I An .

Insight into
I

'j
Chemical Engineering ,j

Through Instant Notes, Objectiye Types and Pr~bl~ms

ct,n'~AL Ll6.BAIO' ...i

A,nmai Enginet:ri~~g College
Tvuv•nnamaw - 606 603

(Useful for GATE and other Aptitude Tests)

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,~ jRlsbal Publicatio~ Chennai-5

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 ARUNAI ENGINEERING C0\.,1: I
An Insight into
Chemical Engineering
msubbu
TIRUVANNAMALAI . 60G uv..,
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 FOREWORD
Competitive examinations have become inevitable nowadays for admission to graduate
courses and placement in chemical and allied industries, for undergraduate students in chem-
ical engineering. For such examinations, apart &om a wide knowledge of all aspects of unit
operations of chemical engineering a quick wit to solve the questions/problems is absoluteley
essential. Exhaustic revision of all these operations studied in earlier semesters is a tedious
procedure. A quick insight into the same a.long with solutions to short answer objective
questions or problems is =iated. With this objective in view, the author has ma.de an
attempt to prepare this monograph after going through many question papers of this type
from several universities along with an intensive study of the operations covered.
I had the oppurtunity of revising the text and providing academic advice wherever nec-
essary. I am confident this effort of the author will be well received by the budding chemical
engineers taldng their first degree from engineering colleges.

Dr. N. SUBRAMANIAN
Former Professor & Head
Department of Chemical Engineering
Indian Institute of Technology Madras

Chennai
October 5, 2003
 PREFACE
For competitive examinations to pursue higher studies or get jobs, depth of knowledge in
problem solving and answering objective type questions should be the essential qualities of
a successful Chemical Engineer.
A set of instant notes are given for vaxious important topics in the core s ubjects of
Chemical Engineering. I hope this set of topics detailed in this book will be of extreme use
to the undergraduate students and practicing engineers for enhancing and checking their
knowledge in the core concepts of the subject. Io any competitive examination due weightage
is being given to objective type questions. Io this book I have also given objective type
questions which will be useful for the chemical engineers and students for their preparation.
By lecturing for the past few years in core subjects of Chemical engineering like Fluid
Mechanics, Thermodynamics and Process Control at Department of Chemical Engineering,
Sri Venkateswara College of Engineering (SVCE), Sriperumbudur I have found that the stu-
dents need additional input for applying theoretical knowledge for solving the problems. In
this book a comprebenslve set of problems in each of the nine subjects of Chemical Engi-
neering are given with the steps in solving the same from the first principles which could be
understood easily by a novice in the field also. Most of the problems are questions that were
asked in GATE (Graduate Apt itude Test in Engineering) and in University examinations.
I extend my heartful thanks to Dr.N.Subramanian (Visiting Pro.fes.50r, SVCE - For-
mer Professor in Indian Institute of Technology Madras, Chennai) for spacing his valuable
time to review this book and provide technical guidance whenever needed.
I sincerely aclmowledge the in.anagement of SVCE for their support.
I am grateful to Dr.V.Ravichandran (Assistant Professor, Dept. of Computer Applica-
tions, SVCE) for introducing and enthusing me to learn WIEX software, with which this
book is typeset. Also he helped me in solving the objective type questions of Mathematics.
Mr.B.Neduma.ran (Assistant Professor, Dept. of Chemical Engineering, SVCE) was al-
ways helpful in conducting GATE coaching to students of SVCE, that initiated me to prepare
these materials.
Always my affection and thanks lie with my students who extended their interest to
the fullest. Also I thank the Chemical Engineering community allover the world for their
encouragement through my website http://www.svce.a£..in/ --.,msubbu for the study materials
provided in the website.
My thanks are due to my wife Mrs.S.P11nchi for her suggestions in publishing this book
and providing administrative assistance. I thank my dear parents and relatives for their
emotional support during these ye.axs.
.
• I thank the publisher for bringing out this edition l.t. the earliest.
Awaiting for your valuable ideas, to be posted at http://www.msubbu.com

-· Chennai
October 15, 2003
msubbu
(M. SUBRAMANIAN)
 ---.

Contents

1 Process Calculations 9
1.1 Instant Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.1.1 Units and Standards . . . . . . . . . . . .. .. .. .' . . . . . . . .
. 9 .
1.1.2 Material B alance Calculations . . · . . . . . . . . . . . . . . . . . . .
. 10.
1.1.3 Energy Bal.a.nee Calculations . . . . . • . . . . . . . . . . . . .
. 11.
1.1.4 Saturation & Humidity . . . . . . . . . . . . . . . . . . . . . .
. 12.
1.1.5 Combustion Calculat ions . . . . . . . . . . . . . . . . . . . . .
. 12.
1.2 Objective Type Questions . . . . . . . . . . . . . . . . . . . . . 13
1.3 Problems wit h Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.3.l Volume of Gas at STP . . . . . . . . · . . . . . . . . . . . . . . . 19
1.3.2 Ornat Analysis of Flue Gas . . . . . . . . . . . . . . . . . . , . . . . . 20
1.3.3 Concentration of S02 in Flue Gas . . . . . . . . . . . . . . . . . . . . 20
1.3.4 Conversion of S02 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.3.5 Percentage Excess Air . . . . . . . . . . . . . . . . . • . . . . . . . . . 21
1.3.6 Calcination of Lime.stone . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.3.7 Percentage of CH4 Burnt . . . . . . . . . . . . . . . . . . . . . . . . 23
1.3.8 Percent age Convezsion of C 2H4. . . . . . . . . . . . . . . . 24
1.3.9 Propane Dehydrogenation Plant . . . . . . . . . . . . . . . . . . . . 25
1.3.10 Methanol Production in Recycle Reactor . . . . . . . . . . . . . . . 26
1.3.11 Recycle Ratio in Reverse Osmosis Desalination . . . . . . . . . . 27
1.3.12 Recycle to the Reactor . . . . . . . . . . . . . . . . . . . . . . .
. . . . 28
1.3.13 Saturator Bypass . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . 29
1.3.14 Drying of CaC03 Slurry . . . . . . . . . . . . . . . . . . . . .
. . . . 30
1.3.15 Crystallization . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . 31
1.3.16 Heat Load on Heater . . . . . . . . . . . . . . . . . . . . . . . .
. . . . 32
1.3.17 Heat of ReactioLL . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . 33
1.3.18 Amount of Heat Requlred . . . . . . . . . . . •. . . . . : . . . . . . . 34
1.3.19 Flame 'lemperature and Excess Air . . . . . . . . . . . . . . . . . . . 35
1.3.20 Beat Released from Reaction . . . . . . . . . . . . . . . . . . 35
1.3.21 Conversion in Exothermic Reaction . . . . . . . . . . . . . . . 36
1.3.22 _Maintaining Isothermal Operation of Reactor . . . . . . . . . 37

