. The
yield of ammonia is 0.45 mol/mol of fresh feed. Flow sheet for the process (along with
available compositions) is shown below:
552 Objective Type Questions

Recycle, 75 mol% H2 , 15 mol% N2,

10 mol% inerts Purge
4- >

Pure ammonia
-> Reactor Separator
Fresh feed, 75 mol% H2
’
24 mol% N2, 1 mol% inerts

The single pass conversion for H 2 in the reactor is 20%. The amount of H 2 lost in the
purge as a percentage of H2 in the fresh feed is
( a) 10 ( b) 20
( c ) 45 (d) 55
233. The following combustion reactions occur when methane is burned.
CH4 + 202 C02 + 2 H20
2CH4 + 302 2CO + 4 H20

20% excess air is supplied to the combustor. The conversion of methane is 80% and
the molar ratio of CO to C02 in the flue gas is 1 :3. Assume air to have 80 mol% N2
and rest 02. The oxygen consumed as a percentage of 02 entering the combustor is
(a) 20 (b) 62.5
( c) 80 (d) 83.3
234. A saturated solution at 30°C contains 5 moles of solute ( MW = 50 ) per kilogram of
solvent ( MW = 20). The solubility at 100°C is 10 moles of the solute per kg of solvent.
If 10 kg of the original solution is heated to 100°C, then the weight of the additional
solute that can be dissolved in it, is
(a) 0.25 kg (b) 1 kg
(c) 2 kg (d) 3.34 kg
.
235 The products of combustion of methane in atmospheric air (21% 02, 79% N2) have the
following composition on dry basis:
C02 = 10.00%, 02 =2.37%, CO = 0.53%, N2 = 87.1%
The ratio of the moles of CH4 to moles of 02 in the feed stream is
( a ) 1.05 (b) 0.60
( c ) 0.51 (d) 0.45
236. At 25°C and 90% relative humidity, water evaporates from the surface of a lake at the
rate of 1 kg/ m 2 h. The relative humidity that will lead to an evaporation rate of 3 kg/
m2 h with other conditions remaining the same, is
(a) 30% (b) 50%
( c) 60% (d) 70%
 Objective Type Questions 553

.
237 Pure water (stream W ) is to be obtained from a feed containing 5 weight % salt using
a desalination unit as shown below:

Recycle ( R )
4-

Feed ( F ) 5 wt% Effluent

> Desalination
unit
Mixed feed,
10 wt% salt Pure water ( FT ) ,
0% salt

If the overall recovery of pure water (through stream W ) is 0.75 kg/ kg feed, the recycle
ratio (.R/F ) is
(a) 0.25 (b) 0.5
(c) 0.75 (d) 1.0
238. A 35 weight% Na2S04 solution in water initially at 50°C is fed to a crystallizer at
20°C. The product stream contains hydrated crystals Na2SO4.10H2O in equilibrium with
a 20 weight% Na2S04 solution. The molecular weights of Na2S04 and Na2SO4.10H 2O
are 142 and 322, respectively. The feed rate of 35% solution required to produce 500
kg/h of hydrated crystals is
(a) 403 kg/ h (b) 603 kg/h
(c ) 803 kg/ h (d) 1103 kg/h
239. 600 kg/ h of saturated steam at 1 bar (Enthalpy = 2675.4 kJ/kg) is mixed adiabatically
with superheated steam at 450°C and 1 bar (Enthalpy = 3382.4 kJ/kg). The product is
superheated steam at 350°C and 1 bar (Enthalpy = 3175.6 kJ/ kg). The flow rate of the
product is
(a) 711 kg/ h (b) 1111 kg/h
(c ) 1451 kg/h (d) 2051 kg/h
240. Carbon black is produced by the decomposition of CH4.
CH4(g) -4 C(s) + 2H2(g)
The single pass conversion of CH4 is 60%. If fresh feed is pure CH4 and 25% of CH4
exiting the reactor is recycled, then the molar ratio of fresh feed stream to recycle stream is
( a) 0.9 ( b) 9
( c) 10 (d) 90
241. Methane and steam are fed to a reactor in molar ratio 1:2. The following reactions take
place:
CH 4 (g ) + 2H 20(g) -> C02 (g ) + 4H 2 (g )

CH 4 (g ) + H 20( g ) -> CO(g ) + 3H 2 (g)

where C02 is the desired product, CO is the undesired product and H 2 is a by- product.
The exit stream has the following composition:
554 Objective Type Questions

Species CH4 Hp C02 K, CO

Mol% 4.35 10.88 15.21 67.39 2.17

The selectivity for desired product relative to undesired product is

(a) 2.3 (b) 3.5
( c) 7 (d) 8
242. Methane and steam are fed to a reactor in molar ratio 1:2. The following reactions take
place:
CH 4 (g ) + 2H 20(g) C02 (g ) + 4H 2 (g )

CH 4 (g ) + H 20(g ) CO(g ) + 3H 2 (g )
where C02 is the desired product, CO is the undesired product and H 2 is a by- product.
The exit stream has the following composition:

Species CH4 Hp C02 Y

Mol% 4.35 10.88 15.21 ^
67.39
CO
2.17

The fractional yield of C02 is (fractional yield is defined as the ratio of the moles of the
desired product formed to that would have been formed if there were no side reactions
and the limiting reactant had reacted completely).
( a ) 0.7 (b) 0.88
( c) 1 (d) 3.5
243. Methane and steam are fed to a reactor in molar ratio 1 :2. The following reactions take
place:
CH 4 (g ) + 2H 20( g) C02 (g ) + 4H 2 (g )

CH 4 (g ) + H20(g ) -> CO(g ) + 3H 2 (g)

where C02 is the desired product, CO is the undesired product and H 2 is a by- product.
The exit stream has the following composition:

Species CH4 Hp C02 HL, CO

Mol% 4.35 10.88 15.21 67.39 2.17

The fractional conversion of methane is

(a) 0.4 (b) 0.5
( c) 0.7 (d) 0.8
244. Air (79% N2 and 21% 02) is passed over a catalyst at high temperature. Oxygen
completely reacts with nitrogen as shown below:

- N,2 + - O,2 -> NO

2 2
 Objective Type Questions 555

-N
2 + o2 NO2

The molar ratio of NO to N02 in the product stream is 2:1. The fractional conversion
of nitrogen is
(a) 0.13 (b) 0.20
( c) 0.27 (d) 0.40
245. A simplified flowsheet is shown in the figure for production of ethanol from ethylene.
The conversion of ethylene in the reactor is 30% and the scrubber following the reactor
completely separates ethylene as top stream and ethanol and water as bottom stream .
The last (distillation) column gives an ethanol-water azeotrope (90 mol% ethanol) as the
final product and water as the waste. The recycle to purge ratio is 34. The reaction is :
C 2 H 4 (g) + H 20(g ) C 2 H 5OH (g )

Recycle
<- - Purge

Wash water
>
Azeotrope
C 2 H4
>
-
Reactor -
*
-
- Distillation
H 20 column
Scrubber

- Wastewater

For an azeotrope product rate of 500 mol/h, the recycle gas flow rate in mol/h is
(a) 30 (b) 420
(c) 1020 (d) 1500
.
246 A simplified flowsheet is shown in the figure for production of ethanol from ethylene.
The conversion of ethylene in the reactor is 30% and the scrubber following the reactor
completely separates ethylene as top stream and ethanol and water as bottom stream.
The last (distillation) column gives an ethanol-water azeotrope (90 mol% ethanol) as
the final product and water as the waste. The recycle to purge ratio is 34. The reaction
is:
C 2 H 4 (g ) + H20(g ) -> C 2 H 5 OH(g )
556 Objective Type Questions

Recycle
-
4 > Purge

Wash water
>
Azeotrope
C 2 H4
> Reactor >
-

> Distillation
H 20 column
Scrubber

> Wastewater

If the fresh H20 feed to the reactor is 600 mol/h, and wash water for scrubbing is 20%
of the condensables coming out of the reactor, the water flow rate from the distillation
column as bottoms is
(a) 170 (b) 220
( c) 270 (d) 430
247. 44 kg of C3H8 is burned with 1160 kg of air (MW = 29) to produc 88 kg C02 and
14 kg of CO.
C3 H8 + 5O 2 — ^ 3CO 2 + 4H 2 O
What is the percent excess air used?
(a) 55 (b) 60
( c) 65 (d) 68
248. 44 kg of C 3H8 is burned with 1160 kg of air ( MW = 29) to produc 88 kg C02 and
14 kg of CO.
C3 H8 + 502 -> 3C02 + 4H 20
What is the percent carbon burned?
(a) 63.3 (b) 73.3
( c) 83.3 (d) 93.3
249. Carbon monoxide (CO) is burnt in the presence of 200% excess pure oxygen and the
flame temperature achieved is 2298 K. The inlet streams are at 25°C. The standard heat
of formation (at 25°C) of CO and C02 are - 110 kJ/mol and -390 kJ/mol, respectively.
The heat capacities in J/mol K of the components are :

Cpo2 - 25 + 14 x 10-3 r

Cpco2 = 25 + 42 x 10 3 T
~

where T is the temperature in K . The heat loss (in kJ) per mole of CO burnt is
(a) 100 (b) 51.6
(c) 34.6 (d) 121.6
 Objective Type Questions 557

250. A reverse osmosis unit treats feed water ( F ) containing fluoride and its output consists
of a permeate stream ( P) and a reject stream (.R). Let CF , Cp and CR denote the fluoride
concentration in the feed, permeate and reject streams, respectively. Under steady state
conditions, the volumetric flow rate of the reject is 60% of the volumetric flow rate of
the inlet stream, and CF = 2 mg/L and Cp = 0.1 mg/L. The value of CR in mg/L is
(a) 4.3 (b) 5.3
( c) 3.3 (d) 2.3
251. A reverse osmosis unit treats feed water (F) containing fluoride and its output consists
of a permeate stream ( P) and a reject stream (F). Let CF , Cp and CR denote the fluoride
.

concentration in the feed, permeate and reject streams, respectively. Under steady state
conditions, the volumetric flow rate of the reject is 60% of the volumetric flow rate of
the inlet stream, and CF = 2 mg/L and Cp = 0.1 mg/L. A fraction / of the feed is
bypassed and mixed with the permeate to obtain treated water having fluoride concen-
tration of 1 mg/L. The flow rate of the reject stream is 60% of the flow rate entering
the reverse osmosis unit (after the bypass). The value of / is
(a) 0.26 (b) 0.22
( c) 0.18 (d) 0.30
.
252 What is the heat required (in kJ up to 1 digit after the decimal point) to raise the
temperature of one mole of the solid material from 100°C to 1000°C? The specific heat
Cp of the material in J/ mol K is expressed
r as CP = 20 + 0.005 T where T is in K. Assume
no phase change.
(a) 21.7 (b) 31.4
( c) 42.3 (d) 11.6
253. An ideal gas is initially at a pressure of 0.1 MPa and a total volume of 2 m3. It is
compressed to 1 MPa by a reversible adiabatic process and then cooled at constant
pressure to a final volume of 0.2 m3. The total work done in kJ on the gas for the entire
process is (take R = 8.314 J /mol K, Cp = 2.5R )
(a) 827 (b) 757
(c) 631 (d) 503
254. Two elemental gases (A and B) are reacting to form liquid (C) in a steady state process
—
as per the reaction A + B > C. The single pass conversion of the reaction is only 20%,
and hence, recycle is used. The product is separated completely in pure form. The fresh
feed has 49 mol% A and B each along with 2 mol% impurities. The maximum allowable
impurities in the recycle stream is 20 mol%. The amount of purge stream ( in moles) per
100 moles of the fresh feed is
(a ) 5 (b) 15
( c) 20 (d) 10
255. For a pure liquid, the rate of change of vapour pressure with temperature is 0.1 bar/K in
the temperature range of 300 K to 350 K. If the boiling point of the liquid at 2 bar is
320 K, the temperature in K at which it boils at 1 bar (up to one decimal place) is
(a) 305 K (b) 310 K
(c) 300 K (d) 330 K
558 Objective Type Questions

.
256 The schematic diagram of a steady state process is shown below. The fresh feed ( F )
to the reactor consists of 96 mol% reactant A, and 4 mol% inert I. The stoichiometry
—
of the reaction is A » C. A part of the reactor effluent is recycled. The molar flow rate
of the recycle stream is 0.3F. The product stream P contains 50 mol% C. The percent
conversion of A in the reactor based on A entering the reactor at point 1 in the figure is
0.3F
i

