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 MASS
TRANSFER
Principles and Applications
 MASS
TRANSFER
Principles and Applications

DIRAN BASMADJIAN

CRC PR E S S
Boca Raton London New York Washington, D.C.
This edition published in the Taylor & Francis e-Library, 2005.
“To purchase your own copy of this or any of Taylor & Francis or Routledge’s
collection of thousands of eBooks please go to www.eBookstore.tandf.co.uk.”

Library of Congress Cataloging-in-Publication Data

Basmadjian, Diran.
Mass transfer : principles and applications / Diran Basmadjian.
p. cm.
Includes bibliographical references and index.
ISBN 0-8493-2239-1
1. Mass transfer. I. Title

QC318.M3B37 2003
660′.28423--dc22 2003060755

This book contains information obtained from authentic and highly regarded sources. Reprinted material
is quoted with permission, and sources are indicated. A wide variety of references are listed. Reasonable
efforts have been made to publish reliable data and information, but the author and the publisher cannot
assume responsibility for the validity of all materials or for the consequences of their use.

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Library of Congress Card Number 2003060755
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ISBN 0-203-59042-2 (Adobe eReader Format)

Preface

The topic of mass transfer has a long and distinguished history dating to
the 19th century, which saw the development and early applications of the
theory of diffusion. Mass transfer operations such as distillation, drying, and
leaching have an even earlier origin, although their practice was at that time
an art rather than a science, and remained so well into the 20th century. Early
textbook publications of that era dealt mainly with the topic of diffusion and
the mathematics of diffusion.
The development of mass transfer theory based on the film concept, which
began in the 1920s and continued during two decades of intense activity,
brought about a shift in emphasis. The first tentative treatments of mass
transfer processes dealing primarily with distillation and gas absorption
began to appear, culminating with the publication, in 1952, of Robert Trey-
bal’s Mass Transfer Operations. It was to serve generations of students as the
definitive text on the subject.
The 1950s and the decades that followed saw a second shift in emphasis,
signaling a return to a more fundamental approach to the topic. Mass transfer
was now seen as part of the wider basin of transport phenomena, which
became the preferred topic of serious authors. The occasional text on mass
transfer during this period viewed the topic on a high plane and mainly
within the context of diffusion. For the most part, mass transport was seen
as one of three players on the field of transport phenomena, and often a
minor player at that. In the 1980s and 1990s, it became fashionable to treat
mass transfer as part of the dual theme of heat and mass transfer. In these
treatments, heat transfer, as the more mature discipline, predominated and
mass transfer was usually given short shrift, or relegated to a secondary role.
This need not be and ought not to be.
The author has felt for some time that mass transfer is a sufficiently mature
discipline, and sufficiently distinct from other transport processes, to merit
a separate treatment. The time is also ripe for a less stringent treatment of
the topic so that readers will approach it without a sense of awe.
In other words, we do not intend to include, except in a peripheral sense,
the more profound aspects of transport theory. The mainstays here are Fick’s
law of diffusion, film theory, and the concept of the equilibrium stage. These
have been, and continue to be, the preferred tools in everyday practice. What
we bring to these topics compared to past treatments is a much wider,
modern set of applications and a keener sense that students need to learn
how to simplify complex problems (often an art), to make engineering esti-
mates (an art as well as a science), and to avoid common pitfalls. Such
exercises, often dismissed for lacking academic rigor, are in fact a constant
necessity in the engineering world.
 Another departure from the norm is the organization of the material
according to mode of operation (staged or continuous contact), rather than the
type of separation process (e.g., distillation or extraction). Phase equilibria,
instead of being dispersed among different operations, are likewise brought