l
2 AN INSIGHT INTO CHEMICAL ENGINEERING - msubbu CONTENTS 3

2 Fluid Mechanics 39 3.3.4 Specific Rate of Grinding , . . . . . - - - • - - . • - 91

2.1 Instant Notes . 39 3.3.5 Speed of Ball Mill . . . . . . . . . . . . . . . . . . . 92
2.1.1 Fluid Statics 39 3.3.6 Diameter of Roll Crusher . . . . . . . . . . . . . . . 92
2.1.2 Fluid Flow . 39 3.3.7 Classification based on Terminal Settling Velocity-I. 93
2.1.3 Flow Meters. 43 3.3.8 Range of Velocities for Classification . . . . . . . . . 95
2.1.4 'lra.nsportation of Fluids . . 44 3.3.9 Classification based on Terminal Settling Velocity-II 95
2.1.5 Flow Pa.st Immersed Bodies . 45 3.3.10 Screening and Classification . . . . . . . . . . . . 97
2.2 Objective Type Questions . . . . 46 3.3.11 Filtration Equation . . . . . . . . . . . . . . • • . • • 98
2.3 Problems with Solutions . . . . 55 3.3.12 Constant Pressure Filtrntion-I 99
2.3.1 Two Layer Buoyancy . . . . . . . . . . . . . . . . . 55 3.3.13 Constant Pressure Filtration-II . . . . . . . . . 100
2.3.2 Floating of Wood on Water . . .. . . . . . . . : . . 55 3.3.14 Washing Time . . . . . . . . , • • •• • . 102
2.3.3 Force Required to Hold a Ball Immersed in Liquid 56 3.3.15 Washing Time in Filter Press . . 103
2.3.4 Average velocity of Mixture . . . . . . . . . . . 57 3.3.16 Optimal Time in Filter Press . . . . 104
2.3.5 Flow Direction . . . . . . . . . . . . . . . . . . . 57 3.3.17 Compressibility of Filter Cake . . . ... 105
2.3.6 Pressure Drop for Flow through Circular Pipe . 58 3.3.18 Speed of Agitator . . . . . . . . . . .. . 106
2.3.7 Velocity of Water in Circular Pipe . . . . . . .. 59 3.3.19 Dimensional Analysis of Agitation . 108
2.3.8 Flow Rate for a given Pressure Drop . . . . . . . 60 3.3.20 Scale-up Criteria of Agitation . . 109
2.3.9 Pressure Drop per Unit Length for a given Flow 61
2.3.10 Pressure Drop for a given Flow . . . . . . . . . . 61 4 Thermodynamics 111
2.3.11 Pressure Drop due to Friction . . . . . . . . . . . 62 4.1 Instant Notes . . . . . . . . . . . . - - - - , .. - • • • • • • • - - - - · - · . 111
2.3.12 Velocity of Water in a Drain Pipe . . . . .. 63 4.1.1 Introduction . . . . . . . . . . . . . . . 111
2.3.13 Time Required to Empty a Conical Vessel . 64 4.1.2 Energy and its Transformations .. , .. 112
2.3.14 Energy Required for Pumping . . . . . 65 4. 1.3 Reversible and Irreversible Processes . 112
2.3.15 Power To Pump . . . . . . . . . . . . 66 4.1.4 First Law of Thermodynamics . . 113
2.3.16 Friction Loss Factor of Bend-Reducer 67 4.1.5 PVT Realtionships . . . . . . . . . 114
2.3.17 Flow through Tank Bottom . . . 68 4.1.6 Second Law of Thermodynamics . 115
2.3.18 Velocity Measurement by Orifice . . . 68 4.1. 7 Refrigeration . . . . . . . . . 115
2.3.19 Orifice Size for a given Flow . . . . . . 70 4.1.8 Thermodynamic Relations .. . 116
2.3.20 Flow Measurement by Venturi Meter . 70 4.1.9 Flow Processes . . . . . . . . 118
2.3.21 Flow Measurement by Pitot Tube . . 71 4.1.10 Solution Thermodynamics . 118
2.3.22 Minimum fiuidization Velocity . . . . 72 4.1.11 Phase Equilibrium . . . . . . 119
2.3.23 Water 'lricl<ling by Gravity through a Pa.eked Bed 73 4.1.12 Reaction Equilibrium . ·. . . ... • • . 119
2.3.24 Particle Size of Powder . . . . . . . . . . . . . . . . . . . . . . 74 4.2 Objective Type Questions . . . . . . 120
4.3 Problems with Solutions . . . . . . . . . .. . 129
3 Mechanical Operations 75 4.3.1 Rise in Temperature of Air . . . . . ... - .. . 129
3.1 Instant Notes . . . . 75 4.3.2 Work Required to Compress an Ideal Gas . . 130
3.1.1 Size Analysis . 75 4.3.3 'lriple Point Temperature and Pressure . . . . . . . .. 131
3.1.2 Size Reduction 76 4.3.4 Thermal Efficiency of Carnot Cycle . . . . . 131
3.1.3 Size Separation . 78 4.3.5 Evaluating a Claim . . . . . . . . . . . . . . . . . . . 132
3.1.4 Filtration . . . . 80 4.3.6 Entropy Change in Mixing of Two Gases . 132
3.1.5 Agitation . . , . 82 4.3. 7 Irreversibility . . . . . . . . . . . . . . . . . .. . 133
3.2 Objective Type Questions . 84 4.3.8 COP of Refrigeration Cycle . . . . . . , . . . . . . . . 134
3.3 Problems with Solutions .. 88 4.3.9 Change in Entropy for Ice to Steam Transformation ... . 135
3.3.1 Surface-Volume Mean Diameter of Particles . 88 4.3.10 Change in Internal Energy of Non-ideal Gas . . . . . . . . . 136
3.3.2 Work Index . . . . . . , . . . . . . . 89 4.3.11 Thermodynamic Relations for a van der Waals gas . . . . 137
3.3.3 Energy Consumption in Crushing. 90 4.3.12 Joule-Thomson Expansion. . - ..... . . . 139
 AN INSIGHT INTO CHEMICAL ENGINEERING - msubbu
4
4.3.13 Work of Compression • . . . . . . . . . . . . . . . . . . . . . . . . . . 139
4.3.14 Fugacity of van der Wa.a.ls Gas . . . . . . . . . . . . . . . . . . . . . . 140
4.3.15 Fugacity and Fugacity Coefficient . . . . . . . . . . . . . . . . . . . . . 142
4.3.16 Partial Molal Volume . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
4.3.17 Bubble Point Vapor . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
4.3.18 VLE of Non-ideal Solution . . . . . . . . . . . . . . . . . . . . . . . . 145
4.3.19 Activity Coefficient 11I1d Excess Gibbs Free Energy . . . . . . . . . . . 146
4.3.20 Activity .Coefficient . • . . • . . . . . . . . . . . . . . . . . . . . . . . . 147
4.3.21 Activity Coefficients as a Function of Compositions . . . . . . . . . . . 147
4.3.22 Activity Coefficients and QE/ R:r . . . . . . . . . . . . . . . . . . . . . 149
4.3.23 Dewpoint Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . : 150
4.3.24 Composition of Vapor . . . . . . • . . . . . . . . . . . . . . . . . . . . 150
4.3.25 P - x - y Data. . . . . . . . . . . . . . . . . . . . • . . . . . . . . . . . 151
4.3.26 Variation of Equilibrium Constant-with Temperature . . . . . . . . . . 152
4.3.27 Partial Pressures at Reaction Equilibrium . . . . . . . . . . . . . . . - 153
4.3.28 Dehydrogenation of Ethane . . . . . . . . . . . . . . . . . . . . . . . . 154
4.3.29 F,quilibrium Composition of Non-ideal Gas phase Reaction . 155
5 Heat '.Iransfer 157
5.1 Instant Notes . . . . . . . . . . . .. . . . . . . . . . .. . . . . . . - . - - - 157
5.1.1 Conduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
5.1.2 Convection . . . . . . . . . . . . • • . . . . . . . . . . . . . . . . . . . . 158
5.1.3 Boiling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 161
5.1.4 Condensation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
5.1.5 Heat Exchangers . . . . . . . • . . . . . . . . . . . . . . . . . . . . . . 162
5.1.6 Evaporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - - . - 165
5.1.7 Radiation . . . . . . . . . . . . . • . . . . . . . . . . . . . . . . . . . . 166
5.2 Objective Type Questions . . . . . . . . . . . . . • . .· . . . . . - . - - . - 167
5.3 Problems with Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
5.3.1 Conduction through Thermopa.ne . . . . . . . . . . . . . . . . - - - - . 175
5.3.2 Conduction through Two Layers . . . . . . . . . . . . . . . . . . . . . 176
5.3.3 Critical Thickness of Insulation . . . . . . . . . . . . ·. . . . . . . . . . 177
5.3.4 Reduction in Heat Loss by Insulation . . . . . . . . . . . . . . . . . . 179
5.3.5 Heat Conduction through Increasing Cross-Section . . . . . . . . ·. . . 180
5.3.6 Expression for Steady State Temperature Profile . . . . . . . . . . . . 181
5.3.7 Time Required for Coqling of Steel Ball . . . . . . . . . . . . . . . . . 183
5.3.8 Unsteady Heat Transfer . ·. . . . . . . . . . . . . . . . . . . . . . . . . 184
5.3.9 Expression for Unsteady Heat Transfer . . . . . . . . . . . . . . . . . - 185
5.3.10 Time Required for Freezing the Tank Contents . . . . . . . . . . . . . 187
5.3.11 Heat Transfer Area fdr Constant Heat.Flux . . . . . . . . . . . . . . . 188
5.3.12 Convective Beat Transfer . . . . . . . . . . . . . . - . . . . . . . . . . 189
5.3.13 Emissivity Measurement , .• · . . . . . . . . . . . . . . . . . . . . . . . 190
5.3.14" Momentum & Heat Transfer Ana.logy . . . . . . . . . . . . . . . • . . 191
5.3.i5 Expressioq. for -OptlllUIIIl Length of Heat Exchanger . . . .. . . . . . . 192
5.3.16 Heat Thansfer Area for Counterflow & Paxallel fl.ow • . . - . • • • • . • 194
5.3.17 Heat Transfer Are~ of Jacketted Vessel. . . . . . . . . . . . . . . . 196
CONTENTS 5
5.3.18 Heat Transfer. Axea & Rate of Condensation of Steam . . . . . . . . . 197
5.3.19 Condensation of Steam . . . . . . . . . . . . . . . . . . . . . . .. - . . 198
5.3.20 Time Required for Beating the Contents of Jacketted Vessel . . . . . . 199
5.3.21 :&timation of Fouling Fa.ct.or . . . . . • . . . . . . . . . . . . . . . . . 200
5.3.22 Heat Transfer Area for 1-2 Exchanger . . • . . . . • . . . . . . . . . . 201
5.3.23 Condenser Load in Evaporation . . . . . . . . . . . . . . . . . . . . . . 202
5.3.24 Steam Economy & Heat Transfer Area . . . . . . . . . . . . . - - . - . 203
5.3.25 Temperature of Radiation Shield . . . . . . . . . . . . . . . . . . . . . 204
6 Mass Transfer 205
6.1 Instant Notes . . . . . . . . . . . . . . . . - - - • .. • • . . . - - - - • • • • 205
6.1.1 Diffusion . . . . . . . . . . . . . . . . . . . . . . . . - . . · . . - . - . . 205
6.1.2 Convective Mass Transfer . . . . . . . . . . . . . . . . . . . . . .. . . . 206
6.1.3 Gas-Liquid Cont.actors . . . . . . . . . . . . . . . . . - . . . . . . • • ~ 208
6.1.4 Tray Efficiencies . . . . . . • . . . . • . . . . . . . . . . - . . . . . - . 209
6.1.5 Absorption . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . 209
6.1.6 Distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
6.1.7 Drying . . . . . . . . . . . . • . . . . . . . . . . . . . . . . . . .. . .. 215
6.2 Objective Type Questions . . . . . . . . . . . . . . . . . . . . . . . • • - - 216
6.3 Problems with Solutions . . . . . . . . - . . . . . . . . . . . . . . . . . . .. 229
6.3.1 Molecular Diffusivity . . . . . . . . . . . . . . . . . . . - . . . - - - . . 229
6.3.2 Diffusion of A through Non-diffusing B •. . . . . . . . . . . . . . . . 230
6.3.3 InterfaciaJ. Gas Concentration . . . . . . . . . . . . . . . . . . . . - .. 231
6.3.4 Heat and Mass Transfer Analogy . . . . . . . . . . . . . . . . . . . . . 232
6.3.5 Shewood Number for Equimola.r Counter Diffusion . . . . . - . - . - 234
6.3.6 Relative Humidity of Mr . . . . . . . . . . . . . . . . . . . . - - . . . 234
6.3.7 Dry-bulb Temperature of Mr . . . . . . . . . . - - ... - . • - - • - . 235
6.3.8 Minimum Liquid Rate for Absorption . . . . . . . . . . . . . . . . . . 236
6.3.9 Height of Absorption Column . . . . . . . . . . . . . . . .. . . - . . . 238
6.3.10 Flash Vaporization . . . . . . . . . . . . . . - . . . . . . .. . . . . . 241
6.3.11 Differential Distillation . . . . . . . . . . . . . . . . . . . : . . .. . . . 242
6.3.12 Equation of q-Line . . . . . . . . . . . . . . . . . . . . . . . . . . . - . 243
6.3.13 Reflux Ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . - - • - • 245
6.3.14 Quality of Feed to.Distillation Column . . . . . . . . . . . . . . . · . . - 246
6.3.15 Reflux Ratio and Composition of Vapor· . . . . . . . . . • . . - . . . . 248
6.3.16 Reflux Ratio and Vapor Rate . . . . . . . . . . . . . . . . : . - . • . - 250
6.3.17 Distillation with Partial Condenser . . . . . . . . , . . . · . . . . - : . . 252
6.3.18 Adsorption of Moisture by Silica Gel . _. . . •.. . . .. - . . . . - . . . . 253
6.3.19 Leaching of Sulfur . . . . . . . . . : . . . . . : . . . . - . . . - . . - - 255
6.3.20 Time Required for Drying . . . . .- . .. ·. . . . . . . . - . . . . . . - - 256
6.3.21 Equilibrium Moisture Content . . . . . . . . . . . . . . . . . . ~ - .. 258
6.3.22 Drying of Solid . . . . . . . . . . . . •.. - . . • . . - . - .. - .. . . . 259
6.3.23 Drying of Slabs' . . . . . . . . . . . . . . . . . . . . . . . . . - . - - . 260
6.3.24 Extraction of Acetone - - 261
 6 AN INSIGHT INTO CHEMICAL ENGINEERING - msubbu CONTENTS 7

