Simultaneous Mass Transfer and Chemical Reactions in Engineering Science: Solution Methods and Chemical Engineering Applications Bertram K.C. Chan

Simultaneous Mass Transfer and
Chemical Reactions in Engineering

Science: Solution Methods and
Chemical Engineering Applications
Bertram K.C. Chan
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SIMULTANEOUS
MASS TRANSFER AND
CHEMICAL REACTIONS
IN ENGINEERING
SCIENCE
Solution Methods and
Chemical Engineering
Applications
BERTRAM K.C. CHAN

PhD (The University of Sydney, Australia)
PE (California, USA)
IEEE (Life Member)
Elsevier
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This book is dedicated to:
the glory of God,
my better half Marie Nashed Yacoub Chan, and
the fond memories of:
my physical science teacher Brother Vincent, B.Sc., at the De La Salle

College, Cronulla, Sydney, New South Wales, Australia, as well as
my professors in Chemical Engineering in Australia, including:
at the University of New South Wales:
Professor Geoffrey Harold Roper
and
Visiting Professor Thomas Hamilton Chilton, from the University of Delaware
and at the University of Sydney:

Professor Thomas Girvan Hunter
and
Professor Rudolf George Herman Prince
PREFACE
Among the unit operations in biomolecular, chemical, and

process engineering, the one item that has uniquely, funda-
mentally, and historically, belonged to the discipline of chemical
engineering is concerned with operations involving mass trans-
fer. The principal mass transfer operations, in alphabetical order,
include[*]:
• Adsorption and fixed-bed separations;
• Crystallization;
• Distillation;
• Drying of solids;
• Equilibrium-stage operations;
• Gas absorption;
• Humidification operations;
• Leaching and extraction;
• Membrane separation processes.
More often than not, such operations involve a combination
of both mass transfer and chemical reactions. Hence, analysis
and design of such unit operations should start with a basic
understanding of simultaneous mass transfer and chemical re-
actions. After about a century of the academic discipline of
chemical engineering, to bring into focus the theory and practice
of the study and research into chemical engineering, it is useful
to take an in-depth look at this important subject, supported by
all available modern computational tools to bring to bear a
cogent review of the discipline. Theoretical approaches to
simultaneous mass transfer and chemical reactions often begin
with mass balances of each of the interacting species at the
differential levels, often resulting in a set of simultaneous partial
differential equations: usually one equation for each partici-
pating species.
In this work, theoretical and mathematical analyses of these
systems of differential equations are undertaken, resulting in
existence and uniqueness theorems for such systems.
Upon assuming a given set of initial and/or boundary con-
ditions, with respect to each system of partial differential
x Preface
equations in both space and time, the system solution is then

reduced to solving the resultant set of partial differential equa-
tions, with radical but realistic assumptions of a set of initial and
boundary conditions with respect to space and time.
Solution methodologies, starting with numerical analyses,
and using various computer methodologies, including:
(1) Programming, in FORTRAN-IV, for digital computation,
(2) Curve fitting, with resultant graphical outputs, using the
open-sourced program R,
(3) Computation and curve fitting graphical outputs using the
programs written in some high-level language, such as
BASIC, etc.
are used to obtain useful parametric curves for equipment
design.
[*](i) McCabe, W. L., and Smith, J. (1956). “Unit Operations of
Chemical Engineering”, 1st Edition, The McGraw-Hill Com-
panies, Inc., Series in Chemical Engineering, McGraw-Hill Book
Company, New York.
(ii) McCabe, W. L., Smith, J. C., and Harriott, P. (2005). “Unit
Operations of Chemical Engineering”, 7th Edition, The McGraw-
Hill Companies, Inc., Series in Chemical Engineering, McGraw-
Hill Book Company, New York.
“Chemical Engineering Science”
A semiofficial recorded documentation of Chemical Engi-
neering Science may be represented by “Perry’s Chemical
Engineers’ Handbook,” published by McGraw-Hill Book Com-
pany, now on its way to the Nineth Edition, spanning over about
a century of the illustrious history of the profession. This latest
version, under the general editorship of Don W. Green and
Marylee Z. Southard, is scheduled to be published in 2019!
Preface xi
“Perry’s Chemical Engineers’ Handbook,” 9th Edition

xii Preface
“Perry’s Chemical Engineers’ Handbook”, 1st through 8th

Editions
This monogram focuses on one single aspect of the vast
literature of chemical engineering science, known as “simulta-
neous mass transfer and chemical reactions,” which is discussed
as a critical theoretical analysis of the subject. It is to be hoped
that it will enhance an important aspect of this subject.
Special Note:
Some introductory materials are taken from well-known en-
gineering literatures, which are thoroughly referenced as they
occur in the text.
Introduction to simultaneous
1
mass transfer and chemical
reactions in engineering
science
Chapter outline
1.1 GaseLiquid Reactions 2
1.1.1 Simultaneous biomolecular reactions and mass transfer 2
1.1.1.1 The biomedical environment 2
1.1.1.2 The industrial chemistry and chemical engineering environment 4
1.2 The modeling of gaseliquid reactions 10
1.2.1 Film theory of mass transfer 10
1.2.2 Surface renewal theory of mass transfer 12
1.2.3 Absorption into a quiescent liquid[*1] 15
1.2.3.1 Absorption accompanied by chemical reactions[*1] 16
1.2.3.2 Irreversible reactions[*1] 17
1.2.4 Absorption into agitated liquids [*4] 21
1.2.4.1 Further references 24
1.2.5 The mathematical theory of simultaneous mass transfer and
chemical reactions[*1] 26
1.2.5.1 Physical absorption 26
1.2.6 Chemical absorption 27
1.2.6.1 Preliminary remarks on simultaneous mass transfer (absorption)
with chemical reactions 27
1.2.6.2 Some solutions to the mathematical models of the theory of
simultaneous mass transfer and chemical reactions 28
1.2.6.3 Approximate closed form solutions** 29
1.2.7 Numerical solutions 37
1.3 Diffusive models of environmental transport 37
In many biochemical, biomedical, and chemical processes, in

both physiological systems and in the chemical industry,
including environmental sciences, mass transfer accompanied
Simultaneous Mass Transfer and Chemical Reactions in Engineering Science. https://doi.org/10.1016/B978-0-12-819192-7.00001-1

Copyright © 2020 Elsevier Inc. All rights reserved. 1
2 Chapter 1 Introduction to simultaneous mass transfer and chemical reactions
with reversible, complex biochemical or chemical reactions in

gaseliquid systems are frequently found. From the viewpoint of
biochemical and/or chemical purposes in design, the absorption
rates of the participating reactants should be accurately esti-
mated. The associated mass transfer rates may significantly affect
the process, such as the yield and selectivity. Much work had
been done in describing these processes analytically. These ap-
proaches will be used later in this work.
For example, the absorption of a gas is followed by a first-
order reversible reaction.
Thus, for all mass transfer models, including the penetration
and surface-renewal models, analytical solutions have been ob-
tained. For other models, limited work had been done, except
for special cases.
In this work, both analytical and numerical solutions are pre-
sented in some detail.
1.1 GaseLiquid Reactions

Reference:
[*1] Danckwerts, P. V. (1970). Gas Liquid Reactions, McGraw-Hill,
NY; van Elk, E. P. (2001). Gas-Liquid ReactionsdInfluence of
Liquid Bulk and Mass Transfer on Process Performance. http://
www.vanelk.nl/edwin/cv/thesis.pdf. It is well-known that many
biochemical and chemical processes involve mass transfer of
one or more species from the gas phase into the liquid phase. In
the liquid phase the species from the gas phase is converted by
one or more (possibly irreversible) biochemical or chemical reac-
tions with certain species present in the liquid phase.
Typical of such examples are the following.
1.1.1 Simultaneous biomolecular reactions and

mass transfer
1.1.1.1 The biomedical environment
In epidemiologic investigations, occurrences of simultaneous
biomolecular reactions and mass transfer are common in many
biomedical environments. Some typical examples are:
(1) Intestinal drug absorption involving bio-transporters and
metabolic reactions with enzymes[*2]: the absorption of
drugs via the oral route is a subject of on-going and serious in-
vestigations in the pharmaceutical industry since good bio-
availability implies that the drug is able to reach the systemic
circulation via the oral path. Oral absorption depends on both
Chapter 1 Introduction to simultaneous mass transfer and chemical reactions 3
the drug properties and the physiology of the gastrointestinal

tract, or patient properties, including drug dissolution, drug
interaction with the aqueous environment and membrane,
permeation across membrane, and irreversible removal by or-
gans such as the liver, intestines, and the lung.
(2) Oxygen transport via metal complexes[*2]: On average, an
adult at rest consumes 250 ml of pure oxygen per minute to
provide energy for all the tissues and organs of the body,
even when the body is at rest. During strenuous activities,
such as exercising, the oxygen needs increase dramatically.
The oxygen is transported in the blood from the lungs to the
tissues where it is consumed. However, only about 1.5% of
the oxygen transported in the blood is dissolved directly in
the blood plasma. Transporting the large amount of oxygen
required by the body, and allowing it to leave the blood
when it reaches the tissues that demand the most oxygen,
require a more sophisticated mechanism than simply dissolv-
ing the gas in the blood. To meet this challenge, the body is
equipped with a finely tuned transport system that centers
on the metal complex heme. The metal ions bind and then
release ligands in some processes, and oxidize and reduce in
other processes, making them ideal for use in biological sys-
tems. The most common metal used in the body is iron, which
plays a central role in almost all living cells. For example, iron
complexes are used in the transport of oxygen in the blood
and tissues. Metaleion complexes consist of a metal ion that
is bonded via "coordinate-covalent bonds” to a small number
of anions or neutral molecules called ligands. For example the
ammonia (NH3) ligand is a mono-dentate ligand; i.e., each
mono-dentate ligand in a metaleion complex possesses a sin-
gle electron-pair-donor atom and occupies only one site in
the coordination sphere of a metal ion. Some ligands have
two or more electron-pair-donor atoms that can simulta-
neously coordinate to a metal ion and occupy two or more co-
ordination sites; these ligands are called polydentate ligands.
They are also known as chelating (Greek for "claw") agents,
because they appear to grasp the metal ion between two or
more electron-pair-donor atoms. The coordination number
of a metal refers to the total number of occupied coordination
sites around the central metal ion (i.e., the total number of
metaleligand bonds in the complex). This process is another
important example of biomolecular reaction and transport.
(3) Carotenoid transport in the lipid transporters SR-BI,
NPC1L1, and ABCA1: The intestinal absorption of carotenoids
in vivo involves several crucial steps:
1) release from the food matrix in the lumen,