together in a single chapter. The reader will find that this approach unifies
and strengthens the treatment of these topics and enables us to accommo-
date, under the same umbrella, processes that share the same features but
are of a different origin (environmental, biological, etc.).
The readership at this level is broad. The topic of separation processes
taught at all engineering schools is inextricably linked to mass transport,
and students will benefit from an early introductory treatment of mass
transfer combined with the basic concepts of separation theory. There is, in
fact, an accelerating trend in this direction, which aims for students to
address later the more complex operations, such as multicomponent and
azeotropic distillation, chromatography, and the numerical procedures to
simulate these and other processes.
Mass transport also plays a major role in several other important disci-
plines. Environmental processes are dominated by the twin topics of mass
transfer and phase equilibria, and here again an early and separate intro-
duction to these subject areas can be immensely beneficial. This text provides
detailed treatments of both phase equilibria and compartmental models,
which are all-pervasive in the environmental sciences. Transport, where it
occurs, is almost always based on Fickian diffusion and film theory. The
same topics are also dominant in the biological sciences and in biomedical
engineering, and the text makes a conscious effort to draw on examples from
these disciplines and to highlight the idiosyncrasies of biological processes.
Further important applications of mass transport theory are seen in the
areas of materials science and materials processing. Here the dominant trans-
port mode is one of diffusion, which in contrast to other disciplines often
occurs in the solid phase. The reader will find numerous examples from
these fascinating fields as well as a considerable amount of preparatory
material of benefit to materials science students.
The text starts in an unconventional way by introducing the reader at
an early stage to diffusion rates and Fick’s law and to the related concepts
of film theory and mass transfer coefficients. This is done in Chapter 1, but
the topics are deemed of such importance that we return to them repeatedly
in Chapters 3 and 4, and again in Chapter 5. In this manner, we develop
the subject matter and our grasp of it in successive and complementary
stages. The intervening Chapter 2 is entirely devoted to the art of setting
up mass balances, a topic that is all too often given little attention. Without
a good grasp of this subject we cannot set about the task of modeling mass
transfer, and the many pitfalls we encounter here are alone sufficient reason
for a separate treatment. The balances include algebraic and ordinary dif-
ferential equations (ODEs). The setting up of partial differential equations
(PDEs) is also discussed, and some time is spent in examining the general
conservation equations in vector form. We do not attempt solutions of PDEs
but instead provide the reader with known solutions and solution charts,
which we use in Chapter 3 to solve a range of important problems. That
chapter also considers the simultaneous occurrence of mass transfer and
chemical reaction.
Chapter 6 deals with phase equilibria, which are mainly composed of
topics not generally covered in conventional thermodynamics courses. These
equilibria are used in Chapter 7 to analyze compartmental models and
staged processes. Included in this chapter is a unique treatment of percola-
tion processes, which should appeal to environmental and chemical engi-
neers. Chapter 8 takes up the topic of modeling continuous-contact
operations, among which the application to membrane processes is given
particular prominence. Finally, in Chapter 9 we conclude the text with a brief
survey of simultaneous mass and heat transfer.
The text is suitable for a third-year course addressed to engineering stu-
dents, particularly those in the chemical, civil, mechanical, environmental,
biomedical, and materials disciplines. Biomedical and environmental engi-
neers will find topics of interest in almost all chapters, while materials science
students may wish to concentrate on the earlier portions of the text (Chapters
1 to 5). The entire text can, with some modest omissions, be covered in a
single term. The professional with a first-time interest in the topic or a need
for a refresher will find this a useful and up-to-date text.
Acknowledgments