7 Reaction Engineering 263 8.3.5 Response of Thermometer to Step Io.put . . . . . . . . . . . . . 319

7 .1 Instant Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263 8.3.6 Time Constant of Thermocouple . . . . . . . . . . . . . . . . . 320
i 7.1.1 Reaction Kinetics . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . 263 8.3.7 Dynamics of Temperature Alarm Unit . . . . . . . . . 320
7.1.2 Design of Reactors . . . . . . . . . . .. .. . . . . . . . . . . . . . . . 263 8.3.8 Analytical E>.."Pression for Unit Impulse Response . . . 320
7.1.3 Non-isothennal Reactors .. . . . . . . . . . . . . . . .. . . . . . . . . 264 8.3.9 Step Input to Setpoint . . . . . . . . . . . . . . . . . . 321
7.1.4 Heterogeneous Reactions . . . . . . . . . . . . . . . . . . . . . . . . . 265 8.3.10 Outp ut from Control Valve . . . . . . . . . . . . . . . 323
7.1.5 Catalytic Reactions . . .. . . . . . . . . . . . . . . . . . .. . . . . . 265 8.3.11 Output of Proportional Conb-oller . . . . . . . . . . . 323
7.2 Objective Type Questions . .. . .. .. .. . . . . . . . . . . . . . . . . . 266 . 8 .3.12 Output from PID Controller . . . . . _. . . . . . . . . . . . . . . . 323
7.3 Prob lems with Solutions . . .. . . . . . .. . .. .. . . . . . . . . . . . . 279 8.3.13 Block Diagram Reduction &lld Offset Calcul!l,t ion . . . . .. . . . . . . . 325
7.3.1 Activation Energy . . .• . . . . . . . . . . . . . . . . . . . . . . . . . 279 8.3.14 Servo _and Regulator Transfer Funct ions . . . . . . . . . . . . . . . . . 326
7.3.2 Expression for Rate for tbe given Mechanism .. . . . . . .. . . . . . 279 8.3.15 Steady State Error in a Closed Loop System .. . . . . . . . . . . . . 327
7.3.3 Relation for Concentrat ions in Multiple Reactions . . ." . . . . . . . . 280 8.3.16 Proportional Band of P neumatic Controller . . . . . . . . . . . . . 328
7 .3.4 Material Balance Equations for Isothermal CSTR . . . . . . . . . . . . 281 8.3.17 Offset in Feedb ack Control System . . . . . . . . . . . . . . . . . . 328
7.3.5 Conversion in CSTR for Zeroth Order R.eaction . . . . . . . . . . . . . 282 8 .3.18 Value of Kc from Routh Test . . . . . . . . . . . . . . . . . . . . . 329
7 .3.6 Conversion in Equal Volume CST R & P FR . . . . . . . . . . . . . . . 283 8.3.19 Ma,.'<irnum Gain for Stable Opera.ti.on . . . . . . . . . . . . . . . . 330
7.3. 7 Conversion in Constant P ressure Batch-Reactor . . . . . . . . . . . . . 284 8.3.20 Maximum Controller Gain for Stable Closed Loop System-I . . . 33i
7.3.8 Conversion in a Batch Reactor . . . . . .. . .. .. . . . . . ·. .. . . 284 8.3.21 MaJCimmn Controller Gain for Stable Closed Loop System-tr . . 331
7.3.9 Order of Reaction from P FR Dat a . . . . . . . . . . . . . . . . . . . . 285 8.3.22 Limits on Controller Gain . . . . . . . - . . . . . . . . . . . . . . 332
7.3.10 Conversion of Second Order Reaction in CSTR . . .. . . . . . . . . . 287 8.3.23 Stabil ity of Closed Loop System . . . . . . . . . . . . . . . . . . 333
7.3.11 Size of P F R for Ga.s--pbase Reaction-I . . .. . . . .· . ... . . . .. .. 287 8.3.24 Steady State Error in tbe Closed Loop System . . . . . . . . . . . 334
7.3.12 Size' of PPR for Gas-phase Reaction-I[ . . . . . . . . . . . . . .. . . 288 8.3.25 Crossover Frequency & Ultimate Controller Gain - I . . . . . . . . 335
7.3.13 Reactors in Series . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
8.3.26 Crossover frequency & Ult imate Controller G ain - II . . . . . . . . . 336
7.3.14 React ors Arrangement . . . . . . . . . . . . . . . . . .. . .. . . . . 291
7.3.15 Increase in P roduction Rate by P FR . . . . . . . . . .. . . . . . . . 292 9 P rocess E conomics & Design 337
7.3.16 Actual Conversion in th e Reactor . . . . . . . . . . .. . . . . . . . . 293 9.1 Inst a .n t Notes . . .. .. .. . .. .. . - . 337
7.3.17 Expected Conversion in the Reactor System . . . . . . . . . . . . . 295 9.1.1 Cost Estim ation . . . . .. .. . . . . 337
7.3.18 Reactors Arrangement for Higher Conversion . . . . . . . . . . . . . 296 9.1.2 Depreciation . . . . . . . . . . . . .. 338
7.3.19 Rate Constants of P arallel Reactions . . . . . . .. . . . . . . . . . . 297 9.1.3 Interest and Investment Costs . . .. . . . . . .. 339
7.3.20 Catalyst Effectiveness Factor . . . . . . . . . . . . . . . . . . .. 298
9.1.4 Mechanical Design of Process Equipments . . . . 341
7.3.21 Rate Controlling Step . .. .. . .. . .. .. .. . . . . .. . . . . . . 299
9.2 O bject ive Typ e Questions . . . . . . . . . . . . . . . . 345
7.3.22 Expression for Catalytic Reaction . . . . . . . . . . . . . . . . . . 300
9.3 Problems w ith Solutions . . . . . . . . . . . . . . . . . . . . . 347
7.3.23 E xpression for Rate of Catalytic Reaction . . . . . . . . . . . . . 301
9.3.1 Cost Index & Capacity Factor . . . . . . . . . . . . . . . . . . . . 347
8 Process Control 3 03 9.3.2 Capit al Cost of Fluid-processing Plant . . . . . . . . . . . . . . 348
8.1 Instant Notes . . . . . . . . . . . . . . . . • . . . . . . . . . . . . . . . . . . 303 9.3.3 Depreciation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
8.1.1 Laplace Transforms . . . .. .. . . . . . . . . . . . . .. .. . . . .. 303 9.3.4 P resent Worth of a Future Amount . . . . . . . . . . 349
8.1.2 Qualitative Response of Systems . . • . . . • . . . . . • . . . . . . . 303 9.3.5 Capit alized Cost . . . . . . , . . . . . . . . . . . . . . 350
8.1.3 Open-loop Response of Dynamic Systems .. ; . . . . . .. .. . . . . 304 9.3.6 Annuity & Periodic P ayment . . .. . . . 350
8.1.4 Dynamics of Controllers . . , . . .. . . . . . .. . .. . . . . . . . . . 305 9.3.7 Net P rofit & Payout Period . • . . . . . . . . . . . . 351
8.1.5 Stability Analysis of Feedback Systems . . . . . . . . . . . . . . . . . . 307 9.3.8 Capitalized Cost - Useful Life for the. Alt ernative . . . . . . . 352 ·
8.2 Obje ctive Type Questions . .. .. . .. .. . . . .. . . . . . . . . . . .. 308 9.3.9 Capitalized Cost as a. Criteria . . . . . . . . .. . . . . ~ .. . 353
8.3 P roblems with Solut ions . . . . . . . . . . . . . . . . . ; . . . . . . . . . . 316 9.3.10 Discounted-Cash-Flow R ate of Ret~m . . .. . . . . . . . . . 354 r
8.3.l Lineariza.t ion of Single Variable . . . .. .. . . ; . · . . . . . . . . . . . 316 9.3.11 Alternative Investments . . . . . . . . .. . . . . . . . . . . . . 354
8.3.2 Temperature of Solution Leaving a Stirred Tank . . . . . . . . . . . . 317 9.3.12 Rate of Return as a P rofitability Criteria . . . . . . . . . . . 355
8.3.3 Transfer Function for First Order Reaction . . . . . . . . . . . . . . . 317 9.3.13 Brealc-Even P oint . . . . . . •, .... . . . 355
8.3.4 Dyna!Illcs of Thermomf}ter . . . . . . . . . . . . . . . . . 318 9.3.14 Economic Pipe Diameter .. . . .. . .. . . . .. . . 356
--,J

8 AN INSIGHT INTO CHEMICAL ENGINEERING - m subbu

10 Chemical Technology 357'.

10.1 Instant Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
10.1.l Water Conditioning . . . . ·. . . . . 357
10.1.2 Fuel Gases . . . . . . . . . . . . . . . . 357
10.1.3 Sulfuric Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359 Chapter 1
10.1.4 Chlor-.Alkali Industries . . . . . . . . . . . . . . . - .. . . _360
10.1.5 Nitrogen Industries . . . . . . . . . . . . . . . . . . . . . . . - : 361
10.1.6 Phosphorus Industries . . . . . . . . . . . . . . . . . . . . • • • • • .. 362
10.1.7 Fertlizers : . . . . . . . . . . . . . . . . . . ·. . . : . . . . . . . . . . - 362
10.1.8 Cement Industries . ·. . . . . . . . . . . . . . . . . . . . . . . . . . - - 363
Process Calculations
10.1.9 Sugar Industries· . . . . . . . • . . . . . . . . . . . . . . - - . • . . . • 363
10.1.lDAlcohol Industries . . . : . . . . . . . . . . . . . . . . - . . . - · 363
10.)...11 Leather Industries . . . . . . . . . . . . . . . . . . - . • • • - - • 364
10.1.12Oils and Fats . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . • • 364
1.1 Instant Notes
10.1.13 Pulp & Pa.per Industries . . . . . . . . . . . . . . . - • • • - 365
10.i.14Petroleum Processing . . . . . . . . . . . . . . . . - • 365 1.1.1 Units and Standards
°',10.1.15 Polymer Industries . . . . . . . . . . . . . . . . . - . . . . . . · . · · - 366
10.l.16Ruhbers or Elastomers . . . . . . . . • . . . . . . . . , . . - • - - - • • 367 • S.I (International System of Units)
10.l.17Common Names . . . . . • . . . . . . . . . . . . . . . - • - 368
10.1.lSSa.fety Tips . . . . . . . . . . . . . . . . . . . . . . . . . - - 368 - Mass in kg, Length in meter, Temperature in Kelvin, Number.of gram-moles as
10.l.19Ma.teria.ls of Construction for the Process Industries - 368 mole, Force in Newton
10.2 Objective Type Questions . . . . . . . . . • . . . . . - . • - - • • • • • 371 - The unit of temperature is Kelvin, K (not degree Kelvin, °K)
377 mass in gra.m
11 Mathematics 1 =
• Moe
11.1 Objective Type Questions . • 0 • o o O • • • • • • • • • o • • 4 I ~
. 377 molecular weight

Recommended Books for Detailed Study 386 • Composition of solids: expres.sed in weight% or in mole%. Whenever no specifica-
tion is made about the composition i.e., whether it is mole % or weight %, it is ta.ken
as weight %.

• Very often, the impurities present in solid or liquid compounds are expressed in ppm
(parts per million parts). This is expressed on a weight basis. When the solution is
watery, 1 mg/lit = 1 ppm. In water treatment and effiuent treatment problems, the
analyses are given in ppm or mg/lit, which are both taken as similar.

• Molarity (M) is defined as the number of gmol of solute dissoJ-ved in 1 litre of solution.

• Normality (N) is defined as the number of gram equivalents dillsolved in 1 litre of

solution. ·

.,, • Concentration in g/lit = Normality (N) x equivalent weight

I
I • Molality is defined as the number of gm.al of solute dissolved in 1 kilogram of solvent.

• The volumetric composition of a. liquid solution will change with the temperature. The
composition of a system expressed in mole percent will not vary with the temperature.