F . - 1 . A —>C —
P

(a) 50.6 (b) 45.5

(c ) 60.0 (d) 35.5
257. A liquid mixture of ethanol and water is flowing as inlet stream P into a stream splitter.
It is split into two streams, Q and R, as shown in the figure below.
Q
P
<
^ R
The flow rate of P , containing 30 mass% of ethanol, is 100 kg/h. What is the least
number of additional specification(s) required to determine the mass flow rates and
compositions ( mass%) of the two exit streams?
(a ) 0 ( b) 1
(c) 2 (d) 3
258. A jacketed stirred tank with a provision for heat removal is used to mix sulphuric acid
and water in a steady state flow process. H2S04 ( /) enters at a rate of 4 kg/ h at 25°C
and H20 ( /) enters at a rate of 6 kg/h at 10°C. The following data are available:
Specific heat capacity of water = 4.2 kJ/ kg K .
Specific heat capacity of aqueous solution of 40 mass% H 2S04 = 2.8 kJ/kg solution K.
Assume the specific heat capacities to be independent of temperature.
Based on reference states of H 2S04 (/) and H20 ( /) at 25°C , the heat of mixing for
aqueous solution of 40 mass% H2S04 = - 650 kJ/kg H 2S04.
If the mixed stream leaves at 40°C, what is the rate of heat removal (in kJ/h)?
(a) 1802 (b) 2558
(c) 5702 (d) 6458
259. A catalytic reforming plant produces hydrogen and benzene from cyclohexane by
dehydroaromatisation. In order to increase the production of hydrogen, the owner plans
to change the process to steam reforming of the same feedstock that produces hydrogen
and carbon dioxide. Stoichiometrically, what is the maximum ratio of pure hydrogen
produced in the proposed process to that in the existing process?
(a) 1 (b ) 2
(c) 5 ( d) 6
 Objective Type Questions 559

ANSWERS TO OBJECTIVE TYPE QUESTIONS

1. ( b) 2. (d ) 3. (a ) 4. (c ) 5. (d) 6. (a )
7. ( b) 8. (c ) 9. (d ) 10. (d ) 11. ( b) 12. (a )
13. ( b) 14. (c ) 15. (c ) 16. (b ) 17. (d ) 18. (c )
19. (c) 20. (a ) 21. ( d) 22. (a) 23. ( d) 24. (a )
25. (d) 26. ( b) 27. (c ) 28. ( b) 29. (c ) 30. (c )
31. (a ) 32. ( b) 33. (c ) 34. ( c) 35. ( c) 36. ( d)
37. (b ) 38. (a ) 39. (C) 40. ( a) 41. ( b) 42 . (a )
43. (a ) 44. ( b) 45. ( b) 46. (a) 47. (d ) 48. (c)
49. (a ) 50. (d) 51. (a ) 52. (c ) 53. ( b) 54. (a )
55. ( b) 56. (a ) 57. (d) 58. (a ) 59. (a ) 60 . (c)
61. ( b) 62. (c ) 63. (a ) 64. (c ) 65. (c ) 66 . ( d)
67. (c) 68. ( a) 69. (a ) 70. (b ) 71. (d ) 72. (c )
73. (c) 74. ( b) 75. (a ) 76. (c ) 77. (b ) 78. ( b)
79. (a ) 80. (d ) 81. ( b) 82. (a ) 83. (b ) 84. (a)
85. (a ) 86. ( b) 87. ( b) 88. (c ) 89. (d ) 90 . (c )
91. ( d) 92. (c ) 93. (a) 94. (d ) 95. (d ) 96. ( b)
97. ( d) 98. (c ) 99. (a ) 100. (c ) 101. (a ) 102. (c )
103. (c) 104. (a ) 105. (b ) 106. (c ) 107. (c ) 108. (b )
109. (c) 110. (b ) 111. (a ) 112. (b ) 113. (b) 114. (c )
115. (d) 116. (c ) 117. (a) 118. ( b) 119. ( d) 120. (a )
121. ( b) 122. (c) 123. (a) 124. (c) 125. ( d) 126. ( b)
127. (c ) 128. ( b) 129. ( d) 130. ( b) 131. ( b) 132 . ( b)
133. (c) 134. (c) 135. ( b) 136. ( c) 137. ( d) 138. (a )
139. (c) 140. (a ) 141. (c ) 142. (d) 143. (b ) 144. (c)
145. (c) 146. (a ) 147. ( b) 148. (c ) 149. (b ) 150 . ( b)
151. (a ) 152. ( b) 153. (c ) 154. (d ) 155. (b) 156 . ( b)
157. (a ) 158. (c ) 159. (c ) 160. (a ) 161. (c ) 162 . (a)
163. (c ) 164. ( b) 165. (a ) 166. (c ) 167. (b ) 168. (c )
169. (d ) 170. ( a) 171. (b ) 172. (a ) 173. (c ) 174. ( b)
175. ( b) 176. (c ) 177. ( b) 178. (c ) 179. (a ) 180 . (c )
181. ( b) 182. (d ) 183. (d ) 184. (c ) 185. (a ) 186. (d )
187. (c) 188. ( b) 189. ( b) 190. (d ) 191. (d ) 192. ( b)
193. ( b) 194. (d ) 195. (c ) 196. ( b) 197. (a ) 198. (c )
199. ( b) 200. ( d) 201. (c ) 202. (a ) 203. (c ) 204. (d)
205. ( d) 206. (c ) 207. ( b) 208. (b ) 209. (c ) 210. (a )
211. (a ) 212. (d) 213. (c ) 214. ( b) 215. (b) 216. ( b)
217. (c ) 218. (c) 219. (d) 220. ( a) 221. ( b) 222. (a )
223. (b ) 224. ( b) 225. (c) 226. ( a) 227. ( d) 228. (c)
229. ( b) 230. (a ) 231. ( b) 232. ( a) 233. ( b) 234. (c)
235. ( d) 236. (d) 237. ( b) 238. (c) 239. (c ) 240 . ( b)
241. (c) 242. (a ) 243. (d) 244. ( b) 245. (c ) 246 . (d)
247. ( d) 248. (c ) 249. (c ) 250. (c ) 251. (a ) 252 . (a )
253. ( b) 254. (d ) 255. (b ) 256. (b ) 257. (c ) 258. (c )
259. (d )
 Bibliography

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Bhat, B.I. and S. M . Vora, Stoichiometry, Tata McGraw -Hill, New Delhi, 1996.
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Henley, E . J. and H. Bieber, Chemical Engineering Calculations: Mass and Energy Balances,
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2004.
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parameter Corresponding States” , AIChE J . , 21, 510, 1975.
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1981.
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New York, 1976.
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1974.
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New Delhi, 2001.
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203-208, 1954.
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of Chemical Engineering by Peppas N. A. (Ed .), Kluwer Academic Publishers, 1989.
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Vapour Pressure and Entropy of Vaporization” , J . Am. Chem. Soc. , 77, 3427 1955.
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Phase Equilibria, 2nd ed., Prentice Hall, New Jersey, 1986.
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Engineering Education Development Centre, IIT Madras, 1981.
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 Answers to Exercises

Chapter 2
3
2.1 (a) 10 Pa s ( b ) 2.419 lb/(ft h )
2.2 1.0197 kgf/cm2, 14.5038 psi
2.3 0.2596 W /m K
2.4 (a) 257.95 kcal/(h m2 °C) (b) 52.832 Btu/(h ft2 °F)
2.5 iron
2.6 5.69 x 10 2 lb/ft 2.s
“

2.7 36.81 kg/s

2.8 66.67 kg, 654 N
2.9 18 W
2.10 15.3 m, 12.5 kJ
2.11 (a) 1286.305 N (b) 1.6378 bar (c) 0.5145 kJ (d) 196.2 J
2.12 F(inch3) = 0.0610 e3600'
2.13 5.6629 x 10 8 W/(m2.K4)

Btu (inch)0 25
'

2.14 (a
ft 2 (h )(°F)125

AT 1.25
(b) q = 1.313 025 , where q is in W /m2, D is in m and A 71 is in K
^
2.15 a = 3.602 atm L 2/( mol)2, b = 4.28 x \0i-2z L/(mol)
~

565
566 Answers to Exercises

kmol kmol
2.16 (a) k { = m 3 (min)(atm)2-2 ; k2
m (min)( atm)0 5
3 '

( b) k\ = 4.795 x 105, k’2 = 24.185

.85
/ 15 0.85

^ ^
•

2.17 AP = 7.5885
DP1.15

where AP is in Pa, p is in lb /(ft s), H is in ft, p is in lb/ft3, V is in ft/s and Dp is in ft .

2.18 (a) A = 18.2773, B = 3799.887, C = -226.296
(b) A = 14.331 28, B = 6839.7966, C = -375.0628
2.19 (a ) CP = 96.55 + 0.1562 r (b) CP = 33.24 + 0.0373 F
2.20 (a) CP = 6.35 + 1.811 x 10-3 r - 2.675 x 10 77* '

(b) CP = 6.825 + 1.665 x 10 3 T - 2.675 x 10 7712

'

(c) CP = 9.495 x 102 + 0.271 T - 4.0 x 10 57^

(d) CP = 6.795 + 0.93 x 10 3 r - 8.256 x 10 8 r2
~ ~

2.21 CP = 26.5386 + 4.24 x 10 2 r - 1.4295 x 10

2.22 (a ) 3.038 (b) 10.94
^
2.23 1.8829 x 10^

Chapter 3
3.1 267.41 g
3.2 3 mol
3.3 266.45 kg
3.4 72 g
3.5 58% C, 3.4% H and 38.6% Br
3.6 9 kg-equivalents
3.7 57.026
3.8 15.82 g.equivalents
3.9 49
3.10 C7H5N
3.11 (a) 125.38 kg (b) 12.685 g
3.12 (a) 684.48 kg ( b) 254.10 kg
3.13 (a) 93.65 kg ( b) 88.68 kg
3.14 (a ) 146.58 g (b) BaCl2: 44.61 g, Na2S04: 30.43 g (c) 25.04 g
3.15 1292.76 kg
3.16 0.41%
 Answers to Exercises 567

3.17 43.74 kg, 22.28 m3 at STP

3.18 (a) 17.64 m3 (b) 164.21 kg
3.19 1053.2 kg, 895.2 kg
3.20 0.8651 N
3.21 1.5
3.22 1.076
3.23 7.273
3.24 (a) 420 kg/m 3 (b) 2.24 kmol/h
3.25 18.91°Be, 30°Tw
3.26 45°Be
3.27 29.1°Be , 29.3°API
3.28 0.25
3.29 947 kg/m3
3.30 (a) 768.37 kg/m3 (b) 52.46
(c) gasoline = 24.66%, kerosene = 26.82%, gasoil = 28.30% and isopentane = 20.22%
3.31 0.9263
3.32 131.53 kg of Mg, 1136.78 kg of Na, 2132.67 kg of Cl2
3.33 75.69
3.34 K 44.87%, S 18.4%, 02 36.73%
3.35 47.23
3.36 Ferrous 44.06%, Ferric 34.43%
3.37 12.38% NaN03, 87.62% water
3.38 567.04 kg
3.39 90.02 %
3.40 0.4959, 0.33
3.41 55.23%
3.42 3.7203 x 105 kg
3.43 557.3 mol
3.44 24.57% Si02 - 2Ca0, 43.43% Si02 - 3Ca0
3.45 95.58% (weight) ethanol
3.46 (a) 1.688% (b) 3.48%
3.47 720 kg
3.48 1.0753
3.49 0.2860
3.50 39.75%, 0.6596
3.51 (a) 622.5 (b) 1.2971 (c) 1.213 kg
568 Answers to Exercises

3.52 (a) 0.4751 (b) 42.77 (c) 33.75

3.53 (a) 40.78% A, 27.18% B, 32.04% C (b) 63.07 (c) 41.38% (d ) 0.6242
3.54 16.66%
3.55 30.73
3.56 t 275.5
3.57 (a) 1.557 g-atom Ca, 3.133 g-atom C (b) CaC2
3.58 (a) 33.27 kg (b) 36.96 kg
3.59 (a) 3.09% (b ) 0.0319
3.60 (a) 23.29% 02, 76.71% N2 (b) 28.85
3.61 Chlorine 74.03%, Bromine 13.73%, Oxygen 12.24%
3.62 7.7 %
3.63 10.43
3.64 1291 kg/m3
3.65 70 000 ppm
3.66 (a) 179.2 (b) 0.046
3.67 2.78 mol/kg, 2.646 mol/L
3.68 (a) 12.94% (b) 65.00% (c ) 5.773 mol/L (d) 8.25 mol/kg solvent
3.69 (a) 29.77% ( b) 8.1467 mol/L (c ) 8.1467 g eq/L (d) 15.27% LiCl, 84.73% water
3.70 (a) 0.293 (b) 0.0727, (c ) 4.35 mol/kg water (d) 8 g eq/L
3.71 (a) 58.59% (b) 9.92 mol/L (c ) 21.716 mol/kg water
3.72 (a) KC1 = 24%, water = 76% (b) 0.0709 (c) 5.15 mol/ L (d) 4.24 mol/kg
3.73 (a ) 0.0287 kg (b) 0.26602 mol/L
3.74 (a ) Nitrogen ( b) 32.76% (c) 30%
3.75 94%, 94.95%
3.76 (a) 90% (b) 100% (c) 75%
0.5£
3.77
n0 + 0.5e
4 + 3e
3.78
8 + 2£
3£J + 4 e 2
3.79
5 + 2e{ + 2e2
3 - ei - e2
3.80
5 - 0.5£ ,
3.81 10%, 94.4%, 5.44%
3.82 (a) carbon 240 kg, silica 865 kg (b) 188 kg (c) 1491 kg
 Answers to Exercises 569

