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MASS AND HEAT TRANSFER

This book allows instructors to teach a course on heat and mass transfer that will equip
students with the pragmatic, applied skills required by the modern chemical industry. This
new approach is a combined presentation of heat and mass transfer, maintaining mathe-
matical rigor while keeping mathematical analysis to a minimum. This allows students to
develop a strong conceptual understanding and teaches them how to become proficient
in engineering analysis of mass contactors and heat exchangers and the transport theory
used as a basis for determining how the critical coefficients depend on physical properties
and fluid motions.
Students will first study the engineering analysis and design of equipment important
in experiments and for the processing of material at the commercial scale. The second
part of the book presents the fundamentals of transport phenomena relevant to these
applications. A complete teaching package includes a comprehensive instructor’s guide,
exercises, design case studies, and project assignments.

T. W. Fraser Russell is the Allan P. Colburn Professor of Chemical Engineering at the

University of Delaware. Professor Russell is a member of the National Academy of
Engineering and a Fellow of the American Institute of Chemical Engineering (AIChE).
He has been the recipient of several national honors, including the AIChE Chemical
Engineering Practice Award.

Anne Skaja Robinson is an Associate Professor of Chemical Engineering at the Uni-

versity of Delaware and Director of the National Science Foundation (NSF) Integra-
tive Graduate Education and Research Traineeship program in biotechnology. She has
received several national awards, including the NSF Presidential Early Career Award for
Scientists and Engineers (PECASE/Career).

Norman J. Wagner is the Alvin B. and Julia O. Stiles Professor and Chair of the Depart-
ment of Chemical Engineering at the University of Delaware. His international teaching
and research experience includes a Senior Fulbright Scholar Fellowship in Konstanz, Ger-
many, and a sabbatical as a Guest Professor at ETH, Zurich, as well as at “La Sapienza,”
Rome, Italy.

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CAMBRIDGE SERIES IN CHEMICAL ENGINEERING

Series Editor:
Arvind Varma, Purdue University

Editorial Board:
Alexis T. Bell, University of California, Berkeley
Edward Cussler, University of Minnesota
Mark E. Davis, California Institute of Technology
L. Gary Leal, University of California, Santa Barbara
Massimo Morbidelli, ETH, Zurich
Athanassios Z. Panagiotopoulos, Princeton University
Stanley I. Sandler, University of Delaware
Michael L. Schuler, Cornell University

Books in the Series:

E. L. Cussler, Diffusion: Mass Transfer in Fluid Systems, Second Edition
Liang-Shih Fan and Chao Zhu, Principles of Gas–Solid Flows
Hasan Orbey and Stanley I. Sandler, Modeling Vapor–Liquid Equilibria: Cubic
Equations of State and Their Mixing Rules
T. Michael Duncan and Jeffrey A. Reimer, Chemical Engineering Design and Anal-
ysis: An Introduction
John C. Slattery, Advanced Transport Phenomena
A. Varma, M. Morbidelli, and H. Wu, Parametric Sensitivity in Chemical Systems
M. Morbidelli, A. Gavriilidis, and A. Varma, Catalyst Design: Optimal
Distribution of Catalyst in Pellets, Reactors, and Membranes
E. L. Cussler and G. D. Moggridge, Chemical Product Design
Pao C. Chau, Process Control: A First Course with MATLAB®
Richard Noble and Patricia Terry, Principles of Chemical Separations with
Environmental Applications
F. B. Petlyuk, Distillation Theory and Its Application to Optimal Design of
Separation Units
L. Gary Leal, Advanced Transport Phenomena: Fluid Mechanics and
Convective Transport
T. W. Fraser Russell, Anne Skaja Robinson, and Norman J. Wagner, Mass and Heat
Transfer

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Mass and Heat Transfer

ANALYSIS OF MASS CONTACTORS
AND HEAT EXCHANGERS

T. W. FRASER RUSSELL
University of Delaware

ANNE SKAJA ROBINSON

University of Delaware

NORMAN J. WAGNER
University of Delaware

v
CAMBRIDGE UNIVERSITY PRESS
Cambridge, New York, Melbourne, Madrid, Cape Town, Singapore, São Paulo

Cambridge University Press

The Edinburgh Building, Cambridge CB2 8RU, UK
Published in the United States of America by Cambridge University Press, New York
www.cambridge.org
Information on this title: www.cambridge.org/9780521886703