•..J
 AN Il'TSIGHT INTO CHEMICAL ENGINEERING - m subbu PROCESS CALCULATIONS 11
10

• For ideal gases, the composition in mole percent.is exactly same as the composition - The feed to the process itself is made up of two streams, the fresh feed and the
in volumetric percent. It should be emphasized that this relation holds only for gases, recycled material: The gross product leaving the process is separated into two
streams, the net product and the material to be recycled.
and does not apply to liquid or solid systems.
• S.T.P: Pressure = 1.01325 x 105 N/ro2 ; T = 273 K. At this conditions, for an ideal • Conversion
gas V = 22.4 rn3 /k.mol. Overall fractional conversion= m,f - mrp
m,..,
1.1.2 Material Balance Calculations where m,1 = mass of reactant in fresh feed
• Without Chemical Reaction m,p = mass of reactant in net product

- Under steady state conditions,

Single-pass (once-through) fractional conversion= m,1 - mr., (1.2)
Input = output m,..1

Under unsteady state conditions where m,1 = mass of reactant fed into the reactor
T1l.rz = mass of reactant existing the reactor
Input = output + accumulation

• Atom balances
• Bypass stream: one that skips one or more stages of the process and goes directly
Input (of some species of atom)= output (of the same species of atom) to another downstream stage.

The chemical reactions that take place in a process which are very complicated can be • Purge stream: a stream to bled off to remove an accumulation of inerts or unwanted
solved by atom balances without knowing the chemical reactions taking place in that. material that might otherwi,;e buildup in the recycle stream.
• Inert substance: In most oxidation process air is used as the source of oxygen, and
air is 79 mol percent nitrogen, an inert substance at the temperatures at which most
1.1.3 Energy Balance Calculations
substances are oxidized.
• The distinction of constant volume and constant pressure processes i;, not so important
• Tie substances: Tie material is defined as a material, of necessarily inert or unre-
in the case of liquids'll.nd solids, as the liquid and solid expands very little with increase
active, which passes through a ~ystem from a single input stream to a single output
in temperature.
stream and ofcourse remains completely unchanged during this process.
• Incomplete reactions: Chemical reactions are generally not complete; that is, the • The specific heats of solids -are lower than liquids.
limiting reactant is not completely used up. This idea is expressed as percent complete
or percent completion, and it is important to note that this completion must be based • The heat of formation is a ; pecial type of heat of reaction from the elements. The
reaction does not necessarily represent a real reaction but can be a fictitious process
on the limiting reactant.
for the formation.
• Percent excess: Percent exe€SS of excess reactant is based on the 100 percent com-
pletion of the limiting reactant. • All oxidation reactions are exothermic Similarly, the dissolution of sulfuric acid or
caustic soda is exothermic.
• Recycle
- Recycle is the operation or a process ~tep whereby a part or fraction of the !
I
• fndustrially important steam-hydrocarbon reforming reaction is endothermic.
products from the reactor is returned and mi,ced with the incoming fresh feed to
the reactor.
- Because of recycle, the overall conversion, which is based on the fresh feed, will
l. I
• The dissolution of common salt in water is also endothermic.

be higher than the conversion per pass, which is based on the mixed feed to the • The temperature of the products under adiabatic conditions of reaction is called t he
adiabatic reaction temperature.
reactor.
r

12 AN INSIGHT INTO CHEMICAL ENGINEERING - m subbu PROCESS CALCULATIONS 13

1.1.4 Saturation & Humidity - When a fuel is burnt, hydrogen combines with oxygen and gets converted into
water. When water vapor is present in the flue gases, the latent heat of vaporiza-
• Bone-dry air: Air that is bone dry contains absolutely no water vapor. Bone-dry tion is lost. Hence this quantity of heat is not available for any useful purpose.
implies mmpletely dry. Therefore, when the calorific value of a fuel is determined, considering that the.
water is present in the vapor form, it is said to be the net calorific value (NCV)
• Molar humidity is also sometimes referred to as absolute humidity. or net heating value or lower heating value.
. . moles of water vapor
NCV = · CCV - weight % of hydrogen x 9 x >-
1
:Molar hurmd1ty = b ,b dry .

l
ones OL one- arr
- Usually, NCV and CCV (Gross Calorific Value) of the fuels are reported at 25°C.
kg of water vapor
= - It is customary to specify the abbreviations NCV or GCV when the calorific
• Humidity, or specific humidity kg b one-dry a.u
.

• Relative humidity: is defined as the ratio of the partial pressure of water vapor
values are reported, as the case may be. However, if no mention is made, the
reported calorific value is taken as GCV. ·
i
in air to the vapor pressure of water at dry-bulb temperature. Relative humidity is - In comparison to all the three types of fuels, gaseous fuels offer higher heating
widely used in weather reporting but finds little application in engineering where it values.
has been replaced by percentage humidity.
• Nitrogen reduces the flame temperature considerably and also accounts for high heat
• Percentage humidity or percentage saturation: is defined as the ratio of actual loss to the stack.
absolute humidity to the saturation humidity.
• Air requirements
• Relative humidity is always greater than or equal to percentage humidity. Relative
humidity is equal to percentage humidity only at saturation. - The theoretical or stoichiometric amount of air is the minimum amount of air
required to bum the fuel completely so that carbon, hydrogen and sulfur a.re
• Dew point converted to CO2, H20 and S02 respectively.

- Partial pressure of water vapor in the mixture equals the vapor pressure of water
- In actual practice, theoretical air is not sufficient to get complete combustion.
Excess air supply is a must for complete combustion.
at dew point.
- Normally, gaseous fuels require very less excess air. The effect of excess air is
- Dew point is always lower than or equal to dry bulb temperature.
to reduce the flame temperature and to increase the heat losses through the flue
- Dew point is always lower than or equal to wet-bulb temperature. gases.

• At 100% saturation; • The greater the moiEture present in the flue gases, the higher is the dew point.

Dry bulb temperature= Wet bulb temperature = Dew point • The major combustion reactions Me all exothermic.

• The difference between the wet-bulb temperature and the dry-bulb temperature is
proportional to the amount of water vapor in the atmospheric air; it is zero if the air
1.2 Objective Type Questions
is saturated and highest if the air is bone-dry.
1. For a steady state system
>.
I
1.1.5 Combustion Calculations (a) The rate of input is zero
(b) The rate of generation is zero
• Calorific Value (c) The rate of consUD1ption is zero
(d) The rate of accumulation is zero
- The calorific value of a fuel is nothing but the heat of combustion of the fuel It
is defined as the total heat produced when a unit mass of fuel is completely burnt
with pure oxygen. It is also said, to be the heating value of the fuel. Answer: ( d) At steady state, Input= Output (for nonreactive systems)

f
J.
 PROCESS CALCULATIONS 15
4 AN INSIGHT INTO CHEMICAL ENGINEERJNG - m subbu

2. In a paper mill, a wash liq!)Or containing 3% (by weight) solids is concentrated in an Answer: (c) Basis: l mole of A in feed.
evaporator to yield a lye containing 30% (by weight) solids. The quantity of water 1 mole of A gives 3 moles of B for complete conversion.
evaporated per 100 kg of feed is: Therefore for 50% conversion of A, product contains:
1.5 mole B and 0.5 mole A.
(a) 30 kg . (b) 70 kg (c) 60 kg (d) 90 kg Mole fraction of A in product= 0.5/(1.5 + 0.5) = 1/4
G. A liquid mixture contains 30% a-xylene, 60% p--xylene and 10% m-xylene (all per-
A.nswer: (d) Basis: 100 kg offeed containing 3% (by weight) solid.
centages in w/w). Which of the following statements would be true in respect of this
Solid in feed 0.03 x 100 = 3 kg mi'l..1;ure? (GATE-19g8-l.07)

Solid in lye (product) 3 kg (a) The mixture exhibits an azeotrope at 101.3 kPa.
3
Total lye __ = 10 kg (b) The composition of the mixture, in percent by volume is: O-'l..-ylene 30, p--xylene
03 60, and m-xylene 10.
'Nater evaporated 100 - 10 = 90 kg
(c} The composition of the mixture in mole percent is: o-xylene 30, p-xylene 60, and
m-xylene 10. ·

3. The molar composition of a gas is 10% H2 , 10% 02, 30% CO 2 and balance H20. If (d) The mixture contains optical isomers.
50% H 2 Ocodenses; the final mole percent ofH2 in the dry gas will be (GATE-2000--1.07) Answer: (c) For isomers, molecular weights are equal; hence mo!% & weight% are
same. The composition in volume% is equal to mole% for mixture of ideal gases.
(a} 10% (b) 5% (c) 18.18% (d) 20%
7. Pure ethanol vapor is fed to a reactor packed with Alumina catalysts at the rate of 100
Answer: (d} For dry gas analysis H20 amount should not be considered. kmol/hr. The reactor product comprise: Ethylene= 95 kmol/hr, Water vapor= 97.5
Therefore, H 2 in the dry gas= 100 x [0.l/(0.l + 0.1 + 0.3)) = 20% kmol/hr and diethyl ether = 2.5 kmol/hr. The reactions occuring can be represented
by: .
4. A solution of speci£c gravity LO consists of 35% A by weight and the remaining B. If
the specifi<; gravity of A is 0.7, the specific gr-avity of B is (GATE-1999-1.05) C2HsOH __, C2H4 + H20
2C2HsOH -+ C2Hs-O-C2H5 +H2
(a} 1.25 (b} 1.3 (c) 1.35 (d) 1.2
The percent conversion of ethanol in the reactor is: (GATE-1998-1.08)
Answer: (b) Basis: 1 ltr of solution.
Since sp.gr of pure A is 0.7 (Le., p = 0.7 kg/ltr}, (c) 95 (d} 2.5
(a} 100 (b) 97.5
0.7 kg of A lltr
Answer: (a) Basis: 1 hr.
0.35 k~ of A 0.35 x 1/0.7 = 0.5 ltr
Ethanol used: ·
Therefore,
for first reaction 95 kmol (from ethylene rate)
0.65 kg of B 1 - 0.5 = 0.5 ltr for second reaction 2.5 x 2 = 5 kmol (from diethylether rate}

p of B
mass of B
-----=--=13
0.65 Total 95+ 5 = 100 kmol
volume of B 0.5 ·
i.e., Specific gravity of B 1.3 Check for water vapor:

Water from first reaction 95 kmol

5. Pure A in gas phase enters a reactor. 50% of this A is converted to B through the Water from second reaction 2.5 kmol
reaction A --t 3B. Mole fraction of A in the exit stream is (GATE-1999-1.06) Total water produced 95 + 2.5 = 97.5 kmol
(a) 1/2 (b) 1/3 (c) 1/4 (d) 1/5 (since ethanol used "'.' ethanol in feed; conv:ersion is 100%)
16 AN INSIGHT INTO CHEMICAL ENGINEERING - m subbu PROCESS CALCULATIONS 17

8. A sample of well water contains 140 g/m:,, Ca2 + ions and 345 g/m3 Na+ ions. The 11. The ftowsheet is given in figure.
hardness of the sample of water, expressed in terms of equivalent CaCO 3 in g/m3
[assuming atomic masses of Ca= 40, Na= 23, C= 12 and 0= 16] is (GATE-1998-2.07)

(a) 350 (b) 485 (c) 140 {d) 345 s

E
Fresh Feed p
.4.nswer: (a) Sodium ions does not contribute to hardness. 100 mol/b.r A Product, P
:Molecular weight of CaCOa = 40 + 12 + 3 x 16 = 100 REACTOR R
A-->B A
40 g of Ca 100 g of CaC03 (Pure A) T (Pure B)
0
140 g of Ca lOO x 140 = 350 gof C a coa R
40

9. Methane is completely burned with air. The maximum possible volume percent of R (Pure A)
carbon dioxide (on dry basis) in the flue gas is (GATE-1993-8.b)
If the single-pass conversion (once-through conversion) of A to Bis 20%, then the rate
(a) 11.7 (b) 21.0 (c) 44.0 {d) 28.0 of recycle R (mol/hr) is (GATE-1997-2.05)

Answer: (a) Basis: 1 mole of CILt (a) 300 (b) 400 (c) 500 (d) 600

Answer: (b) A--> B. By overall balance, product P = 100 mol/hr.