3.83 (a) 474.8 kg (b) 8.4% S02, 10.11% 02 and 81.49% N2

3.84 (a) Ammonia, 17.97% (b) 53.89 kg
3.85 (a) 25.96 m3 (b) 12.46 m3 (c ) 35.3 m3
(d) 35.25% S03, 23.53% S02, 41.18% 02 (e) 56.47
3.86 (a) 29.5% ( b) 14.71 kPa
3.87 (a) 0.4 (b) 0.343 bar
3.88 20%
3.89 (a) 300 m3 (b) 994.29 m 3 (c ) N2 = 29.32 m 3, H 2 = 87.96 m 3, NH3 = 58.64 m 3
3.90 (a) 0.292 m 3 (b) 40%

Chapter 4
4.1 1010.79 kg
4.2 91.67 m3
4.3 7.688 m3
4.4 (a) 2.167 kg (b) 1.702 kg
4.5 0.3557 m3/kg; 0.65% greater
4.6 12.67 bar
4.7 5.6686 x 105 N/m2
4.8 288.8 K
4.9 (a) 0.7153 kg/m3 (b) 2.8582 kg/m 3
4.10 7.6098 x 104 kg
4.11 78.98 kg
4.12 0.355 kg
4.13 1.0195 x 10 3 m 3
“

4.14 375 K
4.15 1.119 x 10 3 m3
4.16 2.48 g, 7.52 g
4.17 (a) 71.73% ethane, 2.01% hydrogen and 26.26% carbon dioxide
(b) 2.8865 x 10 2 mol /L ethane, 1.2027 x 10 2 mol/ L hydrogen, 7.2163 x 10 3 mol/L
carbon dioxide
(c) 241.82 kg/h
4.18 (a ) 35.74 kPa (b) 11.59 m 3
4.19 3.2462 m3
4.20 (a) 20.14 kPa (b) 4.42 m3 (c) 2.196 m 3/kg
4.21 C3H8
4.22 78%
570 Answers to Exercises

4.23 air: 4.313 x 105 N/m2, methyl alcohol: 1.951 x 105 N/m2, and steam: 1.736 x 105 N/m2
4.24 30.25
4.25 28.96, 1.1836 kg/m3
4.26 (a) C02 2.12%, N2 5.39%, CH4 92.5% (b) 16.64 (c) 0.7424 kg/m3
4.27 20
4.28 (a) 30.53 (b) C02 = 20.18, S02 = 1.05, CO = 1.83, 02 = 2.62, N2 = 74.32
(c) 1.7213 kg/m3 (d) 1.0582
4.29 (a) 19.68 (b) 22.36% C02, 53.44% Cl2, 17.8% N 2, 6.4% H 2
4.30 (a) 34.62 (b) 38.82
4.31 (a) 25.15 ( b) 1.21 kg/ m 3
4.32 (a) 3.0068 kmol (b ) 0.3757 kmol, 0.125 (c) 0.7578 kg, 0.007
(d) 6.25 m3 (e ) 35.95
4.33 (a) 120 kPa (b) 1.3826 m3 (c) 2 kg/m3
4.34 (a) 250 bar, 750 bar (b) 8.5155 (c) 204.84 kg/m3
4.35 (a) CO: 54.34, H2: 4.72, CH 4: 0.36, C02: 13.50, 02: 0.36, N2: 26.72,
(b) 17.93 (c) 0.8
4.36 (a) 38.98
(b) Ethylene: 22.0%, Benzene: 49.05%, Oxygen: 1.07%,
Methane : 6.37%, Ethane : 19.27%, Nitrogen: 2.23% (c) 1.7391
4.37 0.0252 kg
4.38 (a) 0.011, ( b) 0.648% NH 3, 99.352% air, ( c) 27.8, 28.87
4.39 (a ) 121.6 m 3 (b) 24.7 kg
4.40 (a ) 70.76 m 3 (b) 37.1 kg (c) 2.1% HC1, 97.9% Air
4.41 (a) 70.85 m 3 (b) 36.98 kg
4.42 (a) 92.02 m3 (b) 1.082 kg
4.43 (a) 46.44 m3 (b) 34.22 m3 (c) 87.72%
4.44 (a) 81.91 m3 (b) 25.92 kg
4.45 (a) 33.36 (b) 30.28 (c) 20.73 kg (d) 60.28%
4.46 (a) 2.778 m3/min (b) 22.727 m3/min
4.47 (a) 91.43 m3/h (b) 15.05 kg/h (c ) 91.84%
4.48 (a) 37.41 kg (b) 115.838 kg
4.49 0.3177 m3
4.50 (a) Ammonia, 17.97% (b) 53.89 kg
4.51 (a) 25.96 m3 ( b) 12.46 m3 (c) 35.31 m 3 (d) 35.29% S03, 23.53% S02, 41.18% 02
(e ) 56.51
4.52 (a) 29.5% ( b) 14.71 kPa
 Answers to Exercises 571

4.53 (a) 70% (b ) 0.6 bar

4.54 (a) 195.4 m3 (b) 36.036 kg
4.55 (a) 64.34% (b) 15.074 m 3 (c) 8.605 m3
4.56 404
4.57 (a) 4.98% CH3OH, 3.73% 02, 51.48% N2, 19.9% HCHO, 19.9% H20
(b) 395.13 m3
4.58 20%
4.59 30%
4.60 0.333 ethylene, 0.667 ethane
4.61 (a) 11.08% C02, 83.35% N2, 5.57% H20 (b) 26.98 kg (c) 0.0836 bar
4.62 (a ) 1142.58 m 3 (b) 4588.6 m 3/h (c) 259.39 kg, 51.37% HN03

Chapter 5
5.1 380.1 K
5.2 601.3 K
5.3 (a) 68.30 bar (b) 51.8 bar
5.4 23.84 bar
5.5 93.8 kPa, 94.23 kPa by ideal gas equation
5.6 9.78 kg
5.7 1.48 kg
5.8 (a) 3.502 x 10 3 m3/mol, 0.936 (b) 3.5021 x 10 3 m 3/mol, 0.9361
“ “

5.9 0.045 m 3, 0.06751 m 3

5.10 0.3206 x 10 3 m 3/mol
“

5.11 (a) V = 0.249 x 10 3 m3 (b) 0.23 x 10 3 m3/mol

~ “

5.12 (a) 3 x 10 3 m 3/mol (b) 2.98 x 10 3 m3/mol

~ ~

5.13 1.8 x 10^ m3/mol, a = 0.54985 N m4/mol2, b = 6.41 x 10 5 m 3/mol

~

5.14 7.134 x 10 5 m3/mol, 1.712 x 10 3 m3/mol

'

5.15 3.485 x 10 3 m3/mol, 0.8862

~

5.16 (a) 4.157 x 10 5 m 3/mol (b) 6.44 x 10 5 m 3/mol (c) 5.3 x 10 5 m 3/mol
“ '

5.17 76.76 bar

5.18 551 K
5.19 0.1255 m 3, 0.1357 m3 using ideal gas equation
5.20 (a) 3.795 x 10 4 m 3/mol (b) 3.726 x 10 4 m 3/mol
" ”

5.21 (a ) 3.639 x 10 3 m 3/mol (b) 3.52 x 10-3 m 3/ mol (c) 3.514 x 10 3 m 3 /mol
~ ~

5.22 (a ) 2.036 x 10 4 m 3/mol (b) 1.433 x 10^ m 3/mol (c) 1.4575 x 10^ m 3/mol
”

5.23 165.2 bar

572 Answers to Exercises

5.24 V = 1.426 x 10^ m3/mol

5.25 0.1196 m3
5.26 371.8 K
5.27 (a) 3.1178 x 10"1 m3/mol (b ) 2.8635 x lO 4 m3/mol
^

(c) 2.847 x 10 4 m3/mol (Amagat’s law ) 3.046 x 10 4 m3/mol ( Dalton’s law)

(d) 2.962 x 10 4 m 3/mol
5.28 (a) 2.8776 kg/m 3 (b) 2.8769 kg/m 3

Chapter 6
6.1 63.51 kPa and 118.04 kPa
6.2 4.184 x 102 kJ/kg
6.3 2.34 kPa ( 293 K), 7.63 kPa (313 K), 13.04 kPa (323 K),
20.87 kPa (333 K ), 47.95 kPa (353 K)
6.4 0.4653 bar
6.5 234.39 K
6.6 (a) 314.6 K (b) 28.06 kPa
6.7 15.33 kPa
6.8 6.7 kg
6.9 42 kPa, 0.5%
6.10 1.39 kg
6.11 1.29 kg
6.12 27.76 kPa, 0.18%
6.13 350.6 K, 30.55 kPa, 4.5%
6.14 (a) A = 14.655, B = 2209.7, C = 43 (b) 2861 kPa
6.15 370 K
6.16 (a) 181.97 kPa (b) 444.94 kJ/kg
6.17 (a) 27.102 kPa , 1.66% (b) 379.5 K
6.18 27.46 kPa, 3.0% deviation

Chapter 7
7.1 mole fraction of heptane x = 0.853, y = 0.893
7.2 7.47 kPa (benzene), 1.91 kPa (toluene); 76.8% (weight) benzene
7.3 (a) 25.2% A (b) 57.55 kPa
7.4 The liquid contains 67.42% (mol) nitrogen and the vapour contains 90.34% (mol) nitrogen
7.5 92.49% A
7.6 x = 0.5608, y = 0.7344
 Answers to Exercises 573

7.7 (a) 366.82 K (b) 28.05% n -hexane

T’ ( K ) 353.1 358 363 368 373 378 383 383.6

1.0 0.78 0.581 0.411 0.258 0.130 0.017 0
y 1.0 0.90 0.777 0.632 0.456 0.261 0.039 0

7.9 PA = 8.53 and PB = 2.24 kPa. Weight percent of benzene in vapour = 76.4%
7.10 (a) 39.06 kPa (0, 0 ), 66.99 kPa (0.2, 0.5335), 94.92 kPa (0.4, 0.7531), 108.88 kPa
(0.5, 0.8206), 122.84 kPa (0.6, 0.8728), 150.77 kPa (0.8, 0.9482), 178.7 kPa (1, 1 )
(b) 108.9 kPa, 64 kPa
7.11 Between 350.9 K and 357.6 K
7.12 72.32% (Raoult’s law )
7.13 94.7 kPa and 77.2 kPa
7.14 54%
7.15 64.86% A , 34.00% B , 1.14% C
7.16 (a) 25 kPa ( b) 12.5% A , 37.5% B , 50.0% C
7.17 16.7% A , 83.3% B
7.18 (a) 26.7% A , 26.7% B , 46.6% C (b) 11.47% A , 33.25% B , 55.3% C
7.19 (a) T = 330.4 K, y = 0.5886; (b) P = 57.63 kPa, y = 0.5908
7.20 /=
0.1982, x = 0.5608, y = 0.7344
7.21 Exhibits positive deviation from Raoult’s law. If Raoult’s law is obeyed , vapour
composition would be 0.413 mole fraction methanol.
7.22 131.24 kPa, 46.2% A
7.23 (a) 8.245 x 102 kPa,
(b) 25.1 % butane, 46.3% propane, 28.6% ethane,
(c) 6.19 x 102 kPa, 35.17% butane, 64.83% propane
7.24 (a) 342 K (1, 1), 343 K (0.958, 0.983), 348 K ( 0.726, 0.875), 353 K ( 0.527, 0.735),
358 K ( 0.360, 0.581), 363 K (0.210, 0.389), 368 K (0.094, 0.195) 372.4 K (0, 0)
7.25 (a) x and y are given in brackets against P in kPa:
33.79 (0, 0), 43.426 ( 0.2, 0.3775), 53.062 (0.4, 0.6179), 62.698 (0.6, 0.7844),
72.334 ( 0.8, 0.9066), 81.79 (1, 1 )
(b) x and y are given in brackets against T in K:
311.45 ( 1 , 1), 315 (0.787, 0.902 ), 319 (0.581 , 0.773), 323 ( 0.405, 0.623 ), 327
(0.254, 0.449), 331 (0.123, 0.250 ), 335.33 (0, 0)
7.26 (a) 352.8 K, 405.3 K,
(b) 352.8 (1, 1 ), 363.2 (0.685, 0.914), 373.2 (0.446, 0.786),
383.2 (0.266, 0.611), 393.2 (0.129, 0.378), 405.3 (0,0 )
(c) 369 K, 386.5 K
574 Answers to Exercises