© T. W. Fraser Russell, Anne Skaja Robinson, and Norman J. Wagner 2008

This publication is in copyright. Subject to statutory exception and to the provision of

relevant collective licensing agreements, no reproduction of any part may take place
without the written permission of Cambridge University Press.
First published in print format 2008

ISBN-13 978-0-511-38683-1 eBook (EBL)

ISBN-13 978-0-521-88670-3 hardback

Cambridge University Press has no responsibility for the persistence or accuracy of urls
for external or third-party internet websites referred to in this publication, and does not
guarantee that any content on such websites is, or will remain, accurate or appropriate.
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This book is dedicated to our families:

Shirley, Bruce, Brian, Carey
Clifford, Katherine, Brenna
Sabine

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Contents

Preface page xiii

To the Student xv
Acknowledgments xix
Instructors’ and Readers’ Guide xxi

PART I
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
References 19

2 Chemical Reactor Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

2.1 The Batch Reactor 21
2.1.1 Chemical Equilibrium 25
2.2 Reaction Rate and Determination by Experiment 26
2.2.1 Rate Expression 26
2.2.2 Approach to Equilibrium 32
2.3 Tank-Type Reactors 33
2.3.1 Batch Reactors 34
2.3.2 Semibatch Reactors 34
2.3.3 Continuous Flow 37
2.4 Tubular Reactors 42
2.5 Reactor Energy Balance 47
References 51
Problems 51

3 Heat Exchanger Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55

3.1 Batch Heat Exchangers 56
3.1.1 Level I Analysis 57
3.1.2 Level II Thermal Equilibrium 58
3.2 Rate of Heat Transfer and Determination by Experiment 60
3.2.1 Rate Expression 61
3.2.2 Approach to Equilibrium 65

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x Contents

3.3 Tank-Type Heat Exchangers 67

3.3.1 Batch Heat Exchanger 68
3.3.2 Semibatch Heat Exchanger 68
3.3.2.1 Mixed–Mixed Fluid Motions 69
3.3.2.2 Mixed–Plug Fluid Motions 72
3.3.3 Continuous-Flow Tank-Type Heat Exchangers 74
3.3.3.1 Mixed–Mixed Fluid Motions 74
3.3.3.2 Mixed–Plug Fluid Motions 78
3.4 Tubular Heat Exchangers 79
3.4.1 Cocurrent Flow 81
3.4.2 Countercurrent Flow—Double-Pipe Heat Exchanger 88
3.5 Technically Feasible Heat Exchanger Design 94
3.5.1 Design Procedure 96
References 102
Problems 103
Appendix. Energy Balance 109

4 Mass Contactor Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114

4.1 Batch Mass Contactors 118
4.1.1 Level I Analysis 119
4.1.2 Level II Analysis, Phase Equilibrium 120
4.2 Rate of Mass Transfer and Determination by Experiment 125
4.2.1 Rate Expression 127
4.2.2 Approach to Equilibrium 132
4.3 Tank-Type Two-Phase Mass Contactors 134
4.3.1 Batch Mass Contactors 135
4.3.2 Semibatch Mass Contactors 137
4.3.2.1 Mixed–Mixed Fluid Motions 138
4.3.2.2 Mixed–Plug Fluid Motions 139
4.3.3 Continuous-Flow Two-Phase Mass Contactors 143
4.3.3.1 Mixed–Mixed Fluid Motions 144
4.3.3.2 Design of a Continuous Mixed–Mixed Mass Contactor 146
4.3.3.3 Mixed–Plug Fluid Motions 153
4.4 Tubular Two-Phase Mass Contactors 156
4.4.1 Cocurrent Flow 158
4.4.2 Countercurrent Flow 159
4.4.3 Gas–Liquid Countercurrent Contactors 164
4.5 Continuous-Flow Mass Contactor Design Summary 168
References 175
Problems 175
Appendix A. “Log-Mean” Concentration Difference 178
Appendix B. Equivalence Between Heat and Mass Transfer
Model Equations 180

Nomenclature for Part I . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181