2) solubilization into mixed micelles,
3) uptake by intestinal mucosal cells,
4) incorporation into chylomicrons, and
5) secretion into the lymph.
Research has shown that:
A) EZ is an inhibitor of the intestinal absorption of caroten-
oids, an effect that decreased with increasing polarity of
the carotenoid molecule;
B) SR-BI is involved in intestinal carotenoid transport; and
C) EZ acts not only by interacting physically with cholesterol
transporters as previously suggested, but also by downre-
gulating the gene expression of three proteins involved in
cholesterol transport in the enterocyte, the transporters
SR-BI, NPC1L1, and ABCA1.
The intestinal transport of carotenoid is thus a facilitated pro-
cess resembling that of cholesterol; therefore, carotenoid trans-
port in intestinal cells may also involve more than one
transporter.
Hence, the study of biomolecular reaction and transport is an
area of importance in biomedical processes and their occur-
rences in epidemiologic investigations.
In this section, one applies the facilities available in the R envi-
ronment to solve problems that have arisen from these processes.
This study is being approached from two directions:
n Using the R environment as a support to numerical analyt-
ical schemes that may be developed to solve this class of
problems.
n Applying the R functions in the CRAN package ReacTran.[*1]
[*2] Chan, B. K. C., Biostatistics for Epidemiology and Public
Health Using R”, Springer Publishing Company, New York, NY,
2016. Supplemental Chapter: “Research-Level Applications of R’,
available at: www.springerpub.com/chan-biostatistics.
1.1.1.2 The industrial chemistry and chemical engineering

environment
Typical examples of industrial chemical and chemical engineer-
ing processes in which this phenomenon occurs include chlori-
nation, gas purification, hydrogenation, and oxidation
processes. To undertake the process and equipment design of
new reactors and the optimization of existing reactors, applicable
theoretical models for reactors are helpful and most likely
needed. In general, models of liquidegas contactors consist of
two main parts: the micro model and the macro model:
• The micro model describes the interphase mass transfer be-

tween the gas phase and the liquid phase, and the macro
model describes the mixing behavior in both phases.
Both parts of the overall model may be solved sequentially,

but solving micro and macro models simultaneously is preferred
because of optimization of computational time.
Gaseliquid mass transfer modeling has been well studied. The
Whitman Stagnant Film Model was first described in 1923 by
W.G. Whitman, and it was concluded that some phenomena of
gaseliquid mass transfer may be regarded as nearly incompletely
explained. Moreover, the Higbie Penetration Model has been
used as a basis for the development of some new reactor models.
The influence of the bulk liquid on the mass transfer process has
been studied in some detail. More attention has been paid to the
dynamical behavior and stability of gaseliquid reactors and the
influence of mass transfer limitations on the dynamics. Also,
some important differences between the results of the Higbie
Penetration Model and the Whitman Stagnant Film Model have
been found.
Analytical solution of micro models for mass transfer (accom-
panied by chemical reactions) is restricted to asymptotic cases in
which many simplifying assumptions had to be made (e.g., reac-
tion kinetics are simple and the rate of the reaction is either very
fast or very slow compared to the mass transfer). For all other sit-
uations numerical-computational techniques are required for
solving the coupled mass balances of the micro model.
In general, it seems that mostly numerical solution techniques
have been applied. Wherever possible, analytical solutions of
asymptotic cases have been used to check the validity of the nu-
merical solution method.
For example, by modifying one of the boundary conditions of
the Higbie Penetration Model it had been found that the mass
transfer may be affected by the presence of the bulk liquid. For
example, in a packed column, the liquid flows down the column
as a thin layer over the packings. It has been examined whether
or not the Penetration Model may be applied for these configura-
tions. Both physical absorption and absorption accompanied by
first- and second-order chemical reactions have been
investigated.
From model calculations, it is concluded that the original
Penetration Theory, by assuming the presence of a well-mixed
liquid bulk, may be applied also to systems where no liquid
bulk is present, provided that the liquid layer is sufficiently thick!
• For packed columns this means, in terms of the Sherwood

number, NSh ¼ 4, for both physical absorption and absorption
accompanied by a first-order reaction.
• In case of a second-order 1,1-reaction, a second criterion,
[NSh 4O(Db/Da)], has to be fulfilled.
• For very thin liquid layers [NSh < 4, or NSh < 4O(Db/Da)], the
original penetration model may give erroneous results,
depending on the exact physical and chemical parameters,
and a modified model is required.
Analytical solution of models for gaseliquid reactors is
restricted to a few asymptotic cases, while most numerical
models make use of the physically less realistic stagnant film
modeldthis is relatively simplistic and easy to apply using the
“Hinterland Model.” The Hinterland Model assumes the reaction
phase to consist of ONLY a stagnant film and a well-mixed bulk.
Inflow and outflow of species to and from the reactor proceeds
via the non-reaction phase or via the bulk of the reaction phase,
but never via the stagnant film. [“Hinterland” is a German word
meaning “the land behind” (a port, a city, .) in geographic usages!]
By modifying one of the boundary conditions of the Higbie
penetration model it illustrated how the mass transfer may be
affected by the presence of the liquid bulk. Thus, for example,
in a packed column the liquid flows as a thin layer over the struc-
tured or dumped packing. It has been examined whether or not
the penetration model can be applied for these situations. Both
physical absorption and absorption accompanied by first- and
second-order chemical reaction have been investigated.
From model calculations it is concluded that the original
penetration theory, which assumes the presence of a well-
mixed liquid bulk, may be applied also to systems where no liquid
bulk is present, provided that the liquid layer has sufficient
thickness.
For packed columns, this means, in terms of Sherwood num-
ber, Sh > 4 for both physical absorption and absorption accom-
panied by a first-order reaction. In case of a second-order
1,1-reaction a second criterion Sh 4 O(Db/Da) has to be ful-
filled. For very thin liquid layers, Sh < 4 or Sh < O(Db/Da), the
original penetration model may give erroneous results, depending
on the exact physical and chemical parameters, and the modified
model is required.
Most numerical models of gaseliquid reactors make use of the
physically less realistic stagnant film model because implementa-
tion of the stagnant film model is relatively easy using the Hinter-
land concept. The combination of a stagnant film model and
Hinterland concept may successfully predict many phenomena

of gaseliquid reactors.
The Higbie penetration model is however preferred as a micro
model because it is physically more realistic. Direct implementa-
tion of the Hinterland concept is not possible with the Higbie
penetration model. Nevertheless, numerical techniques have
been applied to develop a new model that implements the Higbie
penetration model for the phenomenon mass transfer accompa-
nied by chemical reaction in well-mixed two-phase reactors:
assuming a stagnant film.
A model was developed that simulates the dynamic behavior
of gaseliquid tank reactors by simultaneously solving the Higbie
penetration model for the phenomenon of mass transfer accom-
panied by chemical reaction and the dynamic gas and liquid
phase component balances. The model makes it possible to
implement an alternative for the well-known Hinterland concept,
which is usually used together with the stagnant film model. In
contrast to many other numerical and analytical models the pre-
sent model can be used for a wide range of conditions, the entire
range of Hatta numbers, (semi-)batch reactors, multiple complex
reactions and equilibrium reactions, components with different
diffusion coefficients, and also for systems with more than one
gas phase component. By comparing the model results with
analytical asymptotic solutions it was concluded that the model
predicts the dynamic behavior of the reactor satisfactorily. It
had been shown that under some circumstances substantial dif-
ferences exist between the exact numerical and existing approxi-
mate results. It is also known that, for some special cases,
differences can exist between the results obtained using the stag-
nant film model with Hinterland concept and implementation of
the Higbie penetration model.
[*3] van Elk, E.P., Borman, P.C., Kuipers, J.A.M., Versteeg, G.F.
Modeling of gaseliquid reactorsdimplementation of the pene-
tration model in dynamic modeling of gaseliquid processes
with the presence of a liquid bulk
Received 14 April 1999; received in revised form 8 November
1999; accepted 29 November 1999
Analytical solution of models for gaseliquid reactors is
restricted to a few asymptotic cases, while most numerical
models make use of the physically less realistic stagnant film
model. A model was developed that simulates the dynamic
behavior of gaseliquid tank reactors by simultaneously solving
the Higbie penetration model for the phenomenon of mass trans-
fer accompanied by chemical reaction and the dynamic gas and
liquid phase component balances. The model makes it possible
to implement an alternative for the well-known Hinterland