7.27 (a) x and y are given in brackets against P in kPa:

30.74 (0, 0), 57.58 (0.2, 0.573), 84.42 (0.4, 0.782), 111.26 (0.6, 0.89), 138.1 (0.8,
0.956), 164.94 ( 1, 1)
(b) x and y are given in brackets against T in K:
352.88 ( 1 , 1 ), 360.0 ( 0.7658, 0.9474), 370.0 (0.5160, 0.8512), 380.0 ( 0.3310,
0.7137), 390.0 (0.1900, 0.5273), 400.0 ( 0.0797, 0.2805), 408.9 ( 0, 0 )
7.28 (a) 77.3% benzene (b) 57.5% benzene (c) 37.9%
7.29 (a) 89.26 kPa (b ) 59.5% benzene, 29.5% toluene and 11.0% xylene (c) 92.80, 85.26
7.30 (a) x = 0.5095, y = 0.8866 (b) 338.9 K, 75.7% pentane (c ) 108.5 kPa, 83.4% pentane
7.31 (a) 355.7 K (b) 0.56 (c) mole fraction of alcohol 0.16
7.32 9.0 kPa
4
7.33 0.101 x 10
-
kg oxygen per kg water
-4
7.34 3.074 x 10 m3
7.35 44.73 bar
7.36 HA = 0.23 bar, HB = 0.217 bar
4
7.37 5.0564 x 10 "

mol/kg
7.38 533 bar
7.39 (a) 15.7 kPa (b ) 391.4 K (c) 374.1 K (d) 36.68 kPa
7.40 329.7 K, 356.9 K
7.41 1310 kPa, liquid composition: 6.8% ethane, 66.2% propane, 23.8% isobutene and the
rest n -butane
7.42 (a) 330 K (b) 340.6 K
(c) Mole % in the liquid and vapour given in brackets: Ethane (0.48, 0.09), Propane (36.3,
17.45), Isobutane (18.18, 18.74), ^-Butane (44.98, 63.35), Isopentane (0.13, 0.38)
7.43 500 mol each.
Component Mole % in liquid Mole % in vapour
Methane 3.26 28.78
Ethane 16.30 29.68
Propane 42.10 29.90
Isobutene 16.30 5.70
w-Butane 22.04 5.94
7.44 (a) 930.3 kPa
(b) 337.4 K, Composition of condensate: Ethane (1.8% ), Propane (6.2%), Isobutane
(17.3%), n -Butane (67.1% ), Isopentane (7.50% ) 330.2 K, Composition of the liquid
and vapour: Ethane (3.22%, 16.81%), Propane (9.31%, 18.7% ), Isobutane (19.55%,
18.46%), ^ -Butane (63.38%, 44.57%), Isopentane ( 4.54%, 1.46% )
 Answers to Exercises 575

7.45 2205 kPa, Methane: 41.91, Ethane: 20.25, Propane: 21.96, Isobutane: 8.57, n- Butane:
7.31 706 kPa, Methane: 0.2, Ethane: 1.91 , Propane: 16.14, Isobutane: 30.88, n- Butane:
50.88
7.46 861.4 kPa, 2446 kPa
7.47 758 kPa
7.48 (a) 717 kPa ( b ) Propane : 63.93%, n-Butane: 36.07%
(c) Propane: 36.07%, n -Butane: 63.93%
7.49 (a) 356 K, 58.8% methanol, 24.1% ethanol, 8.4% propanol, 8.7% butanol,
(b) 373 K, 8.8% methanol, 8.9% ethanol, 13.6% propanol, 68.6% butanol
7.50 (a) 84.2 kPa (b) Ether = 51.26%, Water = 48.74%
7.51 (a) 347.97 K, Pure benzene (b) 342.2 K
7.52 3.35 kg
7.53 (a) 107.3 kPa (b) 66.44%
7.54 342 K, 0.0975 kg
7.55 (a) 342 K (b) 0.7 (c) 0.0989 kg
7.56 (a) 372.3 K (b) 3% aniline
7.57 (a) 295.68 K, 32.67% chlorobenzene (b) 341.1 K, 28.96% chlorobenzene
7.58 (a) 343.24 K (b) 80.15% Chloroform (c) 77.09% Chloroform
7.59 (a) 178.65 kPa (b) 361.14 K
7.60 (a) 327.2 K (b) Pure water (c ) 316.7 K
7.61 (a) 369.2 K (b) 4.78% aniline
7.62 (a) 361.6 K, 21.9% toluene, 13.1% ethylbenzene, 65.0% water
(b) 387.8 K, 26.8% toluene, 73.2% ethyl benzene
7.64 (a) 366 K, pure water
(b) 374.9 K, pure toluene , last drop of vapour contains 44.36% toluene
7.65 (a) 388.8 K, pure component 1 (b) 365.5 K, pure component 2
7.66 (a) 78.76 kg (b) 94.18%
7.67 (a) L = 74.6 mol, V = 25.4 mol
(b) Liquid : 0.062 ( A ), 0.737 ( B ), 0.201 ( C) Vapour: 0.409 ( A ), 0.591 ( B )
7.68 2.842 kPa
7.69 372.47 K
7.70 (a) 8.85 K (b) 7.8 K

Chapter 8
8.1 (a) 16.6% ( b) 29.2% (c) 0.1991 (d) 0.4127 (e) 0.4120 kg/m 3
8.2 (a) 3.56% (b) H20 = 1.49%, C02 = 98.51% (c) 0.0369 (d) 0.0151 (e) 0.0257 kg/m 3
576 Answers to Exercises

8.3 (a) 104.86 kPa (b) 0.0351

8.4 25.71 kg
2
8.5 Contains 0.946 x 10 kg benzene per m3
8.6 51.93 m3
8.7 50.99 kg
8.8 4 kg
8.9 18.8%
8.10 262.7 K
8.11 1623 kPa
8.12 43.6%
8.13 (a) 0.1429 ( b) 0.3172 (c) 0.1667 (d) 0.4643 (e) 0.7988 ( f ) 2.2254 (g) 42.67 kg
(h) 20.87% (i) 32.17%
8.14 (a) 10.13 kPa (b) 0.2302 (c) 0.111 (d) 0.2990 (e) 70.44% (f ) 73.41% (g) 106.2 kg
8.15 (a) 0.3710 ( b) 0.7690 (c) 28.4 kPa (d) 85.4% (e) 296.3 K
8.16 (a) 3.6122 kPa ( b) 49.65% (c) 0.023 ( d) 47.79% (e) 340.2 K
8.17 7.35 %
8.18 (a) 0.0537 ( b) 82.42% (c ) 81.48% (d) 327.45 K
8.19 19349 kJ/m 3
8.20 (a) 271 K ( b) 269 K
8.21 0.035
8.22 315.4 K
8.23 (a) 288.9 K (b) 0.0954 m3
8.24 (a) 0.2281, 0.0846 (b) Benzene 7.8% ( V ) , 18.6% ( fV) (c) 49.37%, 45.08%
8.25 (a) 306.8 K ( b ) 420.9 kPa
8.26 322.9 K
8.27 13.25 kg
8.28 344.22 kPa
8.29 (a) 0.3467 kg (b) 41.73%
8.30 309.7 K, 0.0157 kg/kg of dry air
8.31 0.0117 kg, 0.9857 m 3
8.32 (a) 19.2%, 90.6% (b) 0.67% water, 2.2% water (c) 18.63%, 90.3%
( d) 0.487 kg, 1.625 kg (e) 0.484 kg, 1.614 kg
8.33 (a) 2.36% ( b ) 0.244 (c) 0.384 (d) 298.9 K (e) 236.6 kPa
8.34 (a) 0.377 kg of acetone/kg dry of nitrogen , 0.6727 kg of acetone/kg dry nitrogen
(b) 0.2953 kg (c) 28.05 kg (d) 111.3 m3
 Answers to Exercises 577

8.35 285 kPa

8.36 6498.35 m3/h
8.37 (a) 78.8% (b) 24.23 m3/min
8.38 20.5%
8.39 1.65 kg/h
8.40 (a) 0.0191 kmol/kmol of dry air, 0.00494 kmol/kmol of dry air (b) 1.0276 kg
(c) 38.10 m3
8.41 283.03 K
8.42 159.75 kPa
8.43 164.53 m 3/h
8.44 0.0258 kg of water per kg of dry air
8.45 0.0408 kg of water per kg of dry air
8.46 (a) 314.1 K (b) 0.224 kg of benzene per kg of dry air (c ) 216.7 kJ
8.48 (a) 299.3 K (b) 304 K
8.49 (a) 279 K (b) 312.3 K
8.51 (a) 6.25% (b) 1.602 kPa (c) 0.16 kg of water/kg of dry air (d) 20.7 kPa
(e) 7.73% (f ) 287.7 K (g ) 1.0238 kJ/kg (h) 300.7 K
8.52 (a) 0.04 ( b) 0.0644 (c ) 26.5% (d) 1.0036 m3 (e) 310.2 K (f ) 158.05 kJ/kg
8.53 (a) 0.035 kg/kg (b) 0.0564 kmol/kmol (c) 14% (d) 1.0255 m 3/kg
(e) 313 K ( f ) 162.39 kJ/kg
8.54 55.81 kJ
8.55 0.99875 m 3/ kg, 153 kJ /kg, 155 kJ/ kg
8.56 (a) 0.013 kg/kg of dry air, 0.0209 kmol/kmol of dry air, 1 %
(b) 329 K, 0.028 kg/kg dry air, 22.5%
8.57 (a) 0.035 kg/kg of dry air, 0.0564 kmol/kmol of dry air, 30%
(b) 5.407 kPa, 34.4% (c) 310.7 K (d) 1.071 kJ/kg, 0.979 m 3/kg, 150.3 kJ/kg
8.59 0.007 kg
8.60 (a) 299.5 K (b) 0.004 kg
8.61 (a) 298 K (b) 5.55 kg
8.62 (a) 0.04 kg/kg of dry air (b) 313 K (c) 310 K (d) 70%
(e) 0.046 kg/kg of dry air, 318 K ( f ) 0.598 kg
8.63 (a) 0.01 kg/kg dry air (b) 40% (c) 370 K (d) 68.6 kJ
8.64 0.0085 kg, 41.3 kJ /kg
8.65 (a) 333 K ( b ) 298 K (c) 31.82 kJ (d) 27.6 kJ
8.66 (a) 0.0322, 50%, 283.2 K (b) 0.1206, 85%, 316.2 K (c ) 6.07 kg
578 Answers to Exercises

8.67 (a) 289 K (b) 0.01 kg/kg of dry air (c) 0.004 kg
8.68 12122 kg/h wet air
8.69 6514.1 m 3/h
8.70 (a) 44.9% ( b ) 18 912.3 m3/h
8.71 (a) 3604.6 m 3/h (b) 3355.4 m3/h
8.72 (a) 305 K ( b) 0.2489 kg (c ) 8.76 m3/h
8.73 3.15 kg
8.74 (a) 0.017 kg/kg of dry air, 58%, 295 K (b) 6782.5 kJ (c) 2.706 kg (d ) 310 K
8.75 (a) 312 K, 323 K (b) 48% (c) 90.07 m 3
8.76 (a) 0.028 and 0.096 kg/kg of dry air (b) 45.45 kg/h (c) 82612 kJ/ h
8.77 (a) 0.0175, 44%; 0.02, 100%; 0.02, 0.9%, 0.038, 45% (b ) 2778 kg (c ) 2686 m3
8.78 (a) 295.7 K, 300.7 K (b) 16.69 kg/h (c) 342.7 K
8.79 (a) 318.65 K ( b ) 70%
8.80 (a) 311 K (b) 2.43 kg (c) 9.11 kg
8.81 (a) 310 K ( b) 382.2 K (c) 3393.3 kg/h ( d) 2851.9 m3/h

Chapter 9
9.1 25 kg
9.2 3.457 kg
9.3 Urea 214.4 kg, Phosphoric acid 359 kg, KC1 411.5 kg
9.4 0.8F - 0.1 IP = 400; B - 0.675P = 0; 0.2F - 0.215P = 0; F = 573.3 kg,
P = 533.3 kg, B = 360 kg
9.5 6250
9.6 5625 kg
9.7 33.33 kg
9.8 43.48 kg
9.9 Waste acid 419.18 kg; Cone. HN03 397.26 kg, Cone. H 2S04, 183.56 kg
9.10 0.0244 g/L
9.11 106.28 mol/h
9.12 530.95 kg/h
9.13 0.3184 m3
9.14 8 : 3 : 9
9.15 1 : 10.64
9.16 ? 19.19
 Answers to Exercises 579