The author is much obliged to his colleague, Professor Olev Trass, who was
kind enough to make his course notes and problems available. Illustration
1.6, which deals with the analysis of hypothetical concentration profiles, was
drawn from this source.
We were, as usual, immensely aided by the devoted efforts of Arlene
Fillatre, who typed the manuscript, and Linda Staats, who produced impec-
cable drawings from rough sketches, which defy description. My wife, Janet,
and granddaughter, Sierra, provided an oasis away from work.
Author

Diran Basmadjian is a graduate of the Swiss Federal Institute of Technology,

Zurich, and received his M.A.Sc. and Ph.D. degrees in chemical engineering
from the University of Toronto. He was appointed assistant professor of
chemical engineering at the University of Ottawa in 1960, moving to the
University of Toronto in 1965, where he subsequently became professor of
chemical engineering.
He has combined his research interests in the separation sciences, biome-
dial engineering, and applied mathematics with a keen interest in the craft
of teaching. His current activities include writing, consulting, and perform-
ing science experiments for children at a local elementary school. Professor
Basmadjian has authored four books and some fifty scientific publications.
Notation

a specific surface area, m2/m3

A area, m2
A raffinate solvent, kg or kg/s
B extract solvent, kg or kg/s
C concentration, mol/m3
C number of components
Cp heat capacity at constant pressure, J/kg K or J/mol K
d diameter, m
D diffusivity, m2/s
D distillate, mol/s
D′ cumulative distillate, mol
De effective diffusivity, m2/s
erf error function
erfc complementary error function
E effectiveness factor, dimensionless
E extract, kg or kg/s
E extraction ratio, dimensionless
E stage efficiency, dimensionless
Ea activation energy, J/mol
Eh enhancement or enrichment factor, dimensionless
f fraction distilled
F degrees of freedom
F feed, kg or mol, kg/s or mol/s
F force, N
ℑ Faraday number, C/mol
G gas or vapor flow rate, kg/s or mol/s
Gs superficial carrier flow rate, kg/m2 s
h heat transfer coefficient, J/m2 s K
h height, m
H Henry’s constant, Pa m3 mol–1 or kg solvent/kg adsorbent
H enthalpy, J/kg or J/mol
Ha Hatta number, dimensionless
HETP(S) height equivalent to a theoretical plate or stage, m
HTU height of a transfer unit, m
i electrical current, A
Jw water flux, m3/m2 s
k thermal conductivity, J/m s K
kC, kG, kL, kx, ky, kY mass transfer coefficient, various units
ke elimination rate constant, s–1
kr reaction rate constant, s–1
K partition coefficient, various units
K permeability, m/s or m2
Ko overall mass transfer coefficient, various units
 length, m
L length, m
L liquid flow rate, kg/s or mol/s
L liquid mass, kg
Ls superficial solvent flow rate, kg/m2 s
m distribution coefficient, various units
m mass, kg
M mass of emissions, kg, kg/s, or kg/m2 s
M molar mass, dimensionless
N mass fraction (leaching), dimensionless
N molar flow rate, mol/s
N number of stages or plates
NT number of mass transfer units
NTU number of transfer units
p pressure, Pa
P number of phases
P o vapor pressure, Pa
PT total pressure, Pa
Pw water permeability, mol/m2 s Pa
pBM log-mean pressure difference, Pa
Pe Peclet number, dimensionless
q heat flow, J/s
q thermal quality of feed, dimensionless
Q volumetric flow rate, m3/s
r radial variable, m
r recovery, dimensionless
R gas constant, J/mol K
R radius, m
R raffinate, kg or kg/s
R reflux ratio, dimensionless
R residue factor, dimensionless
R resistance, Ω
RO reverse osmosis
S amount of solid, kg or kg/s
S shape factor, m
S solubility, cm3 STP/cm3 Pa
Sc Schmidt number, dimensionless
Sh Sherwood number, dimensionless
St Stanton number, dimensionless
t time, s
T dimensionless time (adsorption)
T temperature, K or °C
u dependent variable
u velocity, m/s
U overall heat transfer coefficient, J/m2 s K
v velocity, m/s
vH specific volume, m3/kg dry air
V voltage, V
V volume, m3 or m3/mol
W bottoms, mol or mol/s
W weight, kg
x liquid weight or mole fraction, dimensionless
x raffinate weight fraction, dimensionless
x solid-phase weight fraction (leaching), dimensionless
X adsorptive capacity, kg solute/kg solid
X liquid-phase mass ratio, dimensionless
y extract weight fraction, dimensionless
y vapor mole fraction, dimensionless
Y humidity, kg water/kg dry air
Y gas-phase mass ratio, dimensionless
z distance, m
zFH heat transfer film thickness, m
zFM mass transfer film thickness, m
Z dimensionless distance (adsorption)
Z flow rate ratio (dialysis)

Greek Symbols
α relative volatility, dimensionless
α selectivity, dimensionless
α separation factor, dimensionless
α thermal diffusivity, m2/s
γ activity coefficient, dimensionless
γ̇ shear rate, s–1
δ film or boundary layer thickness, m
ε porosity, dimensionless
λ mean free path, m
µ viscosity, Pa s
ν kinematic viscosity, m2/s
π osmotic pressure, Pa
ρ density, kg/m3
σ liquid film thickness, m
σ st length of stomatal pore, m
τ shear stress, Pa
τ tortuosity, dimensionless
φ pressure ratio, dimensionless

Subscripts
as adiabatic saturation
b bed, bulk
c cold, molar concentration units (kc)
C cross section, condenser
db dry bulb
D distillate, dialysate
e effective
f, F feed
g, G gas
h hot
i initial
i inside
i impeller
L liquid
m mean
o outside
OW octanol–water
p particle, pellet
p permeate
p pore
v vessel
w bottoms
w water