concept, which is usually used together with the stagnant film
model. In contrast to many other numerical and analytical
models, the present model may be used for a wide range of con-
ditions, the entire range of Hatta numbers, (semi-)batch reactors,
multiple complex reactions and equilibrium reactions, compo-
nents with different diffusion coefficients, and also for systems
with more than one gas phase component.
By comparing the model results with analytical asymptotic so-
lutions it was concluded that the model predicts the dynamic
behavior of the reactor satisfactorily. It has been shown that un-
der some circumstances substantial differences exist between the
exact numerical and existing approximate results. It is also known
that for some special cases, differences can exist between the re-
sults obtained using the stagnant film model with Hinterland
concept and the implementation of the Higbie penetration
model.
1.1.1.2.1 Conclusions
1. The penetration model is preferred for the phenomenon of
mass transfer accompanied by chemical reaction in well-
mixed two-phase reactors.
2. By comparing the model results with analytical asymptotic so-
lutions it is concluded that the model predicts the reactor satis-
factorily. It is shown that for many asymptotic cases the results
of this new model coincide with the results of the stagnant film
model with Hinterland concept.
3. For some special conditions, differences may exist between the
results obtained using the stagnant film model with Hinterland
concept and the implementation of the Higbie penetration
model.
4. An important result is that for 1,1-reactions the saturation of
the liquid phase with gas phase species does not approach
zero with increasing reaction rate (increasing Hatta number),
contrary to what is predicted by the film model with Hinter-
land concept. Another important deviation may be found at
the specific conditions of a so-called instantaneous reaction
in combination with the absence of chemical enhancement
of mass transfer.
5. Application of the penetration model does not provide any nu-
merical difficulties, while application of the stagnant film
model would lead to a discontinuity in the concentration
gradient.
6. Another disadvantage of the Hinterland concept is that it can

strictly only be applied to isothermal systems, whereas in the
systems investigated in this thesis the reaction enthalpy is an
important parameter that may significantly influence the phe-
nomena of gaseliquid mass transfer.
A rigorous model may be developed that simulates the dy-
namic behavior of stirred non-isothermal gaseliquid reactors
by simultaneously solving the Higbie penetration model for the
phenomenon mass transfer accompanied by chemical reaction
and the dynamic gas and liquid phase component and heat bal-
ances. This is achieved by coupling the ordinary differential equa-
tions of the macro model mass and heat balances to the partial
differential equations of the penetration model. This model is
not yet published!
Using the newly developed rigorous reactor model it is shown
that dynamic instability (limit cycles) can occur in gaseliquid re-
actors. The influence of mass transfer limitations on these limit
cycles has been studied and is has been found that mass transfer
limitations make the process more stable.
1.1.1.2.2 Summary
Although the rigorous model is believed to be a very accurate
model, it has the disadvantage that owing to the complex numer-
ical methods applied it is a rather time-consuming model. On
behalf of a more efficient prediction of the possible occurrence
of limit cycles, the reactor model was simplified. The simplified
model is suited for the prediction of limit cycles using a stability
analysis. A stability analysis is a very efficient method to predict
the dynamic behavior and stability of a system of ordinary differ-
ential equations by linearization of the governing non-linear
ODE’s in the neighborhood of the steady state and analyzing
the eigenvalues. This method is very powerful for attaining design
rules for stable operation of stirred gaseliquid reactors. The influ-
ence of mass transfer limitations on the limit cycles is predicted
very well using the simplified model, though small discrepancies
are found with the more accurate rigorous model.
The developed reactor models have been used to model the
dynamics of a new, to be developed, industrial hydro-
formylation reactor. At a certain design of the reactor, the model
predicts serious and undesired limit cycles. These conditions
have to be avoided by an appropriate reactor design. Hydro-
formylation reactions are often characterized by a negative reac-
tion order in carbon monoxide. Model calculations showed that
this may lead to interesting phenomena: at certain process
conditions, an improvement of the mass transfer (higher kla, for

example, owing to improved mixing) may give rise to a less stable
reactor, without increasing the conversion. This unusual phe-
nomenon is explained by the negative reaction order of carbon
monoxide. Apparently, the increasing hydrogen and carbon mon-
oxide concentrations cancel each other out and the overall reac-
tion rate remains unchanged. The increasing hydrogen and
carbon monoxide concentrations do however make the process
more sensitive for the occurrence of limit cycles. Finally, a start
has been made with studying the influence of macro-mixing on
the dynamical behavior of gaseliquid reactors. For this purpose
a cascade of two reactors in series is compared to a single reactor.
Initial results indicate that a cascade of reactors in series provides
a dynamically more stable design. The total required cooling sur-
face to prevent the occurrence of temperatureeconcentration
limit cycles decreases significantly with an increasing number of
reactors in series. The first reactor in the cascade is the one with
the highest risk of dynamic instability.
1.2 The modeling of gaseliquid reactions

This process has evolved through a number of theoretical pro-
cesses, including the following.
1.2.1 Film theory of mass transfer

In typical industrial absorption processes, one should consider
the absorption of gases into liquids which are agitated such
that the dissolved gas is transported from the surface to the inte-
rior by convective motions. The agitation may occur in various
ways, including:
(i) The gas, or vapor, may be blown through the liquid as a
stream of bubblesdas, for example, on a perforated plate or
in a sparged vessel.
(ii) The liquid may be running in a layer over an incline or ver-
tical surface, and the flow may be turbulent (as, for example,
in a wetted-wall cylindrical column operating at a sufficiently
high Reynolds number), or ripples may develop and enhance
the absorption rate by convective motion. Discontinuities on
the surface may cause periodic mixing of the liquid in the
course of its flow, or strings of discs or of spheres.
(iii) The liquid may be advantageously agitated by a mechanical
stirrer, which may also entrain bubbles of gases into the
liquid.
(iv) The liquid may be sprayed through the gas as jets or drops.
First, consider a steady-state situation in which the composi-
tion of the liquid and gas, averaged over a specified region
and also with respect to any temporal fluctuations, are statis-
tically constant. For example, one may consider an agitated
vessel through which liquid and gas flow steadily, both being
so thoroughly mixed that their time-average compositions
are the same at all points; or one may consider a short vertical
section of a packed column (or sphere or disc or wetted-wall
column) operating at steady state, such that the average com-
positions of the liquid and gas in the element remain constant
with time. Clearly the situation is a complicated one: the con-
centrations of the various species are not uniform or constant
when measured over short length and time scales. Diffusion,
convection, and reaction proceed simultaneously. The na-
tures of the convective movements of liquid and gas are diffi-
cult to define: any attempt to describe them completely
would encounter considerable complications. Thus, to
obtain useful predictions about the behavior of such systems
for practical purposes, it is necessary to use simplified models
which simulate the situation sufficiently well, without intro-
ducing a large number of unknown parameters. This
approach may take a number of simplifying steps, as follows:
(A) Physical absorption[*1]. Consider first physical absorp-
tion, in which the gas dissolves in the liquid without any
reaction; it is found experimentally that the rate of ab-
sorption of the gas is given by

Ra ¼ kL a A A0 (1.I)
in which A* is the concentration of dissolved gas at the interface

between gas and liquid, assuming this partial pressure to be uni-
form throughout the element of space under discussion. The area
of interface between the gas and liquid, per unit volume of the sys-
tem, is a and kL is the “physical mass-transfer coefficient.” R is the
average rate of transfer of gas per unit area; the actual rate of
transfer may vary from point to point, and from time to time. A0
is the average concentration of dissolved gas in the bulk of the
liquid.
It is usually not possible to determine kL and a separately, by
measurements of physical absorption. For example, in a packed
column, the fraction of the surface of packings which is effectively
wetted is unknown, and in a system containing bubbles, the
interfacial area is not generally known! Thus the quantity directly

measurable by physical absorption measurements is the com-
bined quantity kLa.
Hence, the validity of Eq. (1.I) has been established in
numerous experimental studies, and an expression of this form
would be predicted from first principles, provided that certain
conditions are met. The chief of these are that the temperature
and diffusivity at the surface (where the concentration is A*)
should be very different from those in the bulk of the liquid;
and that no chemical reaction occurs, so that all molecules of dis-
solved gas are in the same condition. It is sometimes difficult to
decide whether a solute reacts chemically with a liquid or merely
interacts with it physically. For the present purpose, “physical” so-
lution means that its molecules are indistinguishable.
1.2.2 Surface renewal theory of mass transfer