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Contents xi

PART II
5 Conduction and Diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
5.1 Rate of Thermal Conduction 187
5.1.1 Experimental Determination of Thermal Conductivity k and
Verification of Fourier’s Constitutive Equation 187
5.1.2 Definition of the Biot Number for Heat Transfer 195
5.1.3 Definition of the Nusselt Number 199
5.2 Rate of Molecular Diffusion 201
5.2.1 Experimental Determination of Binary Diffusivities DAB and
Verification of Fick’s Constitutive Equation 201
5.2.2 Definition of the Biot Number for Mass Transfer 206
5.2.3 Definition of the Sherwood Number 208
5.3 Geometric Effects on Steady Heat Conduction and Diffusion in
Solids and Quiescent Fluids 209
5.3.1 One-Dimensional Heat Conduction in Nonplanar Geometries 209
5.3.2 One-Dimensional Diffusion in a Conical Geometry 211
5.4 Conduction and Diffusion Through Composite Layered Materials
in Series 212
5.4.1 Overall Heat Transfer Coefficient for Composite Walls:
Resistance Formulation 212
5.4.2 Overall Heat Transfer Coefficient for a Tubular Exchanger 217
5.4.3 Overall Mass Transfer Coefficient for Diffusion Through a
Composite Wall 220
5.5 Molecular Conduction and Diffusion with Generation 222
5.5.1 Radial Heat Conduction with Generation 222
5.5.2 Diffusion with Chemical Reaction 224
5.6 Diffusion-Induced Convection: The Arnold Cell 225
5.7 Basics of Membrane Diffusion: The Sorption–Diffusion Model 230
5.8 Transient Conduction and Diffusion 231
5.8.1 Short-Time Penetration Solution 233
5.8.2 Small Biot Numbers—Lumped Analysis 235
Nomenclature 236
Important Dimensionless Groups 238
References 239
Problems 240

6 Convective Heat and Mass Transfer . . . . . . . . . . . . . . . . . . . . . . . . 246

6.1 The Differential Transport Equations for Fluids with Constant
Physical Properties in a Laminar Boundary Layer 247
6.1.1 Mass Conservation—Continuity Equation 248
6.1.2 Momentum Transport—Navier–Stokes Equation 249
6.1.3 Energy Conservation 250
6.1.4 Species Mass Conservation 252
6.2 Boundary-Layer Analysis and Transport Analogies 254
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xii Contents

6.2.1 Laminar Boundary Layer 254

6.2.2 Reynolds Transport Analogy 257
6.2.3 Effects of Material Properties: The Chilton–Colburn Analogy 260
6.2.4 Turbulent Boundary Layers 263
6.3 Transport Correlations for Specific Geometries 264
6.4 Models for Estimating Transport Coefficients in Fluid–Fluid Systems 273
6.4.1 Film Theory 273
6.4.2 Penetration Theory 273
6.4.3 Surface Renewal Theory 278
6.4.4 Interphase Mass Transfer 279
6.5 Summary of Convective Transport Coefficient Estimations 281
6.5.1 Heat Exchangers 281
6.5.2 Mass Contactors 284
Nomenclature 286
References 287
Problems 287
Appendix A. Derivation of the Transport Equations 293
Appendix B. Vector Notation 299

7 Estimation of the Mass Transfer Coefficient and Interfacial

Area in Fluid–Fluid Mass Contactors . . . . . . . . . . . . . . . . . . . . . . . . 301
7.1 Estimation of Bubble and Drop Size 304
7.2 Tank-Type Mass Contactors 307
7.2.1 Mixed–Mixed Interfacial Area Estimation 307
7.2.2 Mixed–Mixed Km Estimation 309
7.2.3 Mixed–Plug Area Estimation 309
7.2.4 Mixed–Plug Km Estimation 313
7.3 Tubular Contactors 316
7.3.1 Cocurrent Area Estimation 316
7.3.2 Cocurrent Km Estimation 318
7.3.3 Countercurrent Area Estimation 318
7.3.4 Countercurrent Km Estimation 320
Nomenclature 320
References 321
Problems 322
Appendix. Bubble and Drop Breakage 323

8 Technically Feasible Design Case Studies . . . . . . . . . . . . . . . . . . . . 327

8.1 Technically Feasible Design of a Heat Exchanger 328
8.2 Technically Feasible Design of a Countercurrent Mass Contactor 335
8.3 Analysis of a Pilot-Scale Bioreactor 345
Nomenclature 353
References 354
Problems 354
Index 363
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Preface