Flue gas contains: Since conversion within the reactor is only 20%,
CO2= 1 mole
mixed feed to the reactor 100/0.2 = 500 rnol/hr
N2 = 2 x 79/21 = 7.524 mole
Volume % of CO2 (on dry basis) in flue gas= 100 x 1/(1 + 7.524) = 11.7 recycle rate R 500 - 100 = 400 mol/hr
This amount is the maximum possible, since stoichiometric air is used.

10. Pure carbon is completely burnt in oxygen. The flue gas analysis i8 70% CO2, 20%
CO and 10% 02. The percent exc=; oxygen used is (GATE-1997-2.04) 12. For the case of fuel gas undergoing combustion with air, if the air/fuel ratio is increased,
the adiabatic fta.rne temperature will (GATE-2001-1.05)
(a) 20 (b) 12.5 (c) 0 (d) 10
(a) increase
Answer: (c) Basis: 1 mole of flue gas.
The possible reactions a.re:
.-. (b) decrease
(c) increase or decrease depending on the fuel type
(d) not change
C +02 --+ CO2
C + 1/202 -, CO Answer; (b) If air/fuel ratio is increased, N2 content is increased which does not
take part in reaction. Some amount of heat will be used for raising the sensible heat
I. content of N2 , thereby reducing the adiabatic flame temperature:
02 used up 02 used for (CO2 +CO)+ 02 in flue gas
(0. 7 + 0.2/2) + 0.1 = 0. 9 mole 13. An evaporator while concentrating an aqueous solution from 10 to 40% solids evapo-
02 required 0.7 + 0.2 ':"' 0.9 mole. (for complete conversion) rates 30000 kg of water. The amount of solids handled by the system in kg is (GATE,.
Excess 02 =
0.9 - 0.9 0 mole 1995-2.e)

(a) 4DQO (b) 9000 (c) 4600 (d) 3000

)
{
PROCESS CALCULATIONS 19
AN INSIGHT INTO CHEMICAL ENGINEERING - msubbu
3
17. Assuming that CO2 obeys perfect gas law, ca!c:ilate the density of CO 2 (in kg/rn ) at
Answer: (a) Overall mass balance: F = V + P. (where F = feed; V = vapor; P = 263°C and 2 atm. (GATE-1995-2.g)
product)
Balance on solid: 0.lF = 0.4P. Therefore P = (0.1/0.4)F = 0.25F. (c) 3 (d) 4
· (a) 1 (b) 2
F = 30000 + 0.25F ==:, F = 40000.
Amount of solids in feed= 40000 x 0.1 = 4000 kg.
Answer: (b) PV = nRT
,4. A multiple effect evaporat.or has a capacity to process 4000 kg of solid caustic soda
n p
per day when it is concentrating from 10% to 25% solids. The water evaporated in kg
per day is (GATE-1992-2.d)
Molal density v= RT
!!:._M=PM
Mass densityp V . FIT
(a) 600 (b) 24,000 (c) 60,000 (d) 48,000 ·

Answer: (b) Basis: 1 day.

= . .,__
(2 X_ 1.01325
___X 10_ 5"--_
) X 44 = 2 ka/ m 3
8314 X (273 + 263) c:,
10% of solid weighs 4000 kg. Therefore,

•
I
I
Feed

Product
4000
QI =40000 kg
4000
- = 16000 kg
18. Pure 0 2 is rrrixed with air to produce an enriched air containing 50 volume% of 0 2 .
The ratio of moles of air to 0 2 used is (GATE-1995-2.h)
0.25
Water evaporated 40000 - 16000 = 24000 kg (a) 1.72 (b) 0.58 (c) 0.50 (d) 0.20

Answer: (a) Basis: Pure 02 + Air = 1 mole. i.e., P +A= 1.

l ::i. 1000 kg of wet solids a.re to be dried from 60% to 20% moisture (by weight). The mass Balance on 0 2 : P + 0.21A = 0.5(P + A).
of moisture removed in kg is (GATE-1995-2.r) Solving these two equations, A/P = 1.725.
(a) 520 (b) 200 (c) 400 (d) 500

Answer: (d) 1.3 Problems with Solutions

Dry solid in feed 1000 X (1 -0.6) = 400 kg 1.3.1 Volume of Gas at STP
Amount of dried product 400/(1 - 0.2) = 500 kg The gases entering-a reactor contain A and B in the mole ratio of 1:4. The mole ratio of
Moisture evaporated 1000 - 500 = 500 kg 3
these gases in the exit stream from the reactor is 1:4.25. What volume of the gas in m at
STP must encer the reactor to produce 100 kmol of product C per hour? The reaction is
A+ 3B :._. 2C. (GATE-1989-llii)
.lG. 1000 kg of a solution containing 50% by weight of a salt dissolved in it is cooled. 400 kg
of anhydrous salt is separated out. The solubility of the salt at the lower temperature Solution:
in kg/lOOkg of water is (GATE-1993-8.a.)

(a) 80 (b) 50 (c) 40 (d) 20 A:B

Feed
=1:4
IReact IA : B =
or Pr9duct
I : 4.25
A+3B ..... 2c
Answer: (d) '
Water in feed 0.5 X 1000 = 500 kg Let A in feed = 1 mole. Therefore, B in feed = 4 mole.
Water in mother liquor Water in feed = 500 kg Let :r. be the fractional conve.rsi.on of A. Then product contains: A= 1 - x; B =4- 3x;
Salt in mother liquor salt in feed - crystals and C =2x.
(1000 ~ 500) - 400 = 100 kg (1 - x) : (4 - 3:i:) 1: 4.25
kg salt 100 4.25(1 - x) 4-3x
Solubility kg water = 500 = 20 kg sa!t/100 kg water
4.25- 4.25x 4-3x
20 AN INSIGHT INTO CHEMICAL ENGINEERING - msubbu PROCESS CALCULATIONS 21

Solving, x = 0.2. Therefore, 1 mole of A in feed gi~ 0.2 x 2 mole of C. the 11.ue gases a.re perfect. (GATE-1992-11)
0.4 mole of C _ 1 mole of A Solution:
100 mole of C 100/0.4 = 250 mole of A in feed.
Feed contains: Molecular weight of S02 64 kg/kmol
A 0.2 kg/m3 of S02 0.2/64 :' 3.125 x 10-3 kmol/m3
250 km.al
B 4 x 250 = 1000 kmol"
Total = 1250 kmol For a perfect gas at NTP, 1 krn.ol 22.4 m 3
Therefore, 3.125 x 10-3 kmol/m3 = 3.125 x 10-3 x 22.4 = 0.07 m 3 /m3
At STP, 1 kmol of gas occupies 22.4 m 3 • Therefore
= 70000 x 10-6 m 3 /m3 = 70000 ppm
1250 kmol/hr = 1250 x 22.4 = 28000 m /hI 3

1.3.4 Conversion of S02

1.3.2 Orsat Analysis of Flue Gas The analysis of the gas entering the secondary converter in a contact sulphuric acid plant is
The Orsat analysis of a ffoe gas is: CO2 = 12. 7% ; 0 2 = 7.1 % ; N 2 = 80.2% . Detenmne the 4% S02 , I3% 02 and 83% N2 (volume %). In the converter S02 is oxidised to S03. The
percent excess air used fa combustion. The nitrogen present in the flue gas is contributed gases leaving the converter contain 0.45% S02 on an S03 - free basis (volume%). Calculate
by air only. (GATE-1995-11) the percent conversioo of S02 . (GATE-1992-12a)

Solution: Solution:
Basis: 100 mo! of flue gas. Basis: 10() wol of gases entering the convert-er.
Reaction:
21 S02 + 1/202 -> SOa
80.2 mo! of N2 80.2 x
79
= 21.32 mo! of 0 2
i.e., Total 02 entering 21.32 mo! Let x be the.fraction.al conversion of S02 in the converter. Then the gases leaving the
converter will contain:
For the reaction C + 02-+ CO2, 1 mo! of CO2 re.quires 1 mol of 02. Therefore 0 2 used for
CO2= 12.7 mo!. S03 = 4x mo!; S02 =4- 4x mo!; 02 = 13 - 2x mo!; N2 = 83 mol
0~ used for 1ikoN= Total 0 2 ea.t.ering - (0 2 used for CO 2 + 0 2 leaving) Given: S02 in converter outlet gases= 0.45% on SOa free basis. Therefore,
21.32 - (7.1 + 12.7) = 1.52 mo! 4- 4x 0.45
83 + (13 - 2x) + (4 - 4x) = 100
02 needed for combustion 12.7 + 1.52 = 14.22 mo!. ./1 Solving, x = 0.894. Therefore, conversion of S02 in the converter = 0.894 x 100 = 89.4%
21.32 mo! -~P
21.32 - 12.22
% excess a.ir _ X 100 = 50% 1.3.5 Percentage Excess Air
12 22
Pure propa.ne(C3Hs) is burn.t with an excess of s.ir to give the following analysis of combus-
tion products in volume percent:
1.3.3 Concentration of S02 in Flue Gas CO2= 5.0, CO= 3.5, H20= 11.4, 02 = 7.0 and N2 = 73.1
Calculate the percentage of excess air used. (GATE-1990-lli)
The concentration ofSO2 irJ the ffoe gases from a boiler was found to be 0.2 kg/ur at N. T.P.
Determine the concentration of SO2 in parts per million by volume, at N. T.P. Assume that Solution:
 PROCESS CALCULATIONS 23
22 AN INSIGHT CNTO CHEMICAL ENGCNEER.ING - msubbu

Basis: 100 mo! of product gases. Reactions:

The following reactions could be written for the combustion of C3Hs:
Ce.C03 ---> CaO + CO2 (95% conversion of CaCOa)
C:iHs + 502 ...... 3C02 + 4H2O MgCO3 -+ MgO + CO2 (90% conversion of MgCOa)
7 C + 02 ..... CO2
C.1Hs + 02 - 3CO + 4H2O
2
Liinestone : Coke = 5:1. Therefore,
From stoichiometry, 3 mol of CO2 is from 1 rn.ol of C3Hs and also 3 mo! of CO is from 1
mol of C 3 H8 . And for complete combustion of I mol of CaHs, 5 mol of 0 2 is required. Feed coke = 0.2 kg