Models evolved under this theory take as their basis the replace-
ment at time intervals of liquid at the surface by liquid from the
interior which has the local mean bulk composition. While the
liquid element is at the surface and is exposed to the gas, it ab-
sorbs gas as though it were infinitely deep and quiescent: the
rate of absorption, R, is then a function of the exposure time of
the liquid element and will be described by a suitable expression
such as those to be described by the reaction kinetics of the sys-
tem. In general, the rate of absorption is fast or infinite initially,
decreasing with time. The replacement of liquid at the surface
by fresh liquid of the bulk composition may be due to the turbu-
lent motion of the body of the liquid. Moreover, when liquid runs
over the surface of a packing, it may be in a state of undisturbed
laminar flow at the top of each piece of packing, except at the dis-
continuities between pieces of packing, where it may mix thor-
oughly: at the top of each piece of packing a fresh surface would
then be developed and moved discontinuity, when it would
then be replaced again by fresh liquid.
With this scenario, the surface-renewal models propose that
the surface of an agitated liquid, or a liquid flowing over a pack-
ing, is a collection of elements which have been exposed to the
gas for different durations of time, and which may well be, in gen-
eral, absorbing at different specific rates. Thus, different versions
of the model will lead to different specific rates. Moreover,
different versions of the model will lead to different distributions
of surface ages about the mean value.
The form of the surface-renewal model first proposed by Hig-

bie, in 1935, assumed that every element of the surface is exposed
to the gas for the same duration of time, q, before being replaced
by liquid of the bulk composition. During this time, the element of
liquid absorbs the same amount Q of gas per unit area as though it
were infinitely deep and stagnant. The average rate of absorption
is therefore Q/q, and this is also the rate of absorption R per unit
area averaged over the interface in a representative region of a
steady-state absorption system in which the bulk composition is
statistically uniformde.g., in a small, but representative, volume
element of a packed column.
The exposure-time q may be determined by the hydrodynamic
properties of the system, and is the only parameter required to ac-
count for their effect on the transfer coefficient kL. The relation be-
tween q and kL is derived belowdin physical absorption.
Under such circumstances, the variation in time and space of
the concentration a of dissolved gas in the liquid in the absence
of a reaction is governed by the diffusion equation:
DA v2 a=vx2 ¼ va=vt (1.II)
And the rate of transfer of dissolved gas, initial concentration of

the passage of gas across the interface, then the concentration
of the surface might vary with time. For the present, it is assumed
that the diffusion of dissolved gas into the latter. This assumption
generally holds when the solubility of the gas is not very great, so
that A* represents a mole fraction much less than unity.
It would not be true, for example, if ammonia at atmospheric
pressure were diffusing into pure water (in which there will be a
substantial temperature rise). Under these conditions, the varia-
tion in time and space of the concentration, a, of dissolved gas in
the liquid in the absence of a reaction is governed by the diffusion
from bubbles or absorption by wetted-wall columns, the mass
transfer surface is formed instantaneously and transient diffusion
of the material takes place.
Assuming that a bubble is rising in a pool of liquid (where the
liquid elements are swept on its surface) and remains in contact
with it during their motion and finally detached at the bottom.
The basic assumptions of the penetration theory are:
• Unsteady state mass transfer occurring to a liquid element as
long as it is in contact with the gas bubbles
• Equilibrium existing at the gaseliquid interface
• Each liquid element staying in contact with the gas for the
same period of time. (The liquid elements are moving at the
Figure 1.1 Schematic of the penetration model.
same rate, and there is not a velocity gradient within the

liquid.)
Under these assumptions, the convective terms in the diffu-
sion may be neglected and the unsteady-state mass transfer of
gas (penetration) into the liquid element may be written from
Fick’s second law for unsteady-state diffusion as (Fig. 1.1)

vc=vt ¼ DAB v2 c = vz2 (1.1)
and the boundary conditions are:

t ¼ 0; z > 0: c ¼ cAb
and
t > 0; z ¼ 0: c ¼ cAi
where
cAb / The concentration of solute A at an infinite distance
from the surface (viz., the bulk concentration)
cAi/ The interfacial concentration of solute A at the surface.
On solving the above partial differential equation, one obtains:
ðcAi cÞ=ðcAi cAb Þ ¼ erf½z = f2OðDAB tÞg (1.2)
If the process of mass transfer is a unidirectional diffusion and
the surface concentration is very low: i.e., cAb z 0; then the mass
flux of solute A, given by NA (kgm2 s1) may be estimated by the
following equation:
NA ¼ ½f rDAB =ð1 cAb Þgðvc=vzÞz¼0
z rðvc=vzÞz¼0 (1.3)
From the above two expressions, the rate of mass transfer at

time t is given by the following equation:
NA ðtÞ ¼ ½OðDAB =ptÞðcAi cAb Þ (1.4)
And the mass transfer coefficient is given by

kL ðtÞ ¼ OðDAB =ptÞ (1.5)
Moreover, the average mass transfer coefficient during a time
interval tc(t) may be obtained by integrating Eq. (1.2) as
Z tc
kL;av ¼ ð1=tc Þ kðtÞdt ¼ 2OðDAB =ptc Þ (1.6)
0
Thus, from the above equation, the mass transfer coefficient is

proportional to the square root of the diffusivity. This was first
proposed by R. Higbie in 1935 and the theory is called the Higbie
Penetration Theory.
1.2.3 Absorption into a quiescent liquid[*1]

First, consider the case in which no chemical reaction occurs be-
tween the dissolved gas and the liquid. The surface of the liquid
first contacts the gas at time t ¼ 0, and it may be assumed that,
from that instance onward, the concentration in the plane of
the surface is uniformly equal to A*dthis concentration corre-
sponds to the solubility of the gas at the prevailing partial pressure
above the surface of the liquiddand is assumed to be constant. If
this gas were mixed with another gas of different solubility, or if
there were a resistance to the passage of gas across the interface,
then the concentration at the surface may vary with time.
Further, it is assumed that the diffusion of dissolved gas into
the liquid does not appreciably affect the temperature, or other
physical properties of the latter. This is likely to be true only
when the solubility of the gas is not very great, so that A* repre-
sents a mole fraction much less than unity.
Under these special circumstances, the variation in time and
space of the concentration a of dissolved gas in the liquid in the
absence of reaction is governed by the diffusion equation:
DA v2 a=vx2 ¼ va=vt (1.7)
and the rate of transfer of dissolved gas across unit area, Rx of any
plane parallel to the surface is
Rx ¼ DA va=vx (1.8)
Here, x is the distance measured from the surface, where x ¼ 0,

and DA is the diffusivity or diffusion coefficient of the dissolved
gas. Hence, the rate of absorption of gas at any time is
R ¼ DA ðva=vxÞx¼0 (1.9)
The term (va/vx)x¼0 is the concentration gradient at the sur-
face and is a function of time.
Let the initial concentration of A be uniformly equal to A0, and
its concentration remote from the surface remains A0. Then the
solution of Eq. (1.7) with boundary conditions:
9
a ¼ A ; x ¼ 0; t > 0 > =
a ¼ A0 ; x > 0; t ¼ 0 (1.10)
>
;
a ¼ A ; x ¼ N; t > 0
0

is aeA0 ¼ A A0 erfcfx =2OðDA tÞg

¼ A A0 ½1 erffx = 2OðDA tÞg (1.11)
Giving the distribution of concentration in the case where the
initial concentration is A0, and the function
erfcfx = 2OðDA tÞg ¼ ½1 erffx = 2OðDA tÞg (1.12)
is the error function of x/2O(DAt), and is defined by

Z x=2OðDA tÞ

erffx=2OðDA tÞg ¼ ð2 =OpÞ exp z 2 dz (1.13)
0
Values of the error function may be found in standard math-

ematical tables, etc.
From Eqs. (1.9) and (1.11), it follows that

R ¼ A A0 OðDA =ptÞ (1.14)
Thus, the rate of absorption is infinite when the gas and liquid
are first in contact, decreasing with time, and the amount Q
absorbed by a unit area of surface, in time t, is given by
Z t
Q ¼ Rdt
0 (1.15)

¼ 2 A A OðDA t=pÞ
0
1.2.3.1 Absorption accompanied by chemical reactions[*1]

If the dissolved gas reacts with the liquid, or with a substance dis-
solved in the liquid, then Eq. (1.7) should be replaced by
DA v2 a=vx2 ¼ va=vt þ rðx; tÞ (1.16)
in which r(x, t) is the rate per unit volume of liquid at which the
reaction is using up the solute gas at time t and at a distance x
below the surface. This rate will depend on the local concentra-
tion of the gas, and of any other solute with which it reacts. For
some cases, numerical and/or analytical solutions of the
diffusion-reaction equations are available.
It is assumed throughout that the temperature, and the values
such as physico-chemical quantities, diffusivities, reaction-rate
constants, and solubilities remain constant and uniform. More-
over, enhancement factors E may be computed ,which is the ra-
tios of the amount which would be absorbed if there were no
reaction, viz., 2(A* e A0) O(DAt/p).
1.2.3.2 Irreversible reactions[*1]

1.2.3.2.1 First-order reactions
Here
r ¼ k1 a (1.17)
in which k1 is the first-order rate constant for the reaction. The
rate of reaction of dissolved gas at any point is directly proportional
to its concentration. Under these circumstances, the solution to Eq.
(1.16), with boundary conditions (10), and with A0 ¼ 0, is [*]
[*] Danckwerts, P. V. (1950). Transactions of the Faraday Soci-
ety, 46:300
a=A ¼ 1 2 expf xOðk1 =DA Þgerfc ½x=f2OðDA tÞgeOðk1 tÞ
=
þ1 2 expfxOðk1 =DA Þgerfc½x=f2OðDA tÞg þ Oðk1 tÞ

=
(1.18)
so that
R ¼ AOðDA k1 Þ½erfOðk1tÞ þ expðk1 tÞ =Oðpk1 tÞ (1.19)
and

Q ¼ AOðDA =k1 Þ k1 t þ 1 2 erfOðk1 tÞ þ Oðk1 t=pÞexpðk1 t (1.20)
=
Thus, when k1t is large, the distributions of concentration and

absorption rate tend to limiting values and no longer change with
time:
for k1t >> 1.
a = A ¼ expf xOðk1 = DA Þ (1.21)
R ¼ A OðDA k1 Þ (1.22)
and
Q ¼ A OðDA k1 Þft þ ð1 = 2k1 Þg (1.23)
The error in Eq. (1.23) is less than 3% when k1t > 2.
When k1t is large,
Q ¼ tA OðDA k1 Þ (1.24)
to within 5% when k1t > 10.
For short times of exposures, for k1t << 1
R z A OfðDA = ptÞð1 þ k1 tÞ (1.25)
Q z 2A OfðDA t = pÞð1 þ k1 t = 3Þ (1.26)
to within 5% when k1t < 0.5.