Chemical engineers educated in the undergraduate programs of departments of

chemical engineering have received an education that has been proven highly effec-
tive. Chemical engineering educational programs have accomplished this by manag-
ing to teach a methodology for solving a wide range of problems. They first did so
by using case studies from the chemical process industries. They began case studies
in the early part of the 20th century by considering the complete processes for the
manufacture of certain chemicals and how they were designed, operated, and con-
trolled. This approach was made much more effective when it was recognized that
all chemical processes contained elements that had the same characteristics, and the
education was then organized around various unit operations. Great progress was
made during the 1940s and 1950s in experimental studies that quantified the analysis
and design of heat exchangers and equilibrium stage operations such as distillation.
The 1960s saw the introduction of reaction and reactor analysis into the curriculum,
which emphasized the critical relationship between experiment and mathematical
modeling and use of the verified models for practical design. We have built upon this
approach, coupled with the tools of transport phenomena, to develop this text.
Our approach to teaching mass and heat transfer has the following goals:

1. Teach students a methodology for rational, engineering analysis of problems in

mass and heat transport, i.e., to develop model equations to describe mass and
heat transfer based on the relationship between experimental data and model.
2. Using these model equations, teach students to design and interpret laboratory
experiments in mass and heat transfer and then to effectively translate this knowl-
edge to the operation and design of mass and heat transfer equipment.
3. Develop the students’ molecular understanding of the mechanisms of mass and
heat transfer in fluids and solids and application in the estimation and correlation
of mass and heat transfer coefficients.

To achieve these goals we use the following methods:

r Emphasize the critical role of experiment coupled with the development of an
appropriate model.
r Focus attention on analysis and model development rather than on mathemati-
cal manipulation of equations. This is facilitated by organization of the analysis
method into levels.
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xiv Preface

r Provide a rational framework for analyzing mass and heat transfer phenomena
in fluids and the associated equipment based on a simple fluid mechanical model
of the devices.
r Treat mass transfer on an equal level with heat transfer, and, wherever possible,
provide a parallel development of mass and heat transfer phenomena.
The levels of analysis introduced in Chapter 1, Table 1.1, provide a guide to
the rational analysis of engineering transport equipment and transport phenomena
in increasing orders of complexity. The information obtainable from each level of
analysis is delineated and the order of analysis preserved throughout the textbook.
We present the material in a manner also suitable for nonmajors. Students with
a basic college-level understanding of thermodynamics, calculus, and reaction kinet-
ics should be prepared to follow the presentation. By avoiding the more tedious
and sophisticated analytical solution methods and relying more on simplified model
equations and, where necessary, modern mathematical software packages, we strive
to present the philosophy and methodology of engineering analysis of mass and heat
transfer suitable for nonmajors as well. Note that a course in fluid mechanics is not
a prerequisite for understanding most of the material presented in this book.
Engineering starts with careful analysis of experiment, which naturally inspires
the inquiring mind to synthesis and design. Early emphasis on developing model
equations and studying their behavior enables the instructor to involve students in
problem-based learning exercises and transport-based design projects right from the
beginning of the course. This and the ability to challenge students to apply their
analysis skills and course knowledge to transport phenomena in the world around
them, especially in emerging technologies in the nanosciences and environmental and
biological sciences, result, in our experience, in an exciting and motivating classroom
environment. We sincerely hope that you as reader will find this approach to transport
phenomena to be as fresh and invigorating as we have.

Get the habit of analysis—analysis will in time enable synthesis to become your
habit of mind. — Frank Lloyd Wright
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To the Student

This text is designed to teach you how to carry out quantitative analysis of physical
phenomena important to chemical professionals. In the chemical engineering cur-
riculum, this course is typically taught in the junior year. Students with adequate
preparation in thermodynamics and reactor design should be successful at learning
the material in this book. Students lacking a reactor design course, such as chemists
and other professionals, will need to pay additional attention to the material in
Chapter 2 and may need to carry out additional preparation by using the references
contained in that chapter. This book uses the logic employed in the simple analysis
of reacting systems for reactor design to develop the more complex analysis of mass
and heat transfer systems.
Analysis is the process of developing a mathematical description (model) of a
physical situation of interest, determining behavior of the model, comparing the
behavior with data from experiment or other sources, and using the verified model
for various practical purposes.
There are two parts in the analysis process that deserve special attention:
r developing the mathematical model, and
r comparing model behavior with data.