9.17 (a) 1.6349 x 1(T3 m 3 (b) 853 kg

9.18 (a) ? 102105 ( b ) ? 75 958
9.19 3.3322 x 104 kg/h
9.20 9.51 kg
9.21 (a) 2000 kg, 1200 kg (b) 2000 kg/h ( c) 800 kg/h
9.22 (a) 25% NaOH (b) 60% NaOH, 2% NaCl, 38% H20 (c) 4500 kg
9.23 NaCl 62.5%, Water 37.5%
9.24 (a) NaBr 2.68%, MgCl 2 8.04% (b) NaCl 78.95%, NaBr 5.26%, MgCl 2 15.79%
9.25 (a) 35200 kg (b) 4800 kg (c) 10000 kg
9.26 10.526 kg/100 kg of water
9.27 299.7 K
9.28 Na 2S04 5.2%, water 94.8%
9.29 Na 2S04 : Na 2C03 = 1 : 2.37
9.30 30% Ca (N03)2.4H20, 70% CuS04.5H20
9.31 536.86 kg
9.32 (a) Na2S04 = 27.96%, H20 = 72.04% (b) 0.0147 kg
9.33 39.15 kg crystals
9.34 211 kg
9.35 (a) 294.12 kg (b) 85.47 kg
9.36 (a) 251.26 kg (b) 10.3 kg
9.37 (a) 1857 kg of water, 368 kg of crystals (b) 399 kg of crystals
9.38 (a) 6370 kg (b) 6630 kg
9.39 (a) 17.5 kg ( b ) 18.61 kg
9.40 700 kg, 94.7%
9.41 (a) 3.58 m3 ( b ) 534 kg
9.42 (a) 844 kg ( b ) 285.69 kg
9.43 10.1%
9.44 (a) 47.42 kg (b) 25.91 kg
9.45 (a) 7607.1 kg (b) 1085.7 kg
9.46 (a) 332.74 kg (b) 16.48 kg MgS04/100 kg of water
9.47 (a) 607.95 kg (b) 130.85 kg
9.48 (a) 29.63 (b) 329.52 kg (c) 8487.14 kg (d) 102.86 kg
9.49 (a) 19.33 kg (b) 66.3%
9.50 75 %
580 Answers to Exercises

9.51 93.1%
9.52 (a) 588.24 kg (b) 420.59 kg
9.53 96.31%
9.54 (a) 229.17 kg/h (b) 55%
9.55 (a) 5.79% ( b) 44.22% (c ) 96.03%
9.56 6250
9.57 (a) 42 kg (b) Pulp = 51.72%, Water = 48.28%
9.58 150 kg
9.59 0.4167 kg
9.60 (a) 1.105 kg of water per kg of dry leather
(b) 1.05 kg of water per kg of dry leather (c) 95.24%
9.61 (a) 125 kg, 102.04 kg (b) 97.22%, 2.55%
9.62 (a) 313.15 K, 318.65 K (b) 70% (c) 89.22 m 3
9.63 (a) 318.65 K ( b) 70%
9.64 (a) 311 K (b) 2.43 kg (c) 9.11 kg
9.65 5279.5 kg of wet air/h
9.66 (a) 820 kg ( b) 105.26 kg (c) 4774.02 kg
9.67 (a) 911.77 kg ( b) 508 kg
9.68 (a) 17.74 kg/h (b ) 97.99 m 3/h
9.69 30 kg, 70 kg
9.70 50.82 g ( upper layer ), 49.18 g (lower layer)
9.71 (a) 68.23 kg, 131.77 kg (b) 74.13%
9.72 (a) 166.93 kg, 133.62 kg (b) 31.72 kg
9.73 (a) 40% acid, 60.0% water (b) 90 kg of raffinate, 160 kg of extract (c) 150 kg
9.74 82.05%
2
9.75 2.2383 x 10 “

kg
9.76 1.318 kg
9.77 36.11 kg
9.78 (a) 1373.93 m 3 (b) N2 = 10.97%, CH 4 = 89.03%
9.79 (a) 2916.37 kg (b) 75.25%
9.80 75 %
9.81 (a) 7.58 kg (b) 986 mol/min (c) 3.41% (d) 14.9 m 3/min
9.82 (a) 157.73 kg (b) 1336.68 kg (c) 221.05 kg (d) 34.9 kg (e) 186.15 kg
9.83 (a) 903.06 kmol/h ( b ) Benzene : 0.554%, Toluene = 99.446%
 Answers to Exercises 581

9.84 (a) 40 kg (b) 4.44 weight % alcohol

9.85 (a) 37.5 kg ( b) 0.6
9.86 462.48 kg
9.87 (a) Feed 44.02%, distillate 97.44%, residue 5.85%
(b) Distillate 41.67 mol, residue 58.33 mol
9.88 (a) 615.84 kg (b ) B = 3.2%, T = 64.32%, X = 32.48%
9.89 (a) 78.95 mol; 49.6% propane, 50.4% butane (b) 35.9 mol
9.90 Overhead: Ethylene 7.79%, Ethane 11.68%, Propylene 19.46%, Propane 56.07%,
Isobutane 5.0%;
Bottoms: Propane 0.8%, Isobutane 31.91%, n - Butane 47.10%, «- Pentane 20.19%
9.91 (a) F = 40 kg/s, G = 60 kg/s, H = 20 kg/s
(b) Feed: B = 36.36%, C = 23.64%; D: B = 4.55%, C = 0.45%;
F: B = 86.35%, C = 8.64%
9.92 (a) 92.33% (b) 240.9 mol/s

Chapter 10
10.1 C02 = 12.34%, 02 = 5.97%, H20 = 13.41%, N 2 = 68.28%
10.2 (a) Ethane : 0.21% , C02 = 3.32%, CO = 0.41%, H20 = 5.6%,
02 = 14.41% and N2 = 76.05%
(b) Ethane : 0.22%, C02 = 3.51%, CO = 0.44%, 02 = 15.27% and N2 = 80.56%
10.3 49.1%
10.4 (a) 195.4 m 3 (b) 36.036 kg
10.5 (a) 11.08% C02, 83.35% N 2, 5.57% H20 (b) 26.98 kg ( c ) 0.0836 bar
10.6 0.3374 ethene , 0.6626 ethane
10.7 (a) C02 = 9.97%, H20 = 15.03%, N 2 = 75.0% (b ) 0.553 kg (c) 28.09 kg
10.8 C02 9.83%, CO 0.52%, 02 6.57%, N2 83.08%
3 3
10.9 (a) 6.93 m ( b) 54.286 m (c) 20.45% C02, 1.34% 02, 78.21% N2
10.10 (a) CO 1.71%, C02 17.5%, 02 2.19%, N2 78.6% (b) 177.29 kg
3
10.11 (a) 6216 m /h (b ) 10.96% C02, 0.61% CO, 85.69% N2 and 2.74% 02
(c) 17 138 m3/h
10.12 (a) 2237.76 kg (b) C02 = 8.76%, H20 = 9.19%, 02 = 6.68%, N 2 = 75.37%
(c ) 28.76
10.13 (a) C02 = 6.61%, 02 = 6.45%, N 2 = 71.88%, H20 = 15.06%
(b) 2784.93 m 3 (c) 327.56 K
10.14 (a) 16.24% ( b ) 1216.7 m 3
582 Answers to Exercises

10.15 0.811
10.16 94.23% C, 5.77% H2
10.17 319.08 K
10.18 37.0%
10.19 25 %
10.20 (a) 24.7% ( b) C : H = 1 : 0.309
10.21 (a) Methane = 50.0%, N2 = 50.0% (b) 7.73%
10.22 (a) 1:7.5 (b) 22.69 kg (c ) 0.812 kmol
10.23 C02 = 11.33%, S02 = 0.33%, CO = 2.12%, 02 = 3.38%, H20 = 6.49%, N2 = 76.35%
10.24 75.3%
10.25 (a) 6.67 kg ( b) 0.834%
10.26 (a) 24.6% (b) 37.62 kmol
10.27 (a) 2.188 kg (b) 4.6% (c ) 14.26 kg
10.28 (a) 33.33% ( b ) 8
10.29 (a) 60% CH4, 40% C2H6 (b) 40%
10.30 24.2 %
10.31 (a) 19.71% (b) 0.374 (c) 13.72 m3
10.32 (a) 40% (b) 3: 1 , C2H6 (c) 18.72 m 3
10.33 (a) 12.19% (b) 60.81% (c) 12.3304 mol (d) 1767.14 m 3
10.34 (a) 1.900 kmol (b) 13.78% C02, 4.59% CO, 4.25% 02, 77.38% N 2
10.35 79.36%
10.36 (a) 2.67:1 , C3H8 (b ) 85:1 (c) 77.81 m 3/min
10.37 (a) 10% ( b ) C4H 10 (C) 5716.7 m3 (d) 3812.8 kg/h
10.38 (a) 12.44% ( b ) 1:0.2778 (c) 15.66 m3 (d) 2.72 kg
10.39 26.57 %
10.40 19.9%
10.41 (a) 251.61 kg ( b) 1.056 (c) 2.28 kmol ( d) 34.7%
10.42 (a) 63.42% ( b) 41.71 m3 (c ) 13.54 m3
10.43 (a) 16.61% (b) 11.41 kg (c ) 16.4517 m3 (d) 22.08% C , 77.92% inerts
10.44 (a) 1190.53 kg (b) 43.02 kmol/h
(c) C02 13.08%, CO 1.44%, H20 6.60%, 02 4.03%, S02 0.09%, N 2 74.76%
3
10.45 (a) 8.92 kmol (b ) 55.3% (c ) 381.93 m
10.46 (a) 196.154 kmol (b) 170.57 kmol (c) 1.75%
10.47 7.88 kg, 5.12 kg
 Answers to Exercises 583

10.48 (a) 1224.5 kg (b) 10.4%

10.49 (a) 3.72% (b) 40% (c ) 10.87 m3
10.50 (a) 50.2% (b ) 1362.6 kg (c) 61.9 kg (d) 1095.7 m3
10.51 (a) 2.572 kg ( b) 1458.6 kg (c ) 982.82 m 3 (d ) 3.897%
(e) C: 73.8%, H: 5.12%, O: 9.77, S: 1.1, Ash: 10.2%
10.52 (a) 27.14% ( b) C02 7.71%, CO 1.94%, N2 83.37%, 02 6.92% (c ) 14.256 kPa
10.53 80.07%
10.54 (a) 60% ( b) 14.23 m3 (c) 8.92 m 3
10.55 95.6%
10.56 (a) 957.08 kg (b ) S02 = 9.45%, 02 = 11.55%, N2 = 79.00%
(c) S02 = 0.5%, S03 = 9.4%, 02 = 7.39%, N2 = 82.71%
10.57 6.34% S02, 1.59% S03, 10.10% 02, 81.97% N2
10.58 89.35 %
10.59 17.02 %
10.60 2.0276 kg
10.61 2.7886 kg
10.62 312.8 m3
10.63 (a) 80.789 kg, 2.24% FeS2, 54.11% Fe203, 18.09% ZnO, 6.99% S03, 18.57% inerts
(b) 7.73%
10.64 (a) 347 m 3 ( b ) 70.0% (c) 864.04 m 3
10.65 76.8%
10.66 0.2975
10.67 (a) 73.64 kg (b ) 1.8501 kmol 02, 14.8371 kmol N2, 1.4511 kmol S02, 0.007 kmol S03
(c) 40.5% (d) 3.47%
10.68 67.6%
10.69 (a) 604.29 kg ( b) S03 7.21%, S02 8.65%, 02 10.90%, N2 73.24%
(c) 110.05 kg (d) S03 7.01%, S02 0.22%, 02 8.87%, N 2 83.91%
(e) 71.57 kg
10.70 (a) 6.043 kg ( b) S02 9.13%, S03 7.66%, N2 73.01%, 02 10.20%
(c) 117.24 kg (d) 87.84%
10.71 (a) 1.2465 kmol (b) 8.8% (c) 182.77 kg
10.72 (a) 1.32 x 105 kg (b) 2.64 x 104 kg
10.73 (a) 9.70% ( b ) 197.5 kg (c) 95.95 (d) 507.84 kg/h
(e) 0.32% S02, 10.30% 02, 89.38% N2
10.74 (a) 523.81 kg ( b) 0.4334 kg (c) 1765 kg
584 Answers to Exercises