Superscripts
* equilibrium
o initial
o pure component
′ cumulative
Table of Contents

Chapter 1 Some Basic Notions: Rates of Mass Transfer .............. 1

1.1 Gradient-Driven Transport .........................................................................2
Illustration 1.1: Transport in Systems with Vanishing
Gradients .............................................................................6
Illustration 1.2: Diffusion through a Hollow Cylinder ..............8
Illustration 1.3: Underground Storage of Helium: Diffusion
through a Spherical Surface ...........................................10
1.2 Transport Driven by a Potential Difference: The Film Concept
and the Mass Transfer Coefficient ...........................................................12
1.3 Units of the Potential and of the Mass Transfer Coefficient ...............16
Illustration 1.4: Conversion of Mass Transfer Coefficients ...... 17
1.4 Equimolar Counterdiffusion and Diffusion through a Stagnant Film:
The Log-Mean Concentration Difference ................................................18
1.4.1 Equimolar Counterdiffusion .........................................................19
1.4.2 Diffusion through a Stagnant Film ..............................................20
Illustration 1.5: Estimation of Mass Transfer Coefficients
and Film Thickness. Transport in Blood Vessels .........22
1.5 The Two-Film Theory .................................................................................24
1.6 Overall Driving Forces and Mass Transfer Coefficients .......................27
Illustration 1.6: Qualitative Analysis of Concentration
Profiles and Mass Transfer ..............................................29
Illustration 1.7: Drying with an Air Blower:
A Fermi Problem .............................................................31
1.7 Conclusion ...................................................................................................33
Practice Problems ................................................................................................33

Chapter 2 Modeling Mass Transport: The Mass Balances ......... 39

2.1 The Compartment and the One-Dimensional Pipe ..............................40
Illustration 2.1: Evaporation of a Solute
to the Atmosphere ...........................................................42
Illustration 2.2: Reaeration of a River..........................................47
2.2 The Classification of Mass Balances ........................................................49
2.2.1 The Role of Balance Space ............................................................50
2.2.2 The Role of Time ............................................................................50
2.2.2.1 Unsteady Integral Balance .............................................50
2.2.2.2 Cumulative (Integral) Balance .......................................50
2.2.2.3 Unsteady Differential Balances .....................................51
 2.2.2.4 Dependent and Independent Variables .......................51
Illustration 2.3: The Countercurrent Gas Scrubber:
Genesis of Steady Integral and Differential Mass
Balances .............................................................................53
Illustration 2.4: Two Examples from Biology:
The Quasi-Steady-State Assumption ............................57
Illustration 2.5: Batch Distillation: An Example
of a Cumulative Balance................................................. 62
2.3 The Information Obtained from Model Solutions ................................64
2.4 Setting Up Partial Differential Equations ...............................................66
Illustration 2.6: Unsteady Diffusion in One Direction:
Fick’s Equation ................................................................. 67
Illustration 2.7: Laminar Flow and Diffusion in a Pipe:
The Graetz Problem for Mass Transfer ........................70
Illustration 2.8: A Metallurgical Problem: Microsegregation
in the Casting of Alloys and How to Avoid PDEs ....73
2.5 The General Conservation Equations .....................................................79
Illustration 2.9: Laplace’s Equation, Steady-State
Diffusion in Three-Dimensional Space:
Emissions from Embedded Sources .............................81
Illustration 2.10: Lifetime of Volatile Underground
Deposits .............................................................................84
Practice Problems..................................................................................................85

Chapter 3 Diffusion through Gases, Liquids, and Solids .......... 91

3.1 Diffusion Coefficients ................................................................................91
3.1.1 Diffusion in Gases ..........................................................................91
Illustration 3.1: Diffusivity of Cadmium Vapor in Air ............93
3.1.2 Diffusion in Liquids ......................................................................95
Illustration 3.2: Electrorefining of Metals. Concentration
Polarization and the Limiting Current Density .........98
3.1.3 Diffusion in Solids .......................................................................101
3.1.3.1 Diffusion of Gases through Polymers
and Metals ......................................................................102
Illustration 3.3: Uptake and Permeation of Atmospheric
Oxygen in PVC ..............................................................104
Illustration 3.4: Sievert’s Law: Hydrogen Leakage
through a Reactor Wall .................................................106
Illustration 3.5: The Design of Packaging Materials ..............108
3.1.3.2 Diffusion of Gases through Porous Solids ................ 110
Illustration 3.6: Transpiration of Water from Leaves.
Photosynthesis and Its Implications for Global
Warming .......................................................................... 112
Illustration 3.7: Diffusivity in a Catalyst Pellet ....................... 115
3.1.3.3 Diffusion of Solids in Solids ........................................ 116
 Illustration 3.8: Diffusivity of a Dopant in a Silicon
Chip .................................................................................. 117
Practice Problems .............................................................................................. 117