The above equations form the basis of methods for measuring
k1 and A*ODA.
In practice, truly first-order irreversible reactions are seldom
found. However, when the solute gas undergoes a reaction with
a dissolved reactant, which is first-order with respect to the con-
centration of the dissolved gas, then, under certain circum-
stances, the concentration of the reactant may be uniform and
the reaction rate of the dissolved w order and the above equa-
tions do apply.
If the product of an irreversible first-order gas reaction has the
same diffusivity as the dissolved gas, then its concentration P* at
the surface is given by Danckwerts (1967)*:
ðP = yA Þ þ 1 ¼ expðk1 t = 2Þ½ð1 þ k1 tÞI0 ðk1 t = 2Þ þ k1 tI1 ðk1 t = 2Þ
¼ VA (1.27)
where y moles of product arise from the reaction of one mole of

dissolved gas.
1.2.3.2.2 Instantaneous reactions

In this case, the dissolved gas reacts instantaneously with a dis-
solved reactant. There is a plane underneath the surface where
the concentration of both is zero, and the rate at which the two
substances can diffuse to the reaction plane. The actual kinetics
of the reaction are immaterial. The initial concentration of the
reactant is uniformly B0, and z moles of it react with each mole
of dissolved gas.
The solution of the equations governing this case (and similar

phenomena involving a moving boundary) has been given by
Danckwerts (1950) [*4]:
[*4] Danckwerts, P. V. (1950). Transactions of the Faraday So-
ciety, 46:712
a=A ¼ ferfc½x = 2OðDA tÞ erfcðb = ODA Þg=erfðb = ODA Þ; 0
< x < 2bOt (1.28)
a=A ¼ 0; x > 2bOt (1.29)
b=B0 ¼ ferf½x = 2OðDB teerfðb = ODB Þg=erfcðb = ODB Þ; x > 2bOt

(1.30)
b=B0 ¼ 0; 0 < x < 2bOt (1.31)
R ¼ fA = erfðb =ODA ÞgOðDA = pÞ ¼ Et A OðDA = pÞ (1.32)
Q ¼ f2A = erfðb =ODA ÞgOðDA t = pÞ ¼ 2Et A OðDA t = pÞ (1.33)
where
Ei ¼ 1=erfðb = ODA Þ (1.34)
and b is defined by:

0

2 =ODB Þ ¼ B = zA OðDB = DA Þ
exp b2 = DB erfcðb
exp b = DA erf ðb =ODA Þ (1.35)
0
Thus, the factor Ei is a function of DB/DA and B /zA*. Here a, b
are the local concentrations of dissolved gas and reactant, respec-
tively, and DA, DB are their diffusivities. The reaction plane is at a
depth of 2bOt beneath the surface. The quantity Ei is the factor by
which the reaction increases the amount absorbed in a given
time, as compared to absorption without reaction.
The concentration p of the product (assuming y moles to be
formed from each mole of reacting gas) is:

¼ yA OðDA = DP Þ erfcðb
p ODp Þexp b2 = DA
=
= erfcðb = ODA Þexp b2 = DP ; 0 < x < 2bOt (1.36)

p¼yA OðDA = DP Þ erfcðx p Þexp b = DA
= 2OD 2
= erfcðb =ODA Þexp b = DP

2
; x > 2bOt (1.37)
where DP is the diffusivity of the product.

When the diffusivities are equal:
p ¼ yB0 =z; 0 < x < 2bOt (1.38)
If, in addition, one mole of reactant reacts with one mole of
gas to produce one mole of product, then y ¼ z ¼ 1, and the
Another random document with
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President in the Philippines sufficed fully, it was contended,
for every purpose of temporary or provisional government
there, except in its lack of ability to grant franchises and
to dispose of the public lands. Hence it was freely charged
that the controlling influences which pressed this measure on
the government came from capitalists and speculators who were
reaching after valuable franchises, mining rights and land
grants in the archipelago. Said Senator Daniel in the debate:
"So far as any legislation which looks forward to the opening
of the way to civil government may be involved to the
softening of the conditions which exist, to the amelioration
of the distresses which are upon the Philippine people, I
would give most cheerful acquiescence. But because we desire
to do these things in a good spirit, in a resolute and
patriotic spirit, let us not permit the provocation of
difficult conditions to lead us into enacting any kind of
provision of law that is not necessary to these ends. Let us
not undertake to give to the President of the United States
any power of disposing of the permanent assets of the
Philippine people; let us not put him in the attitude of being
a franchise giver or a franchise seller or a franchise lessor.
The franchises of those islands—their rivers, their ferries,
their streets, their roads, the thousand and one privileges
which are granted by public authority—are as important and as
valuable to that people and as permanently associated with
their happiness and their prosperity as are their fields or
their mines or their fisheries or anything else which belongs
to their country. … It is true there is the reservation of the
right to alter, amend, or repeal, but while that is legally
broad enough for any remedial legislation whatsoever to
follow, we know that practically it is of very small
consequence. If capital goes in and invests itself in
improvements which are in themselves of a permanent nature, if
railroads are constructed, telegraph lines run, telephones
established, ferries built, steamers and boats, gas
establishments, electrical establishments—if those things are
disposed of, the man who once gets in will never be gotten
out. In all such affairs possession is nine points of the law
before they get into court, where it is generally made the
tenth."
Senator Hoar called attention "to the fact that the report of
the Taft commission urges that power be given to sell the
public lands at once, as it is necessary for their
development, and a large amount of capital is there now
clamoring to be invested," and he remarked: "So I suppose that
one of the chief purposes of this is that the public lands in
the Philippine Islands may be sold before the people of the
islands have any chance whatever to have a voice in their
sale." He then quoted the following passages from the report
of the Taft commission:
"The commission has received a sufficient number of

applications for the purchase of public land to know that
large amounts of American capital are only awaiting the
opportunity to invest in the rich agricultural field which may
here be developed. In view of the decision that the military
government has no power to part with the public land belonging
to the United States, and that the power rests alone in
Congress, it becomes very essential, to assist the development
of these islands and their prosperity, that Congressional
authority be vested in the government of the islands to adopt
a proper public-land system, and to sell the land upon proper
terms. There should, of course, be restrictions preventing the
acquisition of too large quantities by any individual or
corporation, but those restrictions should only be imposed
after giving due weight to the circumstances that capital can
not be secured for the development of the islands unless the
investment may be sufficiently great to justify the
expenditure of large amounts for expensive machinery and
equipments.
{401}
Especially is this true in the cultivation of sugar land. …
Restricted powers of a military government referred to in
discussing the public lands are also painfully apparent in
respect to mining claims and the organization of railroad,
banking, and other corporations, and the granting of
franchises generally. It is necessary that there be some body
or officer vested with legislative authority to pass laws
which shall afford opportunity to capital to make investment
here. This is the true and most lasting method of
pacification." "In other words," said Senator Hoar, "the
leading, principal, bald proposal on which this amendment
rests is that before those 10,000,000 people are allowed any
share in their own government whatever their property is to be
sold by Americans to Americans in large quantities, as on the
whole the best means of pacification—that the best way to
pacify a man is to have one foreign authority to sell his
property and another to buy it." An amendment to the
amendment, offered by Senator Bacon, reserving to Congress the
right to annul any grant or concession made, or any law
enacted, by any governmental authority created under the
powers proposed to be conferred on the President; another
offered, by Senator Vest, providing that "no judgment, order,
nor act by any of said officials so appointed shall conflict
with the Constitution and laws of the United States," and
still others of somewhat kindred aims, were voted down; but
the influence of Senator Hoar prevailed with the Senate so far
as to induce its acceptance of the following important
modification of the so-called "Spooner Amendment":
"Provided, That no sale or lease or other disposition of the

public land, or the timber thereon, or the mining rights
therein, shall be made: And provided further, That no
franchise shall be granted which is not approved by the
President of the United States, and is not, in his judgment,
clearly necessary for the immediate government of the islands
and indispensable for the interests of the people thereof, and
which can not, without great public mischief, be postponed
until the establishment of a permanent civil government, and
all such franchises shall terminate one year after the
establishment of such civil government."
With this proviso added, the "Spooner amendment" was adopted

by the Senate on the 26th of February (yeas 45, nays 27, not
voting 16), and agreed to by the House on the 1st of March
(yeas 161, nays 136, not voting 56).
Congressional Record,
February 25-March 1, 1901.
PHILIPPINE ISLANDS: A. D. 1901 (March).