Tota.I propane in feed . Propane for 5 mo! of CO2 and 3.5 mol of CO Carbon in coke 0.76 x 0.2 = 0.152 kg
5 3.5 Ash in coke 0.21 x 0.2 = 0.042 kg
3+ 3 Moisture in coke 0.03 x 0.2 = 0.006 kg
2.833 mo!
Theoretical air :required Air required for complete combustion of C3 Hs to CO2 Solid products leaving the kiln:
5
2.833 x -
0 .21
= 67.46 mo! Inerts 0.04 kg
Ca..CO3 = 0.&45 x 0.05 = 0.0423 kg
73.1
Air actually used _
0 79
=92.53 mol MgCOa = 0.115 x 0.1 = 0.0115 kg
% excess air
92.53 - 67.46 X 100 -_ 37.2"'
10
Ca.O = 0.845 x 0.95 x 56/100 = 0.4495 kg
67. 46 MgO = 0.115 x 0.9 x 40.3/84.3 = 0.0495 kg
Ash = 0.042 kg

1.3.6 Calcination of Limestone Total solid products = 0.04 + 0.0423 + 0.0115 t 0.4495 + 0.0495 + 0.042 0.6348 kg. =
Weight% of CaO in the products leaving the kiln= (0.4495/0.6348) x 100 = 70.81%
i✓imestone mixed with coke is being burnt in a kiln. An average analysis of limestone is
CaCOa: 84.5%, MgCO3: 11.5% and the rest inerts. The coke contains 76% carbon, 21%
:?Sb and 3% moisture. Tbe calcination ofCaCO3 is only 95% complete and that ofMgCO3 1.3.7 Percentage of CH 4 Burnt
90%. The carbon in the coke is completely burnt to CO2. Tb.e kiln is fed with 1 kg of coke In a laboratory experiment pure methane is burnt with theoretical quantity of air. Only
per 5 kg limestone. Calculate weight percent CaO in tho nroduct leaving the kiln. (GATE- part of the metbBJJe burns but the part that burns goes to CO2 and H2O. If the methane
199I-12ii) and a.ir are foitially at 25" C and the products leave at 40C1'C with water in vapor form. what
% of the methane is burnt?
Solution: Data:
Basis: l kg of limestone in feed. For the oxidation of CO 2 and H 2 O(vapor) the standard heat of reaction l::,.H'Ji. = -802.9
Feed contains: kJ/mol ofCH4 reacted.
Specific enthalpies at 4.00°C in kJ/mol (Reference: Speci.6.c enth.alpy at 2S'C= 0 kJ/mol)
Cs.003 = 0.845 kg
02 ll.64
Mg(X¾ 0.115 kg N2 11.13
inerts l - 0.845 - 0.115 = 0.04 kg CRt 17.22 (GATE-1989-lliii)
CO2 16.43
Molecular weight of H2O 13.2
CaC(h = :-10 + 12 + 3 X 16 = 100 Solution:
24.3 + 12 + 3 X 16 = 84.3 Basis: 1 mol of CH4 in feed.
MgCO3 = The following rea.ctions could be written for the combustion of CH4:
Ca.O = 40+ 16 = 56
MgO = 24.3 + 16 = 40.3
3
24 AN INSIGHT INTO CHEMICAL ENGINEERING - m subbu PROCESS CALCULATIONS 25

Energy balance for adiabatic reaction: C2H2 used for the desirable reaction
% Selectivity = · Total 0.?H4 reacted x l_OO
Heat content of products Heat coDtent of reactants +
0.853
24
Heat released from reaction 0.853 + 0.5 X 5.213 X lOQ = ·66%
Hp = HF+HR
If reference temperature is chosen as 300 K, th~ HF = 0. Total C28' reacted
% Overall conversion
Let x be the fraction of methane unburnt. Then, C2~ in feed x l 00
0.853 + 0.5 X 5.213
(1- x) x 802.9 = 1 x (1 - x) x 16.43 + 2 x (1 - x) x 13.2 + = 0.853 + 0.5 X 5.213 + 2.18 X lOQ ~ Gl.34%
79
2 X X 11.13 +x X 17.22+2 XX X 11.64
21 Ethylene in feed 0.853 + 0.5 x 5.213 + 2.18 = 5.6395 mo!
= 0.845
X

Percentage of methane burnt= (1- x) x 100 = (1 - 0.845) x 100 = 15.5%

Air in feed = 74 33
· = 94.785 mo!
0.79
<1.. •1
3-0'-!~
;).__:,3 ,r
,.., --:::
Air to ethylene mole ratio in feed
94.1ss . _
_
. ~ - ~,.,
. 1 - :6.8k:AL UBKARY 'ulJ
U,o-.v
.
5 6395
1.3.8 Percentage Conversion of C2 H 4 ccNT . . . C olle ge
• £••mne enh9
Exit gases from a.n ethylene oxide reactor had the following analysis (mol% on dry basis): ,l.nlna• .,. y • 6 603
ethylene 2.3, ethylene oxide 0.9, nitrogen 79.0, oxygen 12.3 and carbon dioxide 5.5. Calculate , n,malcu • 60 .
1.3.9 Propane Dehydrogenation Plant Tituvai.
(a) percent selectivity
The process schematic of a propane dehydrogenation plant i.s shown below. It is desired
(b) percent overall coJJversion, and to set up a simplified version of the material balance for this pl.ant. Assume that the only
reaction is the dehydrogenation of propane to propylene; there are no side reactions. The
(c) air to ethylene mole ratio in the feed mixture. (GATE-1988-lli) yield of propylene per pass is 30% (i.e., 30% of propane entering the reactor is converted
to propylene). · Assume that the amount of carbon formed on the c.atalyst is negligible.
The product :Bow rate (stream Ss) i.s 50 kmol/hr. Calculate the Bow rates of all the other
Solutfon: streams. Notice that all streams except stream S3 are pure. (GATE-2001-5)
Basis: 100 mo! of.dry exit gases.
Reactions: I 84 H2
S1 S2 Sa Absorber and
CaHs
Catalytic Reactor
CaHs, Caliil, H2 Distillation Tower s~
CaH6
As per reaction 2,
I
moles of H20produced = moles of CO 2 produced= 5.5 Solution:
Basis: 1 hr of production time; 50 kmol/hr of product fiow(C:Jlli,)
Total number of moles leaving the reactor 100 + moles of H 2 0 = 105.5
Reaction:
Analysis of exit gases on wet basis: CaHs --> CaHs + H2
2.3 1 mole of propylene is formed from 1 mole of propane. Therefore the stream S1 is 50 kmol
Ethylene = - x 100 2.18
105.5 of C3Hs
Similarly, ethylene oxide 0.853 Stream S4 conta.ms hydrogen, and as per reaction the flow rate is 50 kmol/hr.
74.88
11.66 C3H6 in S3 :a 50 kmol
5.213 H~ in S3. 50 kmol
 AN INSIGHT INTO CHEMICAL ENGINEERJNG - m subbu . PROCESS CALCULATIONS 27

As conversion of propane per pass is only 30% Since the fresh feed is having the reactants in stoichiometric ratio, CO and H 2 in the mixed
feed will also be in stoichiometric ratio.
50
C3Hg in S2 = -0.3 = 166.7 kmol From stoichiometry,
C3Hs in S3 = 166.7 X (1- 0.3) = 116.7 kmol
1 mol of CO
2 mol of Hz
Summary:
S1 50 kmol/hr Therefore, to produce 100 kmol of CH3 0H, the fresh feed should have 100 kmol of CO and
S2 166.7 kmol/hr 200 kmol of H2,
S3 116.7 + 50 + 50 = 216.7 kmol/hr i.e., Fresh feed rate (F) = 100 + 200 = 300 kmol/hr.
S4 50 kmol/hr
Ss 50 kmol/hr Since the conversion is only 15%,
S6 116.7 kmol/hr
CO in mixed feed should be 100/0.15 = 666.7 kmol
1.3.10 · Methanol ,Produ'c_tion in Recycle Reactor Similarly, H2 in mixed feed 200/0.15 = 1333.4 lanol
.... . .,/r
,\Mha.u~i is priiduced by the re.ac,~r/ofCOwith Hz as Therefore, mixed feed rate (F + R) = 666.7 + 1333.4 = 2000 kmol/hr.
Recyle flowrate = 2000 - 300 = 1700 kmol/hr.
CO + 2H2 --+ CHaOH
01;ly 15% of carbon monoxide entering the reactor is converted to methanol. The methanol 1.3.11 Recycle Ratio in Reverse Osmosis Desalination
,o~med is condensed and recovered completely. The unreacted COa.nd H 2 are recycled ba.ck
io the reactor. The fresh feed will cont.<un H 2 and CO in the molar ratio of 2:1. For 3200 Sea. water is desalinated by reverse osmosis a.s shown in figure.
/..f;/hr of methanol produced, calculate Recycle R (kg/hr)
(i) kmoJ/br of fresh feed

(ii) /arlol/hr of recyde gas (GATE-1995--6) . F (kg/hr) Reverse Osmosis E (kg/hr)

Mixer 4% salt Cell

All compositions are on mass basis. Calculate R/E. (GATE-1997-12)

Solution:
!3asis: 3200 kg/hr of CHaOHproduction.
Solution:
Recycle R (kg/hr)
r, ---------------------- ------7
F
fRM•I Reactor H Separator ~ Il

l~ I Sea water
1000 kg/hr
:r---------
I

11 Brine wa.5te
.,__ _ __, Reverse Osmosis E (kg/hr)
3% salt ,, Mixer Cell 3 I B (kg/hr)
~ - - - -- - - - - - - - - - - - ____ _ ______ J 5% salt
Mass ftowrate
Molar flowrate of metha.nol(P)
Molecular weight
Desalinated water
3200 , 0.05% salt
32
100 kmol/hr
28 AN INSIGHT INTO CHEMICAL ENGINEERING-msubbu PROCESS CALCULATIONS 29

Mass balance around boundary 1: Ratio of A to I leaving the reactor {also in separator & in purge) = 0.67y/x
Overall:
IO00=B+D (1.3) Amount of I in the purge 0.005
Balance on salt: Amount of A in purge 0.005 x 0.67y/x = 0.00335y/x
1000 x 0.03 = ~-: x D + 0.05 x B (1.4) Overall mass balance:
Solving Egns.(1.3) and (1.4), D = 404 kg/hr; B = 596 kg/hr.
Mass balance around boundary 2: Fresh feed B + Purge
Overall: 1 y + 0.00335y/x + 0.005
F = lOOO+R (1.5)
Solving Eqns.(1.7) and (1.8), x = 0.031; y = 0.855
Balanee Oil salt:
0.03 x 1000 + 0.05 x R = 0.04 x F (1.6) A in purge 0.00335y/x = 0.00335 x 0.855/0.031 = 0.092 mol
Solving Eqns.(1.5) a11d (1.6), R = 1000 kg/hr. A in recycle 0.67y - 0.092 = 0.67 x 0.855 - 0.092 = 0.481 m.ol
From overall mass balance at junction 3, A/I in recycle 0.67y/x = 0.67 X 0.855/0.031 = 18.5
E= B + R = 596 + 1000 = 1596 kg/hr I in recycle 0.481/18.5 = 0.026 mo!
Recycle amount 0.481 + 0.026 = 0.507 mo!
Therefore Rf E = 1000/1596 = 0.627
Total feed to reactor at 1 1 + 0.507 = 1.507 mol
1.3.12 Recycle to the Reactor Ratio of Recycle to total few 0.507/1.507 = 0.336