Chapter 4 More about Diffusion: Transient Diffusion and

Diffusion with Reaction ........................................................... 121
4.1 Transient Diffusion ...................................................................................122
4.1.1 Source Problems ...........................................................................123
4.1.1.1 Instantaneous Point Source Emitting into Infinite
Space ................................................................................123
4.1.1.2 Instantaneous Point Source on an Infinite Plane
Emitting into Half Space ..............................................125
4.1.1.3 Continuous Point Source Emitting into Infinite
Space ................................................................................127
Illustration 4.1: Concentration Response to an Instantaneous
Point Source: Release in the Environment and in a
Living Cell ......................................................................128
Illustration 4.2: Net Rate of Global Carbon Dioxide
Emissions ........................................................................129
Illustration 4.3: Finding a Solution in a Related Discipline:
The Effect of Wind on the Dispersion
of Emissions ....................................................................131
4.1.2 Nonsource Problems ...................................................................133
4.1.2.1 Diffusion into a Semi-Infinite Medium ......................133
Illustration 4.4: Penetration of a Solute into a Semi-Infinite
Domain ............................................................................134
Illustration 4.5: Cumulative Uptake by Diffusion for
the Semi-Infinite Domain .............................................135
4.1.2.2 Diffusion in Finite Geometries: The Plane Sheet,
the Cylinder, and the Sphere .......................................136
Illustration 4.6: Manufacture of Transformer Steel ................138
Illustration 4.7: Determination of Diffusivity in Animal
Tissue ...............................................................................139
Illustration 4.8: Extraction of Oil from Vegetable Seeds.........140
4.2 Diffusion and Reaction ............................................................................140
4.2.1 Reaction and Diffusion in a Catalyst Particle .........................141
4.2.2 Gas–Solid Reactions Accompanied by Diffusion:
Moving-Boundary Problems ......................................................142
4.2.3 Gas–Liquid Systems: Reaction and Diffusion in the Liquid
Film .................................................................................................143
Illustration 4.9: Reaction and Diffusion in a Catalyst Particle.
The Effectiveness Factor and the Design of Catalyst
Pellets ...............................................................................143
Illustration 4.10: A Moving Boundary Problem: The
Shrinking Core Model ..................................................148
 Illustration 4.11: First-Order Reaction with Diffusion in a
Liquid Film: Selection of a Reaction Solvent ............151
Practice Problems ..............................................................................................153

Chapter 5 A Survey of Mass Transfer Coefficients .................. 157

5.1 Dimensionless Groups .............................................................................158
Illustration 5.1: The Wall Sherwood Number .........................159
5.2 Mass Transfer Coefficients in Laminar Flow: Extraction from
the PDE Model ..........................................................................................160
5.2.1 Mass Transfer Coefficients in Laminar Tubular Flow ...........162
5.2.2 Mass Transfer Coefficients in Laminar Flow around Simple
Geometries ....................................................................................163
Illustration 5.2: Release of a Solute into Tubular Laminar
Flow: Transport in the Entry Region ..........................164
5.3 Mass Transfer in Turbulent Flow: Dimensional Analysis
and the Buckingham p Theorem ...........................................................166
5.3.1 Dimensional Analysis ..................................................................167
5.3.2 The Buckingham p Theorem ...................................................... 168
Illustration 5.3: Derivation of a Correlation for Turbulent
Flow Mass Transfer Coefficients Using Dimensional
Analysis ...........................................................................169
Illustration 5.4: Estimation of the Mass Transfer Coefficient
kY for the Drying of Plastic Sheets ..............................172
5.4 Mass Transfer Coefficients for Tower Packings ..................................173
Illustration 5.5: Prediction of the Volumetric Mass Transfer
Coefficient of a Packing ................................................177
5.5 Mass Transfer Coefficients in Agitated Vessels ...................................177
Illustration 5.6: Dissolution of Granular Solids in an
Agitated Vessel ...............................................................179
5.6 Mass Transfer Coefficients in the Environment: Uptake and Clearance
of Toxic Substances in Animals: The Bioconcentration Factor .........180
Illustration 5.7: Uptake and Depuration of Toxins:
Approach to Steady State and Clearance
Half-Lives ........................................................................183
Practice Problems ..............................................................................................185