Organization of provincial governments.
Establishment of a department of public education.
Proposed tariff.
Date fixed for cessation of military regime.
On the 3d of March, the President of the Philippine

Commission, Judge Taft, addressed a cable despatch to the U.
S. Secretary of War in which he reported: "Commission has last
three weeks organized five provincial governments—Pampanga,
Pangasinan, Tarlac, Bulacan, Bataan—last two are Tagalog
provinces. Attended each provincial capital in a body; met by
appointment Presidentes, Councillors, and principal men of
towns; explained provisions general provincial act and special
bill for particular province and invited discussion natives
present of both bills. Conventions thus held very
satisfactory; amendments suggested, considered, special bills
enacted, appointments followed. … In three large provinces
natives appointed provisional Governors. In Bataan, on
petition, eight out of nine towns, volunteer officer
appointed. In Tarlac feeling between loyal factions required
appointment American. … In compliance with urgent native
invitations leave March 11 for south to organize provinces
Tayabas, Romblon, Iloilo, Capiz, Zamboanga, such others are
ready. Returning shall organize Zambales, Union, Cagayan,
Ilocos Norte. Military Governor has recommended organization
Batangas, Cavité, Laguna, Nueva Ecija, but shall delay action
as to these until return from northern and southern trips."
On the 18th of March it was announced from Washington that a

number of recent Acts of the Philippine Commission had been
received at the War Department, among them one which
establishes a general department of public instruction, with a
central office at Manila, under the direction of a general
superintendent, to be appointed by the commission, at a salary
of $6,000 a year. "Schools are to be established in every
pueblo in the archipelago where practicable, and those already
established shall be reorganized where necessary. There are to
be ten school divisions in the archipelago, each with a
division superintendent, and there is to be a superior
advisory board, composed of the general superintendent and
four members to be appointed by the Philippine Commission, to
consider the general subject of education in the islands and
make regulations. The English language, as soon as
practicable, shall be made the basis of all public
instruction, and soldiers may be detailed as instructors until
replaced by trained teachers. Authority is given to the general
superintendent to obtain from the United States 1,000 trained
teachers, at salaries of not less than $75 nor more than $100
a month, the exact salary to be fixed according to the
efficiency of the teacher. The act provides that no teacher or
other person "shall teach or criticise the doctrines of any
church, religious sect or denomination or shall attempt to
influence the pupils for or against any church or religious
sect in any public school." Violation of this section is made
punishable by summary dismissal from the public service. It is
provided, however, that it may be lawful for the priest or
minister of the pueblo where the school is situated to teach
religion for half an hour three times a week in the school
building to pupils whose parents desire it. But if any priest,
minister or religious teacher use this opportunity "for the
purpose of arousing disloyalty to the United States or of
discouraging the attendance of pupils or interfering with the
discipline of schools," the division superintendent may forbid
such offending priest from entering the school building
thereafter. The act also provides for a normal school at
Manila for the education of natives in the science of
teaching. It appropriates $400,000 for school buildings,
$220,000 for text books and other supplies for the current
calendar year, $25,000 for the normal school, $15,000 for the
organization and maintenance of a trade school in Manila and
the same amount for a school of agriculture.
{402}
The new tariff for the Islands, which the Commission had been
long engaged in framing, was submitted, in March, to the
government at Washington for approval. "In his letter of
transmittal Judge Taft says that the proposed bill follows
largely the classification of the Cuban tariff, 'but has been
considerably expanded by the introduction of articles
requiring special treatment here by reason of different
surroundings and greater distance from the markets.' Judge
Taft says also that the disposition of the business interests
of the islands is to accept any tariff the commission
proposes, provided only that the duties are specific and not
ad valorem. The question of revenue was kept steadily in view
in the preparation of the schedules, but it was not the only
consideration. Raw materials of Philippine industries, tools,
implements and machinery of production, materials of
transportation, the producers and transmitters of power and
food products are taxed as lightly as possible. … Export
duties are levied on only six articles—hemp, indigo, rice,
sugar, cocoanuts, fresh or as copra, and tobacco. The free
list admits natural mineral waters, trees, shoots and plants,
gold, copper and silver ores, fresh fruits, garden produce,
eggs, milk, ice and fresh meat, except poultry and game. There
is also a list of articles conditionally free of duty. The
importation of explosives is prohibited, but that of firearms
is not."
It is announced from Washington that "Judge Taft and General
MacArthur have agreed upon July 1 as the date for the
establishment of civil government in the Philippines. The
military regime in the islands will therefore cease on June
30, when General Chaffee will relieve General MacArthur of the
command, and Governor Taft will be inaugurated the next day
with considerable ceremony."
PHILIPPINE ISLANDS: A. D. 1901 (March-April).

Capture of Aguinaldo.
His oath of allegiance to the United States.
His address to his countrymen, counselling peace.
A stratagem, executed with great daring by General Funston of

the American forces, accomplished the capture of the Filipino
leader, Aguinaldo, on the 23d of March. From intercepted
correspondence, it had been learned that Aguinaldo, then
occupying his headquarters at Palanan, Isabela Province, was
expecting to be joined by some riflemen, whom his brother had
been ordered to send to him from central Luzon. On this,
General Funston conceived the plan of equipping a number of
native troops who should pass themselves off as the expected
reinforcements, several American officers going with them
ostensibly as prisoners, the hope being that Aguinaldo might
thus be reached and taken by surprise. General MacArthur
approved the scheme, and it was carried out with success. The
party was made up of 78 Macabebe scouts, four Tagalogs who had
formerly been officers in the insurgent army, and General
Funston, Captain Newton, Lieutenants Hazzard and Mitchel, who
acted the part of prisoners. They were taken by gunboat from
Cavite to a point above Baler, whence they made their way on
foot, sending a message in advance that the expected
reinforcements were on the way and had captured some prisoners
en route. The following brief narrative of what occurred
subsequently is taken from a newspaper account of the
expedition:
"For six days the expedition marched over an exceedingly
difficult country, covering 90 miles. When the men reached a
point eight miles from Aguinaldo's camp they were almost
exhausted from lack of food and the fatigue of the march. They
stopped at this place and sent a message to Aguinaldo,
requesting him to send food to them. The ruse thus far had
worked with the greatest success, and on March 22d, when
Aguinaldo sent provisions, it was seen that he did not have
the slightest suspicion. With the food he sent word that the
Americans were not wanted in his camp, but instructing their
supposed captors to treat them kindly. On March 23d the march
was resumed, the Macabebe officers starting an hour ahead of
the main body of the expedition. The 'prisoners,' under guard,
followed them. When the party arrived at Aguinaldo's camp a
bodyguard of 50 riflemen was paraded, and the officers were
received at Aguinaldo's house, which was situated on the
Palanan River. After some conversation with him, in which they
gave the alleged details of their suppositious engagement with
an American force, they made excuses and quietly left the
house. They at once gave orders in an undertone for the
Macabebes to get in position and fire on the bodyguard. The
order was obeyed with the greatest rapidity, and three volleys
were delivered. The insurgents were panic-stricken by the
sudden turn in affairs, and they broke and ran in
consternation. Two of them, however, were killed and eighteen
wounded. Simultaneously with the delivery of the volleys the
American officers rushed into Aguinaldo's house. Major
Alhambra, one of Aguinaldo's staff, had been shot in the face.
He, however, was determined not to be captured and he jumped
from a window into the river and disappeared. Two captains and
four lieutenants made their escape in a similar manner.
Aguinaldo, Colonel Villa, his chief of staff, and Santiago
Barcelona, the insurgent treasurer, did not have time to make
an attempt to get away before General Funston and the others
were upon them, demanding their surrender. Seeing that the
situation was hopeless, they gave themselves up. Aguinaldo was
furious at having been caught, but later he became
philosophical and declared that the ruse by which he had been
captured was the only one which would have proved successful
if the Americans had tried for 20 years. One of the Macabebes
was wounded. The party stayed two days at the camp and then
marched overland to the coast, where the Vicksburg, whose
arrival was excellently timed, picked them up and brought them
back to Manila."
On the 2d of April, a despatch from General MacArthur to the