For the reaction A -+ B, the process flow diagram is shown in figure. The fresh feed of A
consists of 0.5% of interts by volume. 60% conversion per pass of A fed to the reactor is
obtained. The concentration of inerts going into the reactor at (1) must be held at 2% by 1.3.13 Saturator Bypass
volume. All streams are ideal gases and the process is at steady state. How ma.ny moles
need to be recycled per mole of total feed to the reactor at (1). (GATE-1990-llii) A 4% solution of a salt in water is required in a continuous process. .Fbr thi5 purpose, a part
of the water is by passed through a saturator from which a. 25% solution .is produced. If this
stream is mixed with the ma.in water stream to produce the 4% solution, what percentage
Fresh feed 1 of water must be by passed? {GATE-1989-lli)
Reactor Separator
A,I A,I .__ ___.
Solution:
Recycle Purge Basis: 100 kg of 4% solution (P).
A,I A,I The streams are represented in the diagram as
Solution:
Basis: 1 mole of fresh feed Water Main line M 4% salt soln.
Reaction: A -+ B F--- ~ ------- -~- p
A in fresh feed = l x (1 - 0.005) = 0.995 mo!
I in purge = 1 x 0.005 = 0.005 mo!
Bypass
Let y be the moles of B leaving separator. Then,
Saturator 1-------'B
A to reactor at 1 = y/0.6 = l.67y mo! 25% salt
soln.
A leaving the reactor = l.67y x (1 - 0.6) = 0.67y mo!
Mass balance on water:
Let x be the moles of I to the reactor at 1. T hen,
X
Water in bypass + Water in mainline = Water in product
1 . 67y+x
= 0.02 (1. 7) B.x 0.75+M = Px 0.96 (l.9)
 AN INSIGHT INTO CHEMICAL ENGINEERING - msubbu PROCESS CALCULATIONS 31

Ncrall mass balance: Given: Atmospheric pressure= 103 kPa = (103/101-25) x 760 = 773.1 mm Hg.

partial pressure of water vapor

B+M=P=lOO (1.10) Relative humidity
vapor pressure of water
Partial pressure of water vapor at inlet = =
0.4 x 17.2 6.88 mm Hg
:olving Eqns.(1.9) and (1.10), B = 16 kg; M = 84 kg.
~alt in B = 16 x 0.25 = 4 kg.
Paitial pressure of water vapor at outlet = 0.65 X 186.3 = 121.l = Hg
PA
fherefore, water entering the saturator = 16 - 4 = 12 kg. Absolute molal humidity =
\Vater in F = 84 + 12 = 96 kg.
Pt-PA
6.88 18
:"raction of water bypassed through the saturator = 12/96 = 0.125 Absolute humidity of entering air = x-
773.1 - 6.88 29
5.573 x 10-3 kg water / kg air
121.1 18
Absolute humidity of leaving air = x-
773.1 - 121.1 29
l .3.14 Drying of CaC03 Slurry 0.1153 kg water / kg air
Moisture taken by air 0.1153 - 5.573 X 10-3
'aCO3 slurry has to be dried. The dryer is designed to remm•c 100 kg moisture per hour. 0.1097 kg moisture/ kg air
~ir at 2Cf'C and 40% relative humidity, enters the dryer aud leaves at 65°C and 65% relative
:i,midit_y. What is the weight (in kg) of bone-dry air required per 110111·? The atmospheric If the entering air is 0% relative humidity (bone-dry air), then
m•ssure is 103 kPa. If the humidity of the air entering can be mricd, 1Vhat is the mini-
'"m amount of dry air required? The constants for Antoisie equation for vapor pressure of moisture removed = moisture out - moisture in
Acr iu mm Hg may be taken as A = 18.306, B = 3816.44 and C = -46.13. (GATE-1999-7)
0.1153 - 0 = 0.1153 kg moisture / kg dry air
-;olution:
.'a.~is: 100 kg moisture removal per hour.
Minimum amount of air required 0.~~~
3
= 867.3 kg

2ooql
40% RH
Dr er
y
165:c
65% RH
1.3.15 Crystallization

. utoine equation: 1000 kg/hr of an aqueous solution of 20% Na,.iCO3 is cooled gradually to T°C, to crystallize
out Na 2 CO3 .10H2 O. The solubility of Na,.iCO3 at T°C is 2.1 %. Calculate the percentage of
Na2 CO3 recovered in the form of crystals. (Assume no loss ofNa2COa through the mother
In psat = A - __!!___ = 18.306 - 3816.44 liquor adhering to the crsytals and no carry over of crystals with the mother liquor). Draw
t+C t-46.13 a neat block diagram showing the inlet and exit compositions and Bow rates.
(Molecular weight ofNa2CO3 can be assumed to be 106 and that of water to be 18). (GATE-
1998-12)
·:heck: at t = 100°C = 373 K,
Solution:
P sat = exp (1s 306 - -=-----
. 3816.44 )
373- 46.13
= 757. 7 mm Hg
Basis: 1000 kg/hr of aqueous solution of 20% Na2CO3
Let us denote the fl.ow rates of feed as F and mother liquor as M and crystals as C.
Composition of mother liquor:

herefore, t in Antoine equation is in Kelvin. From Antoine equation for inlet air at 20°c
= 17.2
,, at = Hg; and for outlet air at 65°C, pa.t = 186.3 mm Hg'. '
Weight fraction of Na2CO3
Weight fraction of H2O
0.021
1 - 0.021 = 0.979
 PROCESS CALCULATIONS 33
32 AN INSIGIIT INTO CHEMICAL ENGINEERING - msubbu

Composition of crystals:
Gp.mean
= Jra: Cp<lI'
550 - 380
Moleculai: weight of NazCO3 .l0H2O = 106 + 10 x 18 = 286
106 = 1.436 X (550 - 380) + 0.00218 X !_ X 5502 - 3802
Weight fraction of N32CO3 in N~COa.lOH2O = 286
= 0.371 550 - 380 2 550 - 380
Weight fraction of H2Oin Na2C03 .l0H2 0 = =
1 - 0.371 0.629
= 1.436 + 1.0137
2.4497 kJ/kg.K
Balance for H2O:
1000 x 0.8 = 0.979M + 0.629C (1.11}
Overall balance:
1000 M + C= (1.12) 1.3.17 Heat of Reaction
Solving Eqn.(1.11) and (1.12) simultaneously, M = 488.6kg/hr; and C = 511.4 kg/hr % The heat of reaction at 300 K and at one atm05phere pressure for the following gas phase
Recovery of N32CO3: reaction:
Na2CO3 in feed 1000 x 0.2 = 200 kg A+3B -+C
js -50,000 calories per mole of A con~- Data on the mol.a.r heat CApa.City at constant
Na.:zCOa in crystals = 511.4 x 0.371 = 189. 73 kg
73 pressure (cal/mol.K) of the various components a.re:
% of N~CO3 recovered ~ the form of crystals lS9.
200
X 100 =
94.87%

Block Diagr&ID.: GP for A= -0.4+80 x 10- sT, Tin K

C11 forB=7 ; ·._.
Feed = 1000 kg/hr Mother liquor = 488.6 kg/h.r CP forC=26
Na,CO3 = 20% Crystallizer N3-2C03 = 2.1% Calculate the heat of reaction at 500 Kand at one atmosphere p ~ . (GATE-1994--8)
H2O=80% H2O= 97.9%
Solution:
Crystals = 511.4 kg/hr Reactants _____ j@ K _ _ _ Products
Na2COa 62.9%=
H2O= 37.1%
1.3.16 Heat Load on Heater
1000 kg/hr of a thermic fluid, to be used as a beat transfer medium, is being jndirectly
heated in a beater, from 380 K to 550 K. Calculate the heat load on the heater, in kW. Also
estimate the mean beat capacity of the thermic fluid over the temperature range of interest.
The heat capacity equation for the tbermic fluid is:
Gp = 1.436 + 0.00218T where Cp is in kJfkg.K, and Tis in K. (GATE-1998-13) 4--------,---- 300 K
6.H.°
Solution: Reference T = 300 K. Reactant temperature = 500 K.
Ba&s: 1000 kg/hr of thermic fluid.
550 Heat of reaction at 500 K = Heat of reaction at 300 K
Heat load m
1
380
CpdI
..I =
+Enthalpy of products - Enthalpy of reactants
-50000 + 26 X (500 -:: 300) - 3
C 1::TdT]
X 7 X (500 - 300)
= 1000 x (1.436 + 0.00218T)d:T
- [ (- 4) X (500 - 300) + (80 X 10-
3
)

1000 X 1.436 X (550 - 380) + 1000 X 0.00218

·
X (
5502
2
-
3802
2
) I = : .:...50()00 + 26 X 200 - 21 X
2
200 + 0.4 X 200
'-(0.08/2) X (50Q2 - 300 .)
= 416449 k.J/br
115.68kW
= · -55320 calorie per mole of A oon~.
 l
~4 AN INSIGHT INTO CHEMICAL ENGINEERING - msubbu PROCESS CALCULATIONS 35

Heat of reaction at 300°C = Heat content of products - Heat content of reactants

+ Standard heat of reaction
1.3.18 Amount of ~eat Required i.e., !:::.HR !:::.Hp - /:::,.Hr+ 6.H'k ·

Pure CO is mixed with 100% excess air 8.Ild burnt. Only 80% ofCO burns. The reactants are
= 47110-12645- 226392
at l()(J'C and the products are at 30(]'0. Calculate the a.moWJt of beat added or removed - 191927 kl
per kmol of CO fed to the reactor.
Heat released during the reaction= 191927 kJ.
Da ta: Mean molal speci.i.c beats between 2S'C and T"C (given below in kJ/mol.K) a.re:

1.3.19 Flame Temperatur1:; and Excess Air

Gas T = l0(J'C T = 30<J'C Dry methane is burned with dry air. Both are initially a t 300 K. The theoretical flame
temperature is 1570 K. H complete combustion is assumed, how much excess air was used?
29.22 30.61
43.77 Data: Mean molar speci.i.c beat values iD J/mol.K are:
29.64 43.77 CO2 = 51.8, H2 0= 40.2, N2 = 32.2 and 02 = 32.4
29.66 Stanihrd heat of formation at 300 K = - 8 x 105 J/ mol ofCH.t (GATE-1988-llii)
29.17

S'ta.ndard beat of formation at 25"C in kJjkmoI are: Solution;

co -110524 (GATE-1995-12)
Reaction:
CO2 -393514
S olution; Energy balance for adiabatic reaction:
lfasis: 1 kmol of CO in feed.
Heat content of products Heat content of reactants + Heat released from reaction
'.l eaction:
Hp Hp +HR

If reference temperature is chosen as 300 K, then HF = 0.