Chapter 6 Phase Equilibria .......................................................... 189

6.1 Single-Component Systems: Vapor Pressure .......................................190
Illustration 6.1: Maximum Breathing Losses from a Storage
Tank ..................................................................................193
6.2 Multicomponent Systems: Distribution of a Single
Component ................................................................................................195
6.2.1 Gas–Liquid Equilibria .................................................................196
Illustration 6.2: Carbonation of a Soft Drink ...........................197
6.2.2 Liquid and Solid Solubilities ......................................................199
 Illustration 6.3: Discharge of Plant Effluent into a River ...... 200
6.2.3Fluid–Solid Equilibria: The Langmuir Isotherm ....................201
Illustration 6.4: Adsorption of Benzene from Water
in a Granular Carbon Bed ............................................205
Illustration 6.5: Adsorption of a Pollutant from
Groundwater onto Soil ................................................. 208
6.2.4 Liquid–Liquid Equilibria: The Triangular Phase
Diagram .........................................................................................209
Illustration 6.6: The Mixture or Lever Rule in the Triangular
Diagram ............................................................................213
6.2.5 Equilibria Involving a Supercritical Fluid ...............................215
Illustration 6.7: Decaffeination in a Single-Equilibrium
Stage .................................................................................218
6.2.6 Equilibria in Biology and the Environment: Partitioning
of a Solute between Compartments ..........................................220
Illustration 6.8: The Octanol–Water Partition Coefficient ......221
6.3 Multicomponent Equilibria: Distribution of Several
Components................................................................................................222
6.3.1 The Phase Rule .............................................................................222
Illustration 6.9: Application of the Phase Rule ......................222
6.3.2 Binary Vapor–Liquid Equilibria ................................................223
6.3.2.1 Phase Diagrams .............................................................224
6.3.2.2 Ideal Solutions and Raoult’s Law: Deviation from
Ideality .............................................................................226
6.3.2.3 Activity Coefficients ......................................................229
6.3.3 The Separation Factor a: Azeotropes........................................ 231
Illustration 6.10: The Effect of Total Pressure on a .................235
Illustration 6.11: Activity Coefficients from Solubilities ........236
Practice Problems ..............................................................................................238

Chapter 7 Staged Operations: The Equilibrium Stage ............. 243

7.1 Equilibrium Stages ...................................................................................245
7.1.1 Single-Stage Processes .................................................................245
Illustration 7.1: Single-Stage Adsorption: The Rectangular
Operating Diagram ........................................................248
Illustration 7.2: Single-Stage Liquid Extraction: The
Triangular Operating Diagram ....................................249
7.1.2 Single-Stage Differential Operation ..........................................251
Illustration 7.3: Differential Distillation: The Rayleigh
Equation ..........................................................................252
Illustration 7.4: Rayleigh’s Equation in the Environment:
Attenuation of Mercury Pollution in a Water
Basin .................................................................................254
7.1.3 Crosscurrent Cascades ................................................................257
 Illustration 7.5: Optimum Use of Adsorbent or Solvent in
Crosscurrent Cascades ..................................................260
Illustration 7.6: A Crosscurrent Extraction Cascade in
Triangular Coordinates .................................................263
7.1.4 Countercurrent Cascades ............................................................264
Illustration 7.7: Comparison of Various Stage Configurations:
The Kremser–Souders–Brown Equation ....................269
7.1.5 Fractional Distillation: The McCabe–Thiele Diagram ...........273
7.1.5.1 Mass and Energy Balances: Equimolar Overflow
and Vaporization ............................................................275
7.1.5.2 The McCabe–Thiele Diagram ......................................278
7.1.5.3 Minimum Reflux Ratio and Number of Plates..........282
Illustration 7.8: Design of a Distillation Column in the
McCabe-Thiele Diagram................................................285
Illustration 7.9: Isotope Distillation: The Fenske
Equation ..........................................................................288
Illustration 7.10: Batch-Column Distillation: Model
Equations and Some Simple Algebraic
Calculations ....................................................................290
7.1.6 Percolation Processes ...................................................................296
Illustration 7.11: Contamination and Clearance of Soils
and River Beds ...............................................................299
7.2 Stage Efficiencies....................................................................................... 299
7.2.1 Distillation and Absorption ........................................................301
7.2.2 Extraction .......................................................................................301
7.2.3 Adsorption and Ion-Exchange ...................................................301
Illustration 7.12: Stage Efficiencies of Liquid–Solid
Systems ............................................................................302
7.2.4 Percolation Processes ...................................................................304
Illustration 7.13: Efficiency of an Adsorption or
Ion-Exchange Column ..................................................305
Practice Problems ..............................................................................................306