War Department announced that Aguinaldo, on the advice of
Chief Justice Arellano, had taken the following oath of
allegiance to the United States: "I hereby renounce all
allegiance to any and all so-called revolutionary governments
in the Philippine Islands, and recognize and accept the
supreme authority of the United States of America therein; I
do solemnly swear that I will bear true faith and allegiance
to that government; that I will at all times conduct myself as
a faithful and law abiding citizen of the said islands, and
will not, either directly or indirectly, hold correspondence
with or give intelligence to an enemy of the United States,
nor will I abet, harbor or protect such enemy; that I impose
upon myself these voluntary obligations without any mental
reservations or purpose of evasion, so help me God."
{403}
On the 19th of April, Aguinaldo issued the following address

to his countrymen: "I believe I am not in error in presuming
that the unhappy fate to which my adverse fortune has led me
is not a surprise to those who have been familiar with the
progress of the war. The lessons taught with a full meaning,
and which have recently come to my knowledge, suggest with
irresistible force that a complete termination of hostilities
and lasting peace are not only desirable, but absolutely
essential to the welfare of the Philippine Islands. The
Filipinos have never been dismayed at their weakness, nor have
they faltered in following the path pointed out by their
fortitude and courage. The time has come, however, in which
they find their advance along this path to be impeded by an
irresistible force, which, while it restrains them, yet
enlightens their minds and opens to them another course,
presenting them the cause of peace. This cause has been
joyfully embraced by the majority of my fellow countrymen who
already have united around the glorious sovereign banner of
the United States. In this banner they repose their trust and
believe that under its protection the Filipino people will
attain all those promised liberties which they are beginning
to enjoy. The country has declared unmistakably in favor of
peace. So be it. There has been enough blood, enough tears and
enough desolation. This wish cannot be ignored by the men
still in arms, if they are animated by a desire to serve our
noble people, which has thus clearly manifested its will. So
do I respect this will, now that it is known to me. After
mature deliberation, I resolutely proclaim to the world that I
cannot refuse to heed the voice of a people longing for peace,
nor the lamentations of thousands of families yearning to see
their dear ones enjoying the liberty and the promised
generosity of the great American Nation. By acknowledging and
accepting the sovereignty of the United States throughout the
Philippine Archipelago, as I now do, and without any
reservation whatsoever, I believe that I am serving thee, my
beloved country. May happiness be thine."
PHŒNICIANS, The:
Modified estimates of their influence upon early
European civilization.
See (in this volume)

ARCHÆOLOGICAL RESEARCH: CRETE.
PILLAGER INDIAN OUTBREAK.

INDIANS, AMERICAN: A. D. 1898.
PLAGUE, The Bubonic.
For years the plague has "continued to breed in various inner

parts of Asia, and in 1894, coming from the Chinese province
of Yunnan, it invaded Canton, taking there 60,000 victims in a
few weeks. Thence it spread to Hong Kong, reached next year
the island of Haïnan and Macao, invaded Formosa in 1896, and
in the autumn of the same year appeared at Bombay. In the big
city of India it found all necessary conditions for breeding,
unchecked, for several months in succession: famine,
overcrowding, and the absence of all preventive measures; and
from Bombay it was carried by rail and road, to different
parts of India. … Happily enough, the plague is no longer the
mysterious, revengeful being which it used to be for our
ancestors. Its cause and modes of propagation are well known.
It is an infectious disease with a short period of incubation.
From four to six days after infection takes place, a sudden
loss of forces—often a full prostration, accompanied by a high
fever-sets in. A bubo appears, and soon grows to the size of
an egg. Death soon follows. If not—there is a chance of slow
and painful recovery; but that chance is very small, because
even under the best conditions of nursing, the mortality is
seldom less than four out of each five cases of illness. As to
the means of propagation of the plague, they are many. The
poison may infect a wound or a scratch; it may be ingested in
food; it may be simply inhaled. Dust from an infected house
was sufficient to infect healthy rats; and when healthy rats
were shut up in one cage with unhealthy ones, all caught the
disease and died. Already in 1881 Netten Redcliffe and Dr.
Pichon indicated that before the plague attacks men it
destroys mice and rats. This was fully confirmed in 1894 by
the Japanese and French bacteriologists Kitasato and Yersin,
at Hong Kong, and by Dr. Rennie, of the Chinese Customs, at
Canton. Masses of dead rats were seen in the streets of the
infested parts of Hong Kong, and the keeper of the west gates
of Canton collected and buried 24,000 of these animals. Dr.
Rennie also pointed out that among those inhabitants of Canton
who lived in boats on the river there were no cases of plague,
except a few imported from town, so that even rich Cantonese
took to living in boats; and he explained the immunity of the
boat-dwellers by the absence of infection through rats. The
worst is, however, that swine, and even goats and buffaloes,
snakes and jackals, are attacked by the plague. …
"As soon as the plague broke out at Hong Kong, the great
Japanese bacteriologist Kitasato and the French doctor Yersin,
who is well known for his work with Roux on the serum
treatment of diphtheria, were already on the spot. Yersin
obtained from the English authorities permission to erect a
small straw hut in the yard of the chief hospital, and there
he began his researches. Both Kitasato and Yersin had no
difficulty in ascertaining that the plague buboes teemed with
special bacteria, which had the shape of tiny microscopic
sticklets, thickened at their ends. To isolate these bacteria,
to cultivate them in artificial media, and to ascertain the
deadly effects of these cultures upon animals, was soon done
by such masters in bacteriology as Kitasato and Yersin. The
cause of the plague was thus discovered. It was evident that
infected rats and swine—especially swine with the Chinese, who
keep them in their houses—were spreading the disease, in
addition to men themselves. The same bacteria teemed in the
dead animals. As to men, the discharges from their buboes, and
even, in many cases, their expectorations, were full of plague
bacteria. Besides, Yersin soon noticed that in his
'laboratory,' where he was dissecting animals killed by the
plague, the flies died in numbers. He found that they were
infested with the same bacteria, and carried them about:
inoculations of bacteria obtained from the flies at once
provoked the plague in guinea-pigs. Ants, gnats, and other
insects may evidently spread infection in the same way, while
in and round the infested houses the soil is impregnated with
the same bacteria. As soon as the pest microbe became known,
experiments were begun, at the Paris Institut Pasteur, for
finding the means to combat it; and in July 1895 Yersin,
Calmette, and Borel could already announce that some very
promising results had been obtained."
P. Kropotkin,
Recent Science
(Nineteenth Century, July, 1897).
{404}
Of the first appearance of the plague in India, at Bombay, and

the early stages of its spread in that country, the Viceroy,
Lord Elgin, made the following report to the Secretary of
State for India, on the 27th of January, 1897: "The first
official intimation of the outbreak which reached us was in a
telegram from the Government of Bombay, dated the 29th
September 1896. The disease was then reported to be of a mild
type, and at first it showed no tendency to increase. …
Throughout the months of October and November the disease made
little or no progress, and the number of deaths reported a day
averaged nine. Early in December there was a marked increase,
and the number of deaths reported daily from the 2nd to the
23rd (inclusive) was about 32. From the 24th December onwards
there was another marked increase, and the number of deaths
reported from that date to the 14th January (inclusive)
averaged about 51. The next week shows a further increase, the
reported number of deaths averaging 74 a day. The total number
of deaths reported during October was 276; during November,
268; during December, 1,160; and from the 1st to the 25th
January, 1,444. The total number of deaths reported from the
beginning of the outbreak thus amounts to 3,148. We have
reason to fear that all deaths from the plague have not been
reported as such, and that the true mortality from the disease
is higher than is shown by the above figures. … For a
considerable time, except for a few imported cases in some
towns in Gujarat, the outbreak was confined to Bombay itself,
but on the 23rd of December we learnt from the Government of
Bombay that the plague had broken out in Karachi. … The total
number of deaths that have been reported in Karachi, from the
beginning of the outbreak up to the 24th January, is 608. It
will be observed that the disease has been very malignant in
Karachi, and that almost all the cases reported have been
fatal. As soon as the Surgeon General with the Government of
Bombay reported to that Government that he had seen cases of a
mild type of bubonic plague in the city, preventive measures
were adopted and a Committee of medical experts were appointed
to report on the disease and the situation. The Municipal
Corporation have from the outset required the infected
quarters to undergo a thorough and systematic cleaning and
disinfection; and they have also pushed on vigorously other
sanitary measures, such as the improvement of house
connections and the construction of surface drains in quarters
where the drainage was defective. A house-to-house visitation
by medical officers has also been instituted. The Corporation
have sanctioned liberal measures towards these ends, and the
executive officers have displayed great energy in carrying
them out. … We have informed the Government of Bombay that we
consider it necessary that the plan of removing all persons
from infected houses, and thoroughly cleansing and
disinfecting the buildings, should be carried out, and we have
asked His Excellency in Council, if he agrees, to report the
measures that are adopted to bring the plan into general
effect."
To the above suggestion that all persons be removed from

infected houses, the government of Bombay replied, on the 12th
of February: "His Excellency is advised that, to give full
effect to such a proposal, at the lowest computation, 30,000
persons belonging to different races, castes, and creeds would
need to be provided with temporary dwellings. There is no site
within the limits of the Bombay municipality which would
accommodate a tenth of this number. Great difficulty has
attended all attempts at the segregation of healthy inmates of
infected houses hitherto made, and very limited success bas
been achieved. From the beginning of the outbreak of this
disease it has been found that the native inhabitants of the
city are very reluctant to leave their houses or to allow any
member of their family afflicted with the disease to be taken
away. Indeed, their dread of the disease itself appears to be
hardly so powerful as their horror of being removed from their
houses. Ignorance and superstition prevent them from
discerning either that removal to a hospital is good for the
sick or removal [from] infected dwellings good for the
healthy, and they are far more easily moved by fear of the
municipal and police authorities than by any realisation of
the benefits that will accrue from a sensible course of
action. It is estimated that not less than 300,000 persons
have already fled from Bombay, moved so to do, not only by
fear of the plague, but quite as much, if not more, by an
unfounded and unreasonable fear of what might happen to them
at the hands of the police and municipal authorities were they
to remain."
Contending with such obstacles to the use of the most

effective measures for checking the spread of the disease, the
authorities at Bombay and elsewhere, who seem to have worked
with energy, saw little to encourage their efforts for some
time. In a second report to the Secretary of State for India,
made February 10, Lord Elgin was compelled to write: "We much
regret that we are unable to report that the plague shows any
signs of abating. In both Bombay and Karachi there has been an
increase in the daily number of seizures and deaths since the
beginning of the current month." But, a month later, on the
10th of March, the Viceroy reported that "the position of
affairs in Bombay is distinctly better. There has been a
decrease in the reported number of plague seizures and deaths,
and the total daily mortality from all causes shows a marked
diminution. During the week ending the 22nd February, the
average daily number of seizures and deaths was 115 and 117,
respectively; during the following week the daily average fell
to 107 and 99, whilst during the period March 2nd to March 8th
it has been 99 and 84. … Persons are now returning to the
quarters of Bombay, which are comparatively free from plague,
from the more infected outlying suburbs, and the Government of
Bombay have therefore found it necessary to watch persons
entering as well as those leaving Bombay. In the suburbs of
Kurla, Bandora, and Bhiwandi the plague continues to be
severe. Outside Bombay in the Presidency proper the number of
indigenous cases has increased, and the disease shows a
tendency to spread, especially in the Thana and Surat
districts. … Outside Karachi the plague shows no tendency to
spread in Sind, and Sukkur is the only other place from which
indigenous cases have been reported."
Great Britain, Parliamentary Publications