10.75 (a) CaC03 60.31%, MgC03 35.13%, inerts 4.56% (b ) 9.12% (c) 43.93 kg
10.76 CaC03 70%
10.77 (a) 65% CaC03, 30% MgC03, 5% inerts
(b) 10.92 kmol (c ) 86.2 kg (d) 8.54%
10.78 (a) 40% ( b) Air/Fuel: 15.35:1 (c) 99.55 kg ( d) 71.57 kg
10.79 (a) Phosphate :sand:charcoal = 1 : 0.663:0.288 (b) 6.04 kg
10.80 (a) 3.36% ( b) 49.886%
10.81 (a) 114.15 kg (b) 718.44 kg (c ) 72%
10.82 (a) 187.12 kg
(b) CaS04 = 70.35%, H 2S04 = 15.11%, HF = 1.03%, inerts = 13.51 %
10.83 51.58 kg
10.84 298.3 kg
10.85 (a) 13.16% (b) 91.52% (c) 595.62 kg; A1203 16.05%, impurities 83.95%
10.86 (a) 276 mol (b) 0.7567 kg
10.87 2.8303 x 107 m3/day
10.88 (a) NO 2%, N2 78%, 02 20% (b) 0.7 kPa 0.68 kPa (c) 29.49 kg
10.89 (a) 131.84 kg (b) Na2S04 63.38%, H 2S04 34%, H20 1.5%, HN03 1.12%
(c) 107.91 kg (d) 72.35 kg, 3.42 kg
10.90 (a) 1244.27 m 3 (b) 300.04 kg
10.91 (a) 1142.86 m 3
(b) 51.34 kmol; 1.19% NH3, 10.58% 02, 71.42% N 2, 6.72% NO, 10.09% H 20
(c) 49.79 kmol, 1.22% NH 3, 7.79% 02, 73.65% N2, 0.69% NO,
6.24% N02, 10.4% H20 (d) 355.16 kg, 36.75%
10.92 (a) 1 :1.2313
(b) HC1 17.98%, Cl 2 26.22%, 02 6.9%, N2 42.24%, H20 6.66%
3 3
10.93 (a) 178.6 m ( b) 297.24 m (c) 117.62 kg
( d ) 9.15% HC1, 8% 02, 18.3% Cl2, 64.55% N2
10.94 (a) 1.136 kg
(b) HC1 = 18.78%, Cl2 = 27.38%, 02 = 6.18%, N2 = 40.70%, H20 = 6.96%
(c) 324.53 K
10.95 (a) 2020.29 kg of CC14, 842.37 kg of S (b) 1660 kg of CC4, 644.42 kg of S
10.96 (a) CS2, 20.28% (b) 71.89% (c) 51.98 kg
10.97 (a) 1417.26 kmol, 1079.76 kmol (b) 44 477.92 kg, 44 477.92 kg
(c) HC1 = 40.98%, Ethylene = 16.54%, 02 = 9.89%, N 2 = 32.58%
(d) HC1 = 4.1 %, Ethylene = 2.36% , 02 = 1.8%, N 2 = 32.58%,
H20 = 9.11 %, EDO = 50.05%
 Answers to Exercises 585

10.98 90.7%, 91.9%

10.99 (a) 97.49% ( b ) 94.55% (c) 1123.4 kg (d) 1255.77 kg
(e) HC1 603.07 kg, H20 266.18 kg
10.100 247.8 kg
10.101 30 300 kg/h
10.102 404
10.103 (a ) 30.1% (b) 4.54 : 1
10.104 (a) 32.88 kg (b) 63.42 kg (c ) 0.52 kg/ h
10.105 (a) 4.98% CH3OH , 3.73% 02, 51.48% N2, 19.9% HCHO, 19.9% H 20
(b ) 395.13 m 3
10.106 50%
10.107 ( a ) 5 mol (b) 50% (c) 86.5 mol (d) 72.57%
10.108 (a) 2677.2 kg ( b) 2369.7 kg (c) 27.81:1
10.109 C2H 4 23.08%, H20 64.23%, ether 0.13%, ethanol 2.31%, inerts 10.26%
10.110 (a) 18.94 kg, 86.28 kg
(b) monosulphonate 7.58%, disulphonate 34.51%, H2S04 51.34%, H 20 6.57%

Chapter 11
11.1 o. i
11.2 55.56%
11.3 0.1667
11.4 0.1837
11.5 (a) 0.3591 ( b ) 4.22 kg (c ) 129.9 m3
11.6 (a) 375 kg (b) 10% (c) 30%
11.7 (a) 100000 kg/h (b) 6.75%
11.8 0.7093 kg/kg
11.9 (a) 26.56% (b) 6000 kg/h (c) 1816.24 kg/h
11.10 6729.63 kg
11.11 23.44 kg/h
11.12 (a) 1.2 ( b) 46.51 (c) 0.973 kg/min
11.13 (a) 3571.43 kg (b) 58 204 kg
11.14 (a) 0.2 ( b) 2.25 kg
11.15 (a) 404.21 m 3 (b ) 57.86 kg (c) 190.97 kg
11.16 (a) Benzene 2%, toluene 55.34%, xylene 42.67%
(b) 2438.21 kg, 6768.62 kg (c ) 96.92% (d) 9752.84 kg
586 Answers to Exercises

11.17 (a) 7205.93 kg/h (b) 6195.52 kg/h (c ) 93.66 kg/h ( d ) 6.05%
11.18 23 295.37 kg; 10.83% NaCl, 84.88% H20, 4.29% KC1
11.19 0.6132
11.20 (a) 926.32 kg/h (b) 818.67 kg (c) 409.33 kg
11.21 (a) 1 :6 ( b) 75.19 kg (c) 12.53 kg
11.22 (a) 2777.78 kg/h (b ) 2177.8 kg/h (c) 17 400 kg/h
(d ) 22 177 kg/h, 11.12% NaCl, 2.71% KC1, 86.17% H20
11.23 (a) 130.16 kg/h (b) 0.838 kg of dry air/kg of dry air in the fresh air feed
11.24 (a) 4.0953 kg/min (b) 52.21 kg/min (c) 45.44 m 3/min ( d) 358.34 kg/min
11.25 (a) 315.8 kg/h (b ) 105.26 kg/h (c ) 894.74 kg/ h
11.26 (a) 0.9067 ( b) 6.9% A , 12.3% B , 6.3% C, 74.5% D
11.27 (a) 0.9 (b) 30% A , 43.33% B , 2.22% C, 24.45% D
(c) A = 13.33% , B = 10.00%, C = 5.00%, D = 71.67%
11.28 (a) 20% ( b ) 9.09%
11.29 20%
11.30 3.1
11.31 0.6312
11.32 (a) 567.31 kg/h (b) 432.69 kg/h (c ) 0.5851
11.33 (a) 2401.3 kg ( b) 121 kg (c) 2562.6 kg
11.34 5! 60 kmol/ h C3H8; S2 200 kmol/h C 3H8; S3 140 kmol/ h C3H8, 60 kmol /h C3H6,
60 kmol/h H 2; S4 60 kmol/h H 2; S5 60 kmol/h C 3 H6; S6 140 kmol/h C3H 8
11.35 (a) 300 (b) 1700
11.36 (a) 3: 11
(b) Mass%: ethanol 29.22%, acetaldehyde 9.31%, H20 3.81% , 02 10.83% , N2 46.82%;
Mol%: ethanol 20.69%, acetaldehyde 6.90%, H20 6.90%, 02 11.03%, N2 54.48%
11.37 77.27%
11.38 (a) 290.35 kg, 91.4% (b) 0.49 (c) 108.9 kmol
11.39 (a) 4 kmol/h (b) 80% (c ) 3 kmol/h
11.40 (a) 1.66 kmol, 2.13 kmol (b) 314.86 kg/h (c ) 28.21% (d ) 37.24 m 3
11.41 (a) 42.86 mol NH3 ( b) 1 :2.14
11.42 (a) 227.6 kmol/h to A , 190.6 kmol/h to B (b) 404.04 kmol/h
11.43 (a) 544 mol
(b) CO 31.27%, CH 3OH 4.82%, CH4 0.69%, H20 0.69%, H 2 62.53%
(c) 28 mol
11.44 4 mol to 100 mol feed
 Answers to Exercises 587

11.45 (a) 177.45 kg/h ( b) 186.9 kg/h

11.46 (a) 0.0079 ( b ) 48.4 mol (c ) 97.0%
11.47 (a) 673.74 mol (b) 6.667 mol
(c) CO 20.38%, H2 76.17%, CH4 3.0% (d) 31.11 mol
11.48 (a) 1:5.71 ( b) 24.13 kmol (c ) 111.41 kg (d) 27.24 kg/h
11.49 (a) 860 kmol (b) 4 kmol (c) 9.43%
11.50 (a) 50.08 kmol ( b) 5.87 kmol (c ) 2.93 kmol
11.51 (a) 0.0157 (b) 0.2 molAr/3 mol N2-H 2 (c) 382 mol
11.52 (a) 130.92 mol (b) 42.71% H 2, 57.29% CH 4 (c) 127.17 mol
11.53 (a) 63.79 kmol (b) 95.69% (c) 6.18 kmol

Chapter 12
12.1 17.845 m , 25 kJ
12.2 13.86 kJ
12.3 89.55 kg, 878.51 N
12.4 30.6305 x 105 J
12.5 1.667 x 102 kJ
12.6 7.355 kJ, 61.29 W
12.7 (a) 14.715, 0 (b) 0, 14.715 (c ) 0.035 K
12.8 16.8 W
12.9 123.46 m3
12.10 (a) 4.164 x 103 N (b) 1.3254 x 105 N/m2 (c) 2.082 x 103 J ( d ) 490.5 J
12.11 17.15 m /s
12.12 (a) 1 J (b) 147.15 J
12.13 2.156 x 105 J
12.14 20.39 m
12.15 3:1
12.16 1.146 x 104 kJ
12.17 6.073 x 104 J
12.18 (a) 183.94 kJ ( b) 1839.4 kJ (c ) 1655.46 kJ (d ) 38.36 m/s (e) 1839.4 kJ
12.19 AC/ = 37.9 kJ /mol; AH = 41 kJ/mol
,
12.20 U = - 0.9045 kJ /kg, Uv = 282.11 kJ /kg, Hv = 320.5 kJ /kg
12.21 58.4 x 104 J
12.22 420.1 kJ, 2214 kJ/kg, 2423.9 kJ/kg
588 Answers to Exercises

12.23 (a) 3.572 kJ (b) 10.97 min

12.24 (a) 4122.2 J (b) CP = 8.85394 + 8.2744 x 10 37 - 3.4150 x lO^ r2
12.25 (a) 41.2339 J/mol K ( b) 39.6355 J/mol K (c) 7927 kJ
12.26 (a) 50.0395 kJ/kmol K (b) 22.3251 x 104 kJ
12.27 (a) 440.22 kJ (b) 4.40 kJ/kg K
12.28 (a) 30.7324 kJ/kmol K (b) 30732.4 kJ/kmol
12.29 31.496 kJ/kmol K
12.30 (a) CP = 7.7844 + 0.13447 - 4.7696 x 10 “

572 ( b) 46 237.6 J
12.31 4525.07 kJ
12.32 46.31 kJ/kmol K, 46 310 kJ/kmol
4
12.33 1.55 x 10 kJ
12.34 14 187 kJ/kmol
12.35 233.55 m3/min
12.36 322.44 kJ
12.37 3105 kJ
12.38 2223.3 kJ/kg
12.39 4.184 x 102 kJ/kg
12.40 255.95 kJ/kg
12.41 397.7 kJ/kg
12.42 117 895 kJ /kmol, 112 582 kJ/kmol
12.43 8918.5 kJ/kg
12.44 (a) 482 624 kJ/h (b ) 178 831 kJ/h
12.45 (a) 181.97 kPa ( b) 444.94 kJ/kg
12.46 389.8 K
12.47 2.6% liquid
12.48 0.9948 kg/s
12.49 759 K
12.50 (a) 125.44 kJ/kg (b) 2622.14 kJ/kg
12.51 (a) 40 kPa (b) 223 kPa (c) 18242 kJ
12.52 18 467 kJ, 148.6 bar
12.53 995.96 kJ/kg of water
12.54 195 814 kJ
12.55 1.246 x 106 kJ
 Answers to Exercises 589

12.56 914.86 kJ, 139.35 kJ

12.57 (a) 11 987.5 kJ ( b) 275.4 K
12.58 442.224 kJ
12.59 (a) 60 522 kJ ( b) 140.3°C
12.60 T = 305.8 K
12.61 62 187.5 kJ
12.62 9.661 x 106 kJ
12.63 250.77 J/kg
12.64 340.62 K
12.65 -10.217 kJ / mol
12.66 178 873 kJ
12.67 5100 kJ removed
12.68 1.2914 x 107 kJ/h
12.69 21 783 kJ
12.70 (a) 38 kJ ( b ) 0 (c ) 4.31 bar ( d) - 47.8 kJ
12.71 (a) - 24.0685 kJ (b) - 17.695 kJ (c) 6.374 kJ
12.72 (a) 250 kJ (b) 173.3 kJ
12.73 (a) 981 J (b ) 981 J (c ) 0.234 K
12.74 6.92 x 105 J
12.75 25 J , 75 J, -100 J, 100 J
12.76 (a) 14 m/s (b ) 0.78 K
12.77 (a) 22 480 kJ ( b ) 8730 kJ
12.78 166.67 kJ
12.79 - 895 879.7 kJ
12.80 (a) 1.48 x 104 kg (b) 3.022 x 10
~
4
(c) 50 h
12.81 2168.6 kJ, 3000 kJ , -125.32 kJ, 2043.28 kJ
12.82 391.4 K, 1.96 Pa
12.83 2328.7 kJ
12.84 1243.6 kJ , 1742.4 kJ
12.85 407.18 kJ
12.86 (a) 2282 kJ (b) 2206 kJ (c) 0
12.87 (a) 472.5 K (b ) - 4863 kJ (c) 0 (d) 4863 kJ (e) 5981 kJ
12.88 (a) 997.68, 1662.8, - 997.68 kJ/kmol (b) - 997.68, - 1662.8, - 665.12 kJ/kmol
(c) 0, 0, 1490, 1490 kJ/kmol (d) 0, 0, -172.8, -172.8 kJ/kmol
590 Answers to Exercises