02 in feed = 1 mo! If complete combustion is assumed, then the product gases will not contain CH4. But it is
79 possible to have N2 and 0 2 io the product gases. Let x be the moles of 02 in the product
N2 in feed = 21
mol
gases. Then heat balance becomes,
For complete conversion 1 mo! of COrequires 0.5 mol of 02
unreacted 0 2 1 - 0.5 x 0.8 = 0.6 mol due to N2
79 79 5
Standard heat of reaction at 25°C: (51.8 + 2 X 40.2 + X X 32.4 + X X X 32..2 + 2 X X 32.2)(1570 - 300) = 8 X 10
21 21
l:::,.H'}i_ = (- 393514 + 110524) x 0.8 = -226392 kJ Solving, x = 1.664 mol.
Heat content of reactants with reference to 25°C: excess 0 2 1.664 mol
0 2 used in reaction 2 mol
6.Hr = [29.22 + 29.64 + ~~ X 29.17] X (100 - 25)
% excess air
1.669
- - X 100 = 83.2%
2
= 12645 kJ

Heat content of products ~th reference to 25°0:

1.3.20 Heat Released from Reaction
b.Hp .- [o.2 ·; ;0.61_+0.~x43,;7 + 0~6 X 30.99 + ;~ X 29.66] X (300 ~ 25) The reaction, A(g) + 2B(g) --+ 2C (g) + 3D(g), with a st andard heat of reaction 6.H'k =
47110 kJ · -ld3 kJ/ mol of A reacted, is carried out in a re8ftor in which the feed enters a t 25°C and
) .
36 AN INSIGHT INTO CHEMICAL ENGINEERING - msubbu PROCESS CALCULATIONS 37

the product stream emerges as a gas at 3(J(f'C. The feed consists of 100. mol A/hr and 250 If reference temperature is taken as 700 K then, enthalpy of reactants = 0. Therefore,
mol B/hI. A is completely consumed during the reactioZJ. Calculate the heat transferred to
or from the reactor, assuming the operation at apprwdmately 1 atm. heat added by reaction = enth,.Ipy of product strea.m
Data: Specinc enthalpies at 3()(J'C
(Datum: Specific enthalpies of all components at 25°C = 0 k.J/rrrol). Let x be the fractional conversion per mol of N2 entering the reactor. Then product stream
Component Sp.enthalpy (kJ/mol) contains: 2x moles of~; (1 - x) moles of N2; and 3(1 - x) moles of H2 •
4- 9 Therefore, the heat balance (tlll = EnCp~T) becomes
··B 10 (GATE-1987-lliii}
c· 12 94.2 x 2x = (2.x x 0.0492 + (1 - x) x 0.03 + 3(1 - x) x 0.0289) x 100
D 15
Solving, x = 0.061. Therefore, the maximum a.llowa.ble conversion of N2 in the reactor is
6.1%.
Solution:
Basis: 100 mol of A as feed
For complete conversion of A, and for the reaction A(g)+2B(g) - 2C(g)+3D(g), the prod-
1.3.22 Maintaining Isothermal Operation of Reactor
uct contains: C: 200 mol; D: 300 mol; B 50 mol. Energy balance: Reference temperature A feed at 1298 K, consisting of .Bue gas (CO2, 02 and N2) and air, is passed th.rough a bed
= 2s c
0
· of pure carbon. The reactions that occur both go to completion.
Heat of reaction at 300°C = Enthalpy of products - Enthalpy of reactants+
CO2 (g) + C(s) -+ 2CO(g), ~H'k at 298 K == 170 kJ/mol
Std. heat of reaction 02(g) + 2C(s) -+ 2CO(g), ~H'k at 298 K = -220.4 kJ/mol
= {200 X 12 + 300 X 15 + 50 X 10) - 0 - 100 X 1C>3
-92600 kJ/hr The combustor is adiabatic 8Ild t.b.e product gases exit at 1298 K. Calculate the required
moles of CO2 per mole ofO2 in the feed stream, so that the .net heat generated is zero and
Heat transferred from the reactor = 92600 kJ/hr. the bed temperature remains co~t at 1298 K.
Data.: Mean molar beat capacities, Cpm
1.3.21 Conversion in Exothermic Reaction Substance Cpm, kJ/mol.K
C 0.02
Ammonia is produced by the following reaction
02 0.03 (GATE-1997-13)
N2 + 3H2 ~ 2NHa co 0.03
CO2 0.05
In a commercial process for ammonia productioZJ, t.b.e feed to an adiabatic reactor contains
1 kmolfsec of nitrogen and stojchiometric a.mount of hydrogen at 700 K. What is the maxi-
mum allowable conversion jn the reactor, if the adiabatic temperature rise llCr06S the reactor Solution:
should not exceed 100 K. Assume the feed and product streams to be ideal gas .mixtures. Reference T = 298 K. Feed & Product temperature = 1298 K
The beat of reaction at 700 K for the above reaction is calculated to be -94.2 kJ/mol. Mean Let x be the moles of CO2 per mole of 02 in the feed stream. Then For the first reaction,
molar heat capacities (Cp), in the range 7()()-M() K, are 0.03, 0.0289 and 0.0492 kJ/mol.K feed will be: x mole of Cand x mole of CO2; and product will be: 2:r mole of CO.
for nitrogen, hydrogen and ammonia respectively. (GATE-2002-13) For the second reaction, feed will be: 2 mole of Cand ~ mole of 02; and product will be: 2
mole of CO.
Solution:
Energy balance:
enthalpy of reactants + heat added by reaction
enthalpy of product stream
Also,
Heat of reaction at 700 K_ Enthalpy of products with reference to 700 K
-Enthalpy of reactants with reference to 700 K
298 K ........,=----,...,...,....,,.,,.
Reaction at 298 K
.....
 38 AN INSIGHT INTO CHEMICAL ENGINEERING - msubbu

Heat of reaction at 1298 K Heat of reaction at 298 K

+Enthalpy of products - Enthalpy of reactants

If heat generated is to be zero, heat of reaction at 1298 K should be zero. And since N 2 Chapter 2
doesn't take part in reaction ( also the amount of N2 in outlet is equal to that io. inlet),

0 = [x X 2 X 170 + 2 X ( -220.4}]

+ [(x X 2 X 0.03 + 2 X 0.03) Fluid Mechanics

-(x X 0.05 +XX 0.02 + 0.03 + 2 X 0.02)] X (1298 - 298)

~ -S-ol_ving
_ ,_x_=_l_.3_6_6_ _ __ _ _ _ __ _ _ _ _ _ _ _ __ _ _ _ __
2.1 Instant Notes
2.1.1 Fluid Statics
• Manomet€f principle: pressure· at the same level in a continuous body of fluid are
equal.
• Buoyant force = weight of fluid displaced.

2.1.2 Fluid Flow

• At room temperature kinematic viscosity is 1 centiStoke for water and 15 centiStoke
for air at atmospheric pressure.

• An ideal :Buid has a viscosity of :zero, and incompressible one. The flow of such an
ideal fluid is called potential flow. Potential flow hall two important characteristics:
(i) Neither circulations nor eddies can form within the stream, so that pot.ential flow
is also called as irrotational flow, and (ii) friction cannot develop, so that there is no
dissipation of mechanical energy into heat.

• Newtonian and Non-Newtonian fluids

- Newtonian fluids: the slope of shear stress (T) / strain rate (du/dy) = µ is a
constant regardless of the strain rate. Eg: gases, watar, liquid hydrocarbons, and
most organic liquids of rela.tively low molecular weight.
- Pseudoplastic {or shear-thinning) fluids: exhibit a viscosity that decreases with
increasing strain rate. Eg: most polymet solutions and polymer melts.
- Dila.tant (or shear-thickening) fluids exhibit a viscooity that increases with in-
·creasing strain rate. They are less common than pseudoplastic fluids. Eg: sand
or corn-starch suspension in water.
- Bingham plastic: a minimum stress is required before the fluid flows. Oncei,he
fluid flows, the viscosity JS constant. Eg: ketchup, t.oothpaste.

39
4
40 AN INSIGHT INTO CHEMICAL ENGINEERING - msubbu FLUID MECHANICS 41

- Time-dependent behaviors: - The thickness of the boundary layer varies with the distance from the leading
edge as: .
* Thbcotropic: viscosity decreases with time at constant strain rate. Eir. paint
* Rheopectic: viscosity increBSeS with time at a constant strain rate. 0 4.79
for le.minar flow
- Visco-elastic: exhibit ch.araderistics common to both viscous fl.uids and elastic :t' ~
solids. Bir. egg-white. 6 0.376
Rel/5
for turbulent flow
X
Inertial force :r
• Reynolds number = y·
lSCOUS
fo
rce The transition from laminar to turbulent flow occurs in the boundary layer at
• For circular tubes the flow is laminar when Re is less than about 2100, although ~=3.2xH>5.
a stable sinuous motion sets in at a Reynolds number of about 1225. Above 2100
laminar motion may be maintained temporarily if the tubes are very smooth and free
• Friction factor
from vibrations; but if the system is disturbed or if there is any appreciable surlace - Fanning Friction factor:
roughness the laminar motion will give way to the random motion that characterizes Tw
turbulent flow. f = pv2/2

=
• The curve of v versus y (v = velocity; 11 distance from the wall) is refened to as the - BLG$iWi or Darcy friction factor is also commonly encountered in fluid I)'.lechanics
velocity distribution or profile. At a sufliciently large distance from the tube entrance, literature, and is4"'times-the-F.mning &i.ction fact.or. Care should be ta.ken in
the velocity profile assumes a constant shape; the flow is said to be fully developed. reading friction factor charts, that whether the friction factor is Darcy or Fanning.
The velocity distribution for developed flow depends on whether the ii.ow is laminar
or turbulent. • Relation between Pressure drop due to skin friction (.t..P.) and wall shear stress (rw)
for flow through circular pipe:
• For ordinary Laminar fl.ow there is a parabolic variation of velocity from zero at the wall .6.P~ = 4rwL
to Vmax at the center of the tube. For pseudo plastic fluids, a relatively flat profile is D
obtained, and in the limit of an infinitely pseudopla.stic fluid there is rodlike flow. For • Skin friction and friction factor are related as;
dilatant fluids, the profile is sharper, and for the limiting case of an infinitely dila.tant
fluid, the velocity is a. linear function of the radius. The velocity profile is conical.
• A fundamental principle of :fluid mechanics, originally stated by Prandtl in 1904, is
tha.t, except for fluids moving at low velocities or possessing high viscosities, the effect • Laminar flow: Average velocity is precisely one-half the ma.xi.mum velocity (u.,,vg =
of the solid boundary on the flow is confined to a layer of fluid immediately adjacent Vmax/2). Relation for velocity profile;
to the solid wall. This layer is called the boundary Jayw, and shear forces are confined
to this part of the fluid.
• Boundary layel"
where V,ne.x is the CJmterline velocity.
- The boundary layer is the region near a solid where the fluid motion is affected
by the solid boundary. Outside the boundary layer potential flow survives. • Hagen Poiseuille equation; for laminar flow the following relation is valid:
- If a. fluid flowing with a uniform velocity enters a conduit, a boundary layer builds
up and eventually fills the pipe. Thus, in fully developed laminar or turbulent ll,P, = 32.Lvµ
flow, the entire radius of the pipe is in the boundary layer. • n2
- If the boundary layer is turbulent and fills the pipe, as it usually does except very One of its use is in the experimental measurement of ~ t y ; by measuring the
near the entre.nce to the pipe, a viscous sublayer peysists near the walls. pressure drop and wlumetric flow rate through a tube of known lengt_h and diameter.
- Boundary !~,-separation: Necessary condition dP/ch > 0, i.e., when pressure • Velocity profile in turbulent flow: In pipe flow, the following equation is valid up to
energy P increases in the direction of flow. This is the situation normally encoun- Re= 106 •
tered in :flow of :fluid in the diverging section of venturi, if the angle of diverging
section is more (> 12°).