Chapter 8 Continuous-Contact Operations ................................ 313

8.1 Packed-Column Operations ....................................................................314
Illustration 8.1: The Countercurrent Gas Scrubber
Revisited ..........................................................................314
Illustration 8.2: The Countercurrent Gas Scrubber Again:
Analysis of the Linear Case .........................................319
Illustration 8.3: Distillation in a Packed Column: The Case
of Constant a at Total Reflux ......................................322
Illustration 8.4: Coffee Decaffeination by Countercurrent
Supercritical Fluid Extraction ......................................324
8.2 Membrane Processes ................................................................................326
8.2.1 Membrane Structure, Configuration, and Applications .........327
 8.2.2Process Considerations and Calculations .................................333
Illustration 8.5: Brian’s Equation for Concentration
Polarization ......................................................................335
Illustration 8.6: A Simple Model of Reverse Osmosis ............ 336
Illustration 8.7: Modeling the Artificial Kidney: Analogy
to the External Heat Exchanger ...................................338
Illustration 8.8: Membrane Gas Separation: Selectivity a
and the Pressure Ratio f ...............................................342
Practice Problems ..............................................................................................345

Chapter 9 Simultaneous Heat and Mass Transfer .................... 349

9.1 The Air–Water System: Humidification and Dehumidification,
Evaporative Cooling ................................................................................350
9.1.1 The Wet-Bulb Temperature ........................................................350
9.1.2 The Adiabatic Saturation Temperature and the
Psychrometric Ratio .....................................................................352
Illustration 9.1: The Humidity Chart ........................................353
Illustration 9.2: Operation of a Water-Cooling Tower ............357
9.2 Drying Operations ....................................................................................361
Illustration 9.3: Debugging of a Vinyl Chloride Recovery
Unit ..................................................................................363
9.3 Heat Effects in a Catalyst Pellet: The Nonisothermal
Effectiveness Factor ..................................................................................365
Illustration 9.4: Design of a Gas Scrubber:
The Adiabatic Case ........................................................369
Practice Problems................................................................................................371

Selected References ...................................................................... 373

Appendix A1 The D-Operator Method ..................................... 379

Appendix A2 Hyperbolic Functions and ODEs ....................... 381

Subject Index .................................................................................. 383

1
Some Basic Notions: Rates of Mass Transfer

We begin our deliberations by introducing the reader to the basic rate laws
that govern the transport of mass. In choosing this topic as our starting point,
we follow the pattern established in previous treatments of the subject, but
depart from it in some important ways. We start, as do other texts, with an
introduction to Fick’s law of diffusion, but treat it as a component of a
broader class of processes, which is termed gradient-driven transport. This
category includes the laws governing transport by molecular motion, Fou-
rier’s law of conduction and Newton’s viscosity law, as well as Poiseuille’s
law for viscous flow through a cylindrical pipe and D’Arcy’s law for viscous
flow through a porous medium, both of which involve the bulk movement
of fluids. In other words, we use as common ground the form of the rate law,
rather than the underlying physics of the system. This treatment is a depar-
ture from the usual pedagogical norm and is designed to reinforce the notion
that transport of different types can be drawn together and viewed as driven
by a potential gradient (concentration, temperature, velocity, pressure),
which diminishes in the direction of flow.
The second departure is the early introduction of the reader to the notion
of a linear driving force, or potential difference as the agent responsible for
transport. One encounters here, for the first time, the notion of a transport
coefficient that is the proportionality constant of the rate law. Its inverse can
be viewed as the resistance to transport and in this it resembles Ohm’s law,
which states that current transport i is proportional to the voltage difference
DV and varies inversely with the Ohmian resistance R.
Associated with the transport coefficients is the concept of an effective film
thickness, which lumps the resistance to transport into a fictitious thin film
adjacent to a boundary or interface. Transport takes place through this film
driven by the linear driving force across it and impeded by a resistance that
is the inverse of the transport coefficient. The reader will note in these
discussions that a conscious effort is made to draw analogies between the
transport of mass and heat and to occasionally invoke as well the analogous
case of transport of electricity.
The chapter is, as are all the chapters, supplemented with worked exam-
ples, which prepare the ground for the practice problems given at the end
of the chapter.