12.89 3407, 1077, -2329, -3252 kJ/kmol

12.90 (a) 1 bar, 56 K, 4656, 6518, 0, 4656 kJ
(b ) 5 bar, 1400 K, 22 380.3, 32 592.0, 0, 22 380.3 kJ
12.91 (a) 0.373 kg ( b ) 0.304 kg
12.92 418.5 K, 7.65 bar
12.93 (a) 600 K, 2 bar, 4605 kJ (b) 132.9 K, 0.443 bar, 2376 kJ (c) 900 kJ
12.94 70 kJ
12.95 313.46 hp
12.96 722.51 kW
12.97 435.5 hp
12.98 92.9 hp
12.99 144.1 kW
12.100 (a) Q = 3122 kJ/kg, Ws = 0, AH = 3122 kJ/kg
(b ) Q = 0, Ws = 588.34 kJ/kg, AH = -588.34 kJ/kg
12.101 1744 hp
12.102 35 kJ
12.103 (a) 402.64 m/s (b) 5.751 x 10^ m2
12.104 344 K
12.105 (a) 46.88 J /kg (b) 50 J/kg
12.106 15.35 hp
12.107 2453 kJ /kg
12.108 2.03 hp
12.109 1.72 K
12.110 30.523 kW
12.111 2.95 x 105 N/m2, 1481.3 W
12.112 4.316 kW, 86.22 kPa, 966 kPa
12.113 81.51 kW
12.114 ( a) 6259 kg/h ( b ) 378 kg/h
12.115 0.824 hp
12.116 82.785 kPa
12.117 (a) 5725.2 kWh /day (b) 1.099 m
12.118 122 155 kg/ h , 7759 kg/ h
12.119 3.174 x 106 kJ /h
12.120 35 kg
 Answers to Exercises 591

12.121 (a) 9.4313 x 105 kJ/h (b) 12.3470 x 105 kJ/h

12.122 214 030 kJ/h, 17.26 kg
12.123 1 029 025 kJ
12.124 3314.8 kJ
12.125 ( a) 2976.1 kg/h ( b) 1.94 x 105 kJ/h
12.126 178 354 kJ/h

Chapter 13
13.1 -1207.43 kJ
13.2 -194.9 kJ / mol
13.3 -323.53 kJ /kmol
13.4 -81.69 kJ
13.5 -102.933 kJ/mol
13.6 -110.52 kJ/mol
13.7 -74.79 kJ
13.8 -110.52 kJ/mol
13.9 (a) 358.2 kg/h (b) 142.86 kmol/h
13.10 49.819 x 103 kJ/m3 and 45.224 x 103 kJ/m3 at STP
13.11 AHCgHi 2 = 6 A//CH30H + 142216
13.12 -114.408 kJ
13.13 -904.7 kJ / mol
13.14 -1654.27 kJ/mol
13.15 -241.83 kJ/mol
13.16 -2204.14 kJ/mol
13.17 49.02 kJ/mol
13.18 2.24 J/mol
13.19 117.715 kJ/mol
13.20 -5.623 x 103 kJ/kg
13.21 -177.0 kJ
13.22 -286.46 kJ
13.23 -110.52 kJ/mol
13.24 -199.5 kJ / mol
13.25 5.7 K
592 Answers to Exercises

13.26 -886.83 kJ/mol

13.27 155.52 kJ/mol, 158.74 kJ//mol
13.28 2.072 x 105 kJ
13.29 118.5 x 103 kJ/h
13.30 32 525.5 kJ/kmol of acid to be added
13.31 19 662.7 kJ
13.32 -42.62 kJ/mol
13.33 -183.950 kJ
13.34 -185.342 kJ/mol
13.35 23 178 kJ/kg of methane
13.36 -393.83 kJ / mol
13.37 -224.5 kJ
13.38 328 299.8 kJ/kmol of CH4
13.39 -377.45 kJ/mol
13.40 617.88 kJ
13.41 -3283.43 kJ/mol
13.42 70.35 x 103 kJ/mol
13.43 5641.26 kJ /mol
13.44 -191.88 x 103 kJ/kmol
13.45 28 098 kJ
13.46 320.97 kJ
13.47 (a) 6.91 kg/h (b) 804.3 m3/h (c) 8646 kJ/h
13.48 2.103 x 106 kJ/h
13.49 2285.3 K
13.50 2079.6 K
13.51 1308 K
13.52 82%
13.53 854 K
13.54 1215 K
13.55 1990 K
13.56 351.1 K
13.57 857 K
13.58 2237 K
 Index

Absolute humidity, 201, 210 Average molecular weight, 85, 86

Absolute saturation humidity, 202, 210 Avogadro’s law/ principle, 78, 92
Absorption, 10, 77, 244, 272 Avogadro’s number, 42
columns, 10, 272
Acentric factor, 116, 118, 119, 137
Adiabatic Basis for calculation, 92, 246, 251
cooling curves, 220 Batch process, 243-244
flame temperature, 492 Baume scale, 48
humidification, 223 Benedict-Webb-Rubin equation, 111, 112
process, 440 Bernoulli’s equation, 445, 446
reaction, 491, 492 Biochemical oxygen demand , 341
reaction temperature, 492 Biot number, 34
saturation chamber, 219 Biotechnology, 5, 338
saturation curves, 220 Blast furnace, 328
saturation temperature, 218, 219, 220 Blending, 252
Adsorbate, 265 Blowdown, 378, 379
Adsorbent, 265 Boiling point, 131, 133, 143, 144, 182
Adsorption, 11, 77, 88, 252, 265 diagram ( T-x-y diagram), 152, 153
isotherm, 265 elevation, 181
Air conditioning, 198, 369 Boll man extractor, 262
Air oxidation of ammonia, 329 Boyle’s law, 78
Amagat’s law, 84, 122 Brix scale, 49
American Institute of Chemical Engineers, 1, 4, 7 Bubble point, 149, 164
Antoine curve, 152
constants, 137 pressure, 164, 166
equation, 136, 140 temperature, 164, 167
API scale, 48 Buckingham -/? theorem, 33
Arthur D. Little, 7, 9 Bulk density, 48
Atomic heat capacity, 417 Bypass, 368, 369
Atomic weight, 41, 507, 508, 509 operation, 369
Available hydrogen, 301 streams, 368

593
594 Index

Calcination of limestone, 322 Dalton’s law, 123, 151, 164, 166

Cellular products, 338 Deacon process, 333
Cement industries, 322 Degree of
CGS system, 15 completion, 62
units, 48 reduction, 341
Change in enthalpy, 439, 471, 474, 484 freedom, 249
Charles’ law, 78 Dehumidification, 11, 88
Chemical engineering, 1-2, 5-9, 13, 34, 41, 150, 198, Density, 47-49, 85-86
252, 399 DePriester, 164
achievements in, 4 Derived
chemistry versus, 1 quantities and their conversion, 21
future avenues and opportunities in, 5 quantity, 15
history of, 6 unit, 14, 16, 17, 18
official definition of, 1 Desorption, 10, 272
Chemical oxygen demand , 341 Deviation from ideal behaviour, 161
Chemical process industries, 1, 2, 10, 399 Dew point, 164, 165, 200, 207
Chemisorption, 265 curve, 152
Chlorination, 333 pressure, 167
of carbon disulphide, 334 temperature, 149, 164, 165, 168
of glacial acetic, 334 Differential distillation (also see simple distillation),
of methane, 334 243
Cinder, 315 Dilute solution, 162, 163
Clapeyron equation, 134, 138, 422, 423 Dimension, 14, 15, 29
Classification of material balance problems, 243 Dimensional
Clausius-Clapeyron equation, 134-136, 421, 423 analysis, 32, 33
Combustion, 510 equations, 29
process, 298 similitude, 32
of solid, liquid and gaseous fuels, 298 Dimensionless
Component balance, 242, 248, 279, 298 equations, 32
Components of energy balance equations, 401 group, 32, 33, 34
Compressibility Distillate, 10, 278, 371
charts, 114, 117 Distillation, 2, 10, 77, 252, 272, 276
factor, 114 116, 118 119, 123
- - differential (or simple), 243
Condensation, 131 flash distillation, 154, 277
Constant pressure process, 439 Distribution diagram, 153
Constant temperature process, 440 Drag coefficient, 34
Constant volume process, 439 Dry basis, 52
Continuous process, 243, 244 Dry- bulb temperature, 210, 216, 217, 223
Conversion, 62, 64, 368, 379 Drying, 11, 52, 77, 88, 215, 246, 252, 265, 371
of empirical equations, 28 operations, 198
factors, 21, 22 Dryness fraction, 133
of reactants, 64 Duhring line, 143, 144, 181
of units, 21 Duhring’s plot, 424
Cox chart, 139, 140, 143 Dulong and Petit, 416
Critical
point, 108, 109, 133
pressure, 108, 110 Effect of temperature on
properties, 107, 108, 111, 137 heat of reaction, 484
temperature, 108, 110, 131 standard heat of reaction, 483
Crystallization, 11, 252, 256, 257 Electrolysis of brine, 333
Cyclic process, 405, 436 Elemental balance, 339
 Index 595

Empirical equation, 14, 28, 32 Fanning friction factor, 34

Endothermic reactions, 471 Filtration, 12, 252
Energy, 24 First law of thermodynamics, 400, 401, 405, 436,
kinetic (KE), 24, 401, 402, 405, 437, 444 482
potential (PE), 24, 401^102, 405, 437, 444 for non-flow process, 436
Energy balance, 60, 338, 399, 400, 401 Fixed carbon, 301
in cyclic processes, 436 Flash distillation, 154, 277
for flow processes, 443 Flash vaporization, 154, 164, 153, 169, 277
in non-flow processes, 436 calculations, 165
thermochemistry, 471 Flow energy, 402, 403
thermophysics, 399 Fluid flow operations, 9, 252
English system (FPS system), 15 Flux, 328
Enthalpy, 18, 223, 224, 405, 406, 427, 428, 434, 445, Force, 21
471, 475, 484, 492 Fourier number, 34
change, 409, 410, 419, 484 FPS, 17, 32
change of mixing, 429 system, 23, 24, 42, 79
change of phase changes, 419 units, 29, 48
of humid air, 223 Fractionation (fractional distillation), 10, 278
of vaporization, 424 column, 278, 371
-composition diagrams, 434 Frank H. Thorpe, 7
-concentration diagrams, 434 Freeze driers, 265
Entrance work, 403 Froude number, 34
Entropy, 427, 428 Fuel ratio, 322
of vaporization, 427 Fusion
Equal - pressure reference-substance plots, 138, 143, curve, 133
424 line, 132
Equal-temperature reference-substance plots, 138, 139, temperature, 132
424
Equation of state, 106-109, 111, 122
Equilibrium conversion, 62 Gangue, 315
Equilibrium curve/diagram ( y-x diagram), 153, 154 Gas absorption, 88, 252
Equilibrium (flash) distillation, 153, 277 Gas constant, 79
Equilibrium moisture content, 265 Gauge pressure, 23
Equivalent weight of, General guidelines on the use of SI units, 19
acid , 46 General material balance equation, 297
base, 46 Generalized
element, 46 charts, 117, 118
oxidiser, 47 compressibility chart, 115-116, 123
reducer, 47 compressibility factor, 117, 120
salt, 46 compressibility factors correction, 120
Euler number, 34 Genetic engineering, 5
Evaporation, 10, 253, 276 George E . Davis, 6, 9
Evaporator, 10 Gibbs phase rule, 177
crystallizer, 256 Graetz number, 35
Excess oxygen, 298 Gram mole, 42
Excess reactant, 60, 61 Gram- atom, 42
Exothermic reactions, 471 Gram-molecule, 42
Extent of reaction, 64 Grashof number, 35
Extracellular products, 338 Green chemistry, 5
Extract, 11, 269, 270 Gross heating value, 474
596 Index

H. Von Helmholtz, 400 mixture, 414

H.L . Roy, 7 processes, 439
Handbook of Chemical Engineering, 7 Ideal solutions, 149 150, 161 162, 166, 181, 417
- -