Our experience with teaching analysis for many years has shown that the model
development step can be effectively taught by following well-developed logic. Just
what constitutes agreement between model behavior and data is a much more com-
plex matter and is part of the art of analysis. This is more difficult to learn and requires
one to consider many different issues; it always depends on the reasons for doing the
analysis. Time constraints have a significant impact on this decision, as do resources
available. We will illustrate this aspect of analysis by examining chemical reactors,
heat exchangers, and mass contactors, equipment of particular interest to chemical
professionals.
Determining model behavior requires you to remember some calculus—how to
solve algebraic equations and some simple differential equations. This step in anal-
ysis is often given too much emphasis because it is the easiest part of analysis to
do and is the step for which students have the best background. Do not fall into
the common trap of assuming that analysis is primarily concerned with determin-
ing model behavior—it is not! Analytical methods to solve algebraic or differential
equations are most useful if the manipulations leading to solution give insights into
xv
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xvi To the Student

the physical situation being examined. Tedious algebraic manipulations are not help-
ful and seriously distract one from the real purpose of analysis. You should stop and
ask questions of any instructor who performs a lot of algebra at the board without
constantly referring back to what the manipulations mean in terms of the physical
situation being studied. In this day and age, computer programs that solve sets of
equations are so readily available that tedious algebra is not required.
Once you have mastered how to obtain the model equations, you need to devote
your creative energies to deciding if behavior matches experiment. Just what consti-
tutes a match is not trivial to determine.
The model development step is simplified by considering the level of complexity
required to obtain useful practical results. We define six levels of complexity in this
text:

The first level employs only the laws of conservation of mass and/or energy.
Time is the only dependent variable in the differential equations considered
in Level I analysis, but many problems of considerable significance assume
steady state and eliminate time as a variable. In this case the model equations
become algebraic.
The second level also employs these two conservation laws, but, in addition,
phase, thermal, or chemical equilibrium is assumed. The model equations in
a Level II analysis are algebraic because time is not an independent variable
when equilibrium is assumed.
A Level III analysis requires a constitutive relationship to be employed. The six
constitutive relations needed in studying reactors, heat exchangers, and mass
contactors are shown in Tables 1.4 and 1.5. These relations have been verified
by various experiments that we will discuss in some detail. Level III analy-
sis assumes simple fluid motions, either well mixed or plug flow. Completely
stagnant fluids or solid phases can also be handled at this level of analysis.
A background in fluid mechanics is not required. A Level III analysis allows
one to complete equipment design at the laboratory, pilot, and commercial
scales for most single-phase systems. The Level III model equations for well-
mixed fluids contain time as the only independent variable if steady state is
not assumed. Plug-flow fluid motions require one independent spatial variable
in the steady state and time if the steady state cannot be assumed.
To deal effectively with multiphase systems, a Level IV analysis needs to be per-
formed. The Level IV analysis also assumes simple fluid motions but requires
application of the conservation laws of mass and energy coupled with consti-
tutive relations for both phases.
A Level V analysis is restricted to single-phase systems but can employ all the
conservation laws. It is the first level in which the law of conservation of
momentum is used. In its most complicated form, the model equations of
Level V can have time and all three spatial coordinates as independent vari-
ables. A Level V analysis considering time and only one spatial direction will
be sufficient for most problems we will analyze in this book.
Multiphase systems with complex fluid motion require a Level VI analysis, which
we will not consider in this text.
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To the Student xvii

There are two parts to this book. An introduction to the material and method
of approach is followed by chapters on chemical reactor analysis (Chapter 2), heat
exchanger analysis (Chapter 3), and mass contactor analysis (Chapter 4). These chap-
ters have been developed to highlight the similarities in the analysis methods and in
the process equipment used. By using experimentally determined values of the rate
constant (k), the heat transfer coefficient (U), the mass transfer coefficient (Km ), and
the interfacial area (a), you will be able to solve problems in mass and heat transfer
and develop operating and design criteria.
Part II features additional chapters that focus on the microscopic analysis of
control volumes to estimate U or Km for a broad range of systems. Correlations for
Km and U are developed that facilitate the design of equipment.
Chapter 7 provides methods for calculating the area for mass transfer in a variety
of mass contacting equipment. Chapter 8 illustrates the technically feasible design
procedure through case studies of common mass contactors and heat exchangers.
On successful completion of a course using this textbook, you should understand
the basic physical principles underlying mass and heat transfer and be able to apply
those principles to analyze existing equipment and design and analyze laboratory
experiments to obtain data and parameters.
Finally, you should be capable of performing technically feasible designs of mass
contactors and heat exchangers, as well as reading the technical literature so as to
continue your education and professional development in this field.
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xviii
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