1
2 Mass Transfer: Principles and Applications

1.1 Gradient-Driven Transport

The physical laws that govern the transport of mass, energy, and momentum,
as well as that of electricity, are based on the notion that the flow of these
entities is induced by a driving potential. This driving force can be expressed
in two ways. In the most general case, it is taken to be the gradient or derivative
of that potential in the direction of flow. A list of some rate laws based on
such gradients appears in Table 1.1. In the second, more specialized case,
the gradient is taken to be constant. The driving force then becomes simply
the difference in potential over the distance covered. This is taken up in Section
1.2, and a tabulation of some rate laws based on such potential differences
is given in Table 1.2.
Let us examine how these concepts can be applied in practice by taking
up a familiar example of a gradient-driven process, that of the conduction
of heat.
The general reader knows that heat flows from a high temperature T, which
is the driving potential here, to a lower temperature at some other location.
The greater the difference in temperature per unit distance, x, the larger the
transport of heat; i.e., we have a proportionality:

TABLE 1.1
Rate Laws Based on Gradients
Name Process Flux Gradient
1. Fick’s law Diffusion dC Concentration
N / A = -D
dx
2. Fourier’s law Conduction dT Temperature
q / A = -k
dx
3. Alternative d (rCpT ) Energy
formulation q / A = -a concentration
dx
4. Newton’s Molecular Velocity
dv
viscosity law momentum Fx / A = t qx = -m x
transport dy
5. Alternative
d (rvx ) Momentum
formulation Fx / A = t yx - n concentration
dy
6. Poiseuille’s law Viscous flow in Pressure
d 2 dp
a circular pipe q/A = vx = -
32m dx
7. D’Arcy’s law Viscous flow in K dp Pressure
a porous q / A = vx = -
medium m dx
Some Basic Notions: Rates of Mass Transfer 3

TABLE 1.2
Rate Laws Based on Linear Driving Forces
Process Flux or Flow Driving Force Resistance
1. Electrical current i = DV/R DV R
flow (Ohm’s law)
2. Convective mass N/A = kCDC DC 1/kC
transfer
3. Convective heat q/A = hDT DT 1/h
transfer
4. Flow of water due to NA/A = PwDp Dp 1/Pw
osmotic pressure p

DT
qµ- (1.1)
Dx

The minus sign is introduced to convert DT/Dx, which is negative quantity,

to a positive value of heat flow q. In the limit Dx Æ 0, the difference quotient
converts to the derivative dT/dx. Noting further that heat flow will be pro-
portional to the cross-sectional area normal to the direction of flow and
introducing the proportionality constant k, known as the thermal conduc-
tivity, we obtain

dT
Heat flow q( J / s) = - kA (1.2a)
dx

or equivalently

dT
Heat flux q / A( J / sm 2 ) = - k (1.2b)
dx

These two expressions, shown graphically in Figure 1.1b, are known as

Fourier’s law of heat conduction. It can be expressed in yet another alterna-
tive form, which is obtained by multiplying and dividing the right side by
the product of density r (kg/m3) and specific heat Cp (J/kg K). We then
obtain (Item 3 of Table 1.1)

d(rCp T )
q / A = -a (1.3)
dx

where a = k/rCp is termed the thermal diffusivity. We note that the term
rCpT in the derivative has the units of J/m3 and can thus be viewed as an
energy concentration.
The reason for introducing this alternative formulation is to establish a
link to the transport of mass (Item 1 of Table 1.1). Here the driving potential
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