Harold Hartley, 6 Incomplete reactions, 472

Hausbrandt chart, 178 Independent material balance equations, 248
Heat, 24, 401, 402 Indian Institute of Chemical Engineers, 8
Heat capacity, 214, 408, 409, 415, 430, 439, 484 Individual balances, 243, 251
of aqueous solutions, 418 Infinite point, 140
at constant pressure, 409 Internal energy, 401, 405, 428, 436-437, 439-440,
at constant volume, 408 444, 482
of gases, 410 Ion-exchange, 12, 252
of liquids, 416, 417 Isothermal process, 440
of mixtures of gases, 414
of solids, 416, 417
Heat effects accompanying chemical reactions, 471 Joule’s experiments, 400, 401
Heat of Journal of Industrial and Engineering Chemistry, 7
combustion, 473, 475
condensation, 419
formation, 474, 475 K factors ( values), 163, 164
fusion, 419, 421 Key component, 88, 244, 245, 251
mixing, 429, 429, 430 Kilogram mole ( kilomole), 42
reaction, 475 Kinetic energy (KE), 24, 401, 402, 405, 437, 444
reaction at constant pressure, 482 Kistyakowsky equation, 424
reaction at constant volume, 482 Kopp’s rule, 417
solution, 431 Krystal crystallizers, 256
vaporization, 419, 422, 424
Heat transfer
coefficient, 33 Latent heat of
operations, 9, 252 fusion, 419
Heating value, 474 vaporization, 134-135, 138 139, 223, 419, 422
-

Henry’s law, 162, 163 Law of

and gas solubility, 163 combining proportions, 92
Hess’s law of constant heat summation, 475 conservation of energy, 400
Higher heating value, 474 conservation of mass, 241
Humid heat, 214 Leaching, 11, 252, 261
Humid volume, 223 Lee and Kesler, 137
Humidification, 11, 88, 215, 219 Lee Kessler modifications, 119
-

-dehumidification operations, 198 Lewis M . Norton, 7

operations, 198, 246, 252 Lewis
Humidity, 198, 200, 207, 210, 216, 217, 220, 223, 371 number, 35
chart, 210, 216 relation, 216
Hydration, 337 Limiting reactant, 60, 61
Hydrogenation of, 337 Liquid-liquid extraction, 11, 252, 269-270
carbon monoxide, 337 Lower heating value, 474
fatty acids, 337 Lydersen et al . method , 116
oils, 337

Mach number, 35
Ideal gas, 77, 78, 80, 84, 92, 106, 114 Manufacture of
constant, 79 nitric acid, 329
law (equation), 78, 80, 92, 106, 109 urea, 329
 Index 597

Mass balance, 44 Newton’s law conversion factor, 23

Mass fraction, 51 Nomographs, 164
Mass percent, 51 Non-cyclic process, 405
Mass ratio, 52 Non-flow process, 406
Mass transfer operations, 10, 252 Non-ideal solutions, 161
Material and energy balance, 13, 41, 88 Normal boiling point ( NBP), 131
Material balance, 60 241-243, 248 249, 252,
- Normal molar volume, 45, 81, 92
257, 273, 334, 337, 372, 400 Normality, 57
calculation, 328, 329 Number of degrees of freedom, 177
with chemical reaction, 297 Nusselt number, 33, 35, 36
without chemical reactions, 252
in combustion process, 300
principles, 241 Observed (or apparent ) yield , 339
in recycle operation, 373 Oleum, 315
in unit operations, 241 Once- through material balance, 372
steps for solving, 250 Orsat
Mean compressibility factor, 122 analysis, 298
Mean heat capacity, 413 apparatus, 299
Mechanical Outlines of Industrial Chemistry, 7
energy balance, 445 Overall conversion, 372
operations, 252 Overall yield , 63
separations, 12 Overflow, 262, 263
Membrane separation, 12, 252 Oxidation of sulphur compounds, 314
Metallurgical industries, 2, 328 Oxychlorination of ethylene, 334
Metric system (MKS system), 15, 16, 23, 24, Oxygen requirement, 341
Mixing, 13, 252
Mixture of
ideal gases, 82, 122 P-T diagram, 132
real gases, 122 P-x-y curve/diagram , 151, 152, 161
MKS/CGS, 17 Packed column, 272, 273, 278
Molal humidity, 200, 201, 204 Partial pressure, 82, 83, 84, 151, 162, 163, 198, 199,
at saturation, 201, 202, 204 201, 204, 207, 216
Molality, 57 Partial volume, 83
Molar volume, 45 Parts per million ( ppm), 57
Molarity, 57 Peclet number, 35
Mole, 16, 42 Peng Robinson equation, 111, 112
-

concept, 41, 43 Percent excess, 61

fraction, 54, 55, 84, 85 oxygen, 298
percent, 54, 55 Percent humidity, 200, 203, 204, 210
ratio, 55 Percent saturation, 204
Molecular engineering, 5, 6 Perfect gas law, 108
Molecular weight, 41 Perpetual motion machine, 400
Multiple-effect evaporator, 254 Phase diagram for immiscible system, 178
Phase rule, 427
Phosphorus compounds, 325, 326
Nanotechnology, 5, 6 Physical adsorption, 265
Negative deviation from ideality, 161 Pitzer, 116, 119
Nelson and Obert, 115 Pitzer method , 118
Net heating value, 474 Plant yield , 63, 64
Net hydrogen, 301 Plate column/tower, 272, 278
Net oxygen demand, 62 Porosity, 48
598 Index

Positive deviation from ideality, 161 saturation, 203, 204, 207, 210
Potential energy, 24, 401^102, 405, 437, 444 vapour pressure, 181
Pound mole, 42 volatility, 130
Power, 24, 402 Respiratory quotient, 340
Power number, 36 Reynolds number, 33, 35, 36
Prandtl number, 33, 35, 36 Rotary dryer, 265, 266
Pressure, 23, 24 Rotating- disk extractor, 270
atmospheric, 23
gauge, 23
Primary Saturated
dimensions, 14, 15, 16, 32 liquid , 107, 131, 133, 134
quantities, 15 liquid state, 107
Principle of corresponding states, 115 steam table, 427
Processes in biological systems, 338 vapour, 107, 131, 133, 134
Proximate analysis, 301 Saturation, 198
Pseudo-critical humidity, 210, 216, 220
properties, 123 pressure, 107, 132, 133
temperature, 122, 123 temperature, 132, 133
Psychrometric Schmidt number, 36
chart, 210, 211, 217, 224 Screening, 12
line, 216, 217, 220 Sedimentation, 12, 252
ratio, 216 Selectivity, 63
Pure-component volume, 55, 83 Semiempirical equations, 13
Purge/ purging operation, 368, 378-379 Sensible heat, 419
Shell-and -tube heat exchanger, 400
Sherwood number, 36
Short-tube vertical evaporator, 253
Quality, 107, 133, 428
SI, 17
of steam, 134
base units, 16
of vapour, 133
derived units, 17
Quality or dryness fraction, 427
prefixes, 18
system, 15, 23, 24, 32, 401
units, 16, 18, 19, 21, 42, 48, 79
Raffinate, 11, 269, 270 Simple distillation ( see also differential distillation),
Raoult’s law, 149 151, 155, 161, 162, 163, 164, 181
-
243, 244
Reaction coordinate, 64 Single pass conversion, 372
Reactor yield , 63 Single-effect evaporators, 254
Real gases, 106 Single-stage extraction, 269
Recovery of metals, 328 Size reduction, 12
Rectification, 278 Solutions and phase behavior, 149
Recycle, 368, 371, 372, 378, 379 Specific gravity, 47, 48, 85, 86
ratio, 371 scales, 48
Redlich-Kwong equation, 111 Specific heat, 215, 408
Redlich-Kwong-Soave equation, 112 Specific volume, 427, 428
Reduced Spray chamber, 369
pressure, 115, 116, 122 Spray driers, 266
temperature, 115, 116, 137 Standard heat of
Reference substance plots, 138, 424 combustion, 473
Reflux, 277, 278, 371 formation, 474, 510
ratio, 278 reaction, 430, 471, 472, 482, 484, 485
Relative Standard state, 81, 472, 473
humidity, 203 pressure, 472
 Index 599

Stanton number, 36 Ultimate analysis, 301

State function ( property), 405, 484 Underflow, 262, 263
Steady-state Units, 15
flow processes, 443 Unit operations, 7, 8, 9, 13, 41, 77, 252
non-flow process, 437 Unit processes, 8, 13, 41, 337
process, 243 Unsteady-state process, 243
Steam distillation, 177
Steam tables, 133, 427
Stoichiometric van der Waals equation, 109, 122
coefficient, 60, 341 Vaporization, 130
number, 472, 483 (equilibrium) constant, 163, 164, 165
ratio, 60 curve, 133
Stoichiometry, 13, 41, 43, 338 of liquid , 132
Stripping, 10, 272 Vapour, 107, 108
Sublimation curve, 133 Vapour pressure, 130, 131, 134, 135, 138, 139, 140,
199, 202
Substrate, 338
of immiscible systems, 177
Superheat steam tables, 428
plots, 138
Superheated vapour, 131
of pure hydrocarbons, 137
Superphosphate, 325
of solutions of non-volatile solute, 181
Swenson-Walker crystallizer, 256
over solutions, 149
Synthesis of ammonia, 329 Vapour-liquid equilibrium , 108, 133, 134, 150
System of units, 15 calculations, 163, 166
(VLE) problems, 166
Virial coefficients, 112
Temperature of reaction, 491 Virial equations, 111, 112
Theoretical flame temperature, 492 Volatile combustible matter, 301
Theoretical oxygen, 298 Volume atomic heat capacities, 416
demand , 341 Volume fraction, 55
Theoretical yield, 339 Volume percent, 55, 56
Thermochemistry, 471
Thermodynamic properties of
saturated steam, 511, 512 Watson equation, 424
superheated steam , 514, 515, 516, 517, 518, 519 Weight fraction, 51
Three- phase temperature, 177, 178 Weight percent, 51
Tie element, 88, 244, 245, 251 Wet basis, 52
Wet-bulb depression, 216
Tie line, 153
Wet-bulb temperature, 215, 216, 217, 218
Total energy balance, 444, 445
line, 216
Twaddell scale, 49
Work, 24, 401
Total material balance, 242, 248, 279, 298
Total oxygen demand , 341
Tower packings, 273 Yield , 63, 64, 339, 368, 372
Tray driers, 265 coefficients, 339
Triple point, 15, 133 observed, 339
Triple superphosphate, 325 overall, 63
Trouton’s rule, 424 plant, 63, 64
Stoichiometry and Process Calculations
K. V. Narayanan • B. Lakshmikutty Second Edition
Designed as a textbook for the undergraduate students of chemical engineering and related disciplines such as biotechnology,
polymer technology, petrochemical engineering, electrochemical engineering, environmental engineering and safety engineering,
the chief objective of the book is to prepare students to make analysis of chemical processes through calculations and to develop
systematic problem- solving skills in them.
The text presents the fundamentals of chemical engineering operations and processes in a simple style that helps the students to
gain a thorough understanding of chemical process calculations. The book deals with the principles of stoichiometry to formulate
and solve material and energy balance problems in processes with and without chemical reactions. With the help of examples, the
book explains the construction and use of reference - substance plots, equilibrium diagrams, psychrometric charts, steam tables
and enthalpy composition diagrams. It also elaborates on thermophysics and thermochemistry to acquaint the students with the
thermodynamic principles of energy balance calculations.
The book is supplemented with Solutions Manual for instructors containing detailed solutions of all chapter - end unsolved
problems.
NEW TO THE SECOND EDITION
Incorporates a new chapter on Bypass, Recycle and Purge Operations
Comprises updations in some sections and presents new sections on Future Avenues and Opportunities in Chemical
Engineering, Processes in Biological and Energy Systems
Contains several new worked - out examples in the chapter on Material Balance with Chemical Reaction
Includes GATE questions with answers up to the year 2016 in Objective - type questions
KEY FEATURES
SI units are used throughout the book .
All basic chemical engineering operations and processes are introduced, and different types of problems are illustrated with
worked - out examples.
Stoichiometric principles are extended to solve problems related to bioprocessing, environmental engineering, etc.
Exercise problems (more than 810 ) are organised according to the difficulty level and all are provided with answers.
THE AUTHORS
K .V. NARAYANAN, PhD, is former Professor and Head, Department of Chemical Engineering, Government Engineering College,
Thrissur. Before that, he was Professor and Head, Department of Chemical Engineering, Government Engineering College,
Kozhikode. Dr. Narayanan has about 30 years of teaching experience and is a member of several professional bodies. He has also
served as Principal in various engineering colleges for about 10 years. He has contributed a number of research articles to
reputed international journals.
B. LAKSHMIKUTTY, PhD, is former Professor and Head, Department of Chemical Engineering, Government Engineering College,
Thrissur. She has about 30 years of teaching experience and has contributed several research articles in the area of polymer
science and engineering. She is an active member of several professional bodies.

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