(Papers by Command: C.-8386, 1897; and C.-8511, 1897).
{405}
From that time there appears to have been a nearly steady

subsidence of the disease until the following September, when
it showed renewed virulence at Poona, and began to be newly
spread, invading districts in the Punjab and elsewhere outside
of the Bombay Presidency. By the middle of November Poona was
substantially empty of inhabitants, except those stricken with
the disease and those who bravely cared for the sick and dying.
In December there was a fresh outbreak in Bombay, which soon
became more deadly than that of the previous winter and
spring. By the beginning of February, 1898, and through March,
the deaths from plague alone in Bombay had risen above a
thousand a week. Then another subsidence occurred, followed by
another recrudescence of the disease in August, and another
decline in October. But the variations in other districts were
not uniform with those in Bombay. At the end of 1898, the
total of mortality from plague in all the afflicted districts
of India, reckoning from the beginning, was believed to exceed
100,000, including 70,000 in the Bombay Presidency and Sind
(28,000 in the city of Bombay), and 2,000 in the Punjab. In
Calcutta there had been but 150 deaths. Although the measures
taken for checking the spread of the pestilence were far less
stringent than they would have been among people more capable
of understanding what they meant and what their importance
was, they alarmed the religious jealousies of both the Hindus
and the Mohammedans, and were resisted and resented with
dangerous fury at a number of times. At Poona, in June, 1897,
two British officials were murdered by young Brahmins, who had
been excited to the deed by native journals, the language of
which was so violent that the government found it necessary to
prosecute several for sedition. At Bombay, in March, 1898,
when the plague was at its worst, there were very serious
riots, in which a number of Europeans were killed, and troops
were called to the help of the police before the frenzied mob
could be overcome.
Again, in 1899, there was a revival of the disease in India,

especially at Bombay, during the winter, with a decline in
April and fresh virulence in September. At the end of the year
the estimate of total mortality from plague in India since the
beginning was 250,000.
Of the wider spreading of the pestilence during 1900 the

following summary of information is given in the annual report
of the United States Secretary of the Treasury, in connection
with details of quarantine measures: "The Surgeon-General
reports that plague has been more widely distributed during
the year than was ever known in history, and for the first
time obtained lodgment in the Western Hemisphere, at Santos,
Brazil, in October, 1899. By this it is not meant that the
disease has been actually more prevalent than before, but that
its points of contact have embraced nearly every civilized
country in the world, though its prompt recognition and
application of modern methods have either entirely prevented
its spread or have caused it to disappear after a short period
of infection. The scientific knowledge of the disease renders
it far less to be dreaded than before, but increase in rapid
communication between different parts of the world facilitates
its transportation. In illustration, the fact is cited that 20
vessels have been reported, arriving at as many principal
seaports in different parts of the world, on which plague was
discovered on arrival or had manifested itself during the
voyage. As heretofore, its chief ravages have been in India,
where preventive measures have been hindered by religious
fanaticism. In India during the year there were 66,294 deaths.
Notable outbreaks of the disease occurred in Kobe and in
Formosa, Japan, at Oporto, Santos, Rio de Janeiro, Honolulu,
Sydney, Mauritius, Hongkong, and Glasgow.
"In December, 1899, on account of the apparent spread of this

disease, 12 commissioned officers were detailed by order of
the President for duty in the offices of the United States
consuls at the principal ports in England and on the
Continent. In June, the disease fortunately not having become
as widespread as anticipated, they were recalled, with the
exception of five, who are still retained for the purpose of
furnishing information and for service at any needed point.
Two of those thus retained, when the plague was announced at
Glasgow, Scotland, on August 28, 1900, were immediately sent
to that point and began inspection of vessels for the United
States and also for Canada, by request of that Government,
thus enabling vessels to be entered at ports on this side
without undue restraint. In the laboratory of the Service,
scientific investigations as to the viability of the plague
bacillus and the methods and efficiency of disinfection have
been conducted, and the results, together with excerpts from
all available literature hearing upon the prevention of
plague, have been published in the Public Health Reports,
forming, for this year, a volume containing most complete
information upon this disease. About 700,000 doses of
Haffkine's prophylactic were also prepared in the laboratory
and sent to the United States quarantine officers at home and
abroad, together with large quantities of Yersin's serum,
purchased early in the year from the Pasteur Institute in
Paris. In these two preparations, the one (Haffkine) a
prophylactic and the other (Yersin) both prophylactic and a
cure, the Surgeon-General says that science has effective
methods of combating the spread of this disease."
United States, Secretary of the Treasury,

Annual Report, December 4, 1900.
The "antitoxin, or serum, first prepared by Professor Haffkine

as a plague inoculation, called Haffkine's prophylactic, is
now being used in Bombay and western India with remarkable
results. This prophylactic is prepared by first taking the
plague bacilli, or the young germs, from a person affected
with the plague and cultivating them. These microbes are
killed by artificial means and a high degree of heat. From
these dead germs and their poisonous excrements is produced a
fluid that is believed to have acquired the power, when
injected into the human system, to render the blood immune
from the attack of plague germs and to neutralize their
effect. The injection of such a poison has the effect of an
antitoxin and prevents the system from nourishing plague. A
dead plague germ being inoculated into a person, plague will
not follow. A person after having one attack of the disease is
rarely liable to a second. The person first inoculated is
subject to symptoms of the plague.
{406}
In vaccination for smallpox
a living germ is dealt with, whereas in plague inoculation
dead seed only are injected. … Inoculation is exceedingly
unpopular among the natives. The government has had great
labor in persuading the Hindoo mind of the efficacy of
Haffkine's prophylactic against plague and at the same time of
its utter harmlessness in every other respect. The Hindoo is
suspicious that the dead germs and their toxic excreta may be
of animal rather than vegetable substance, which would make
the injection of the fluid into their body a religious
offense."
United States Consular Reports,
January, 1900, page 101.
"In the present epidemic, plague-spots are scattered over the

whole face of the globe from Sydney to Santos and Hongkong,
and recently from San Francisco suspicious cases have been
reported. The annual pilgrimage of Moslems to worship at the
shrines of Mecca and Medina is now, as in the past, of all
human agencies, the most active in spreading the pest. … Since
Egypt is nearest, plague first appears there in the seaport
towns, particularly Alexandria. Sanitary conditions have
improved vastly, like economics, under British control; and,
last year, what in other times might have been a devastating
epidemic was limited to relatively a few scattered cases.
Recognizing the danger to themselves, the European powers have
been led to take steps, under the Venice Convention, for their
own protection. An international quarantine, under the control
of the Egyptian Sanitary, Maritime, and Quarantine Council, in
which the powers have one vote each and Egypt three, has
established stations at two points on the Red Sea."
American Review of Reviews,

May, 1900.
PLATT AMENDMENT, The.

CUBA: A. D. 1901 (FEBRUARY-MARCH).
PLURAL VOTING.

BELGIUM: A. D. 1894-1895.
PLYMOUTH COLONY:
Return of the manuscript of Bradford's History to

Simultaneous Mass Transfer and Chemical Reactions in Engineering Science: Solution Methods and Chemical Engineering Applications Bertram K.C. Chan

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Simultaneous Mass Transfer and Chemical Reactions in Engineering Science: Solution Methods and Chemical Engineering Applications Bertram K.C. Chan

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Simultaneous Mass Transfer and

Chemical Reactions in Engineering

BERTRAM K.C. CHAN

Copyright Ó 2020 Elsevier Inc. All rights reserved.

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my physical science teacher Brother Vincent, B.Sc., at the De La Salle

and at the University of Sydney:

Among the unit operations in biomolecular, chemical, and

equations in both space and time, the system solution is then

“Perry’s Chemical Engineers’ Handbook,” 9th Edition

“Perry’s Chemical Engineers’ Handbook”, 1st through 8th

In many biochemical, biomedical, and chemical processes, in

Simultaneous Mass Transfer and Chemical Reactions in Engineering Science. https://doi.org/10.1016/B978-0-12-819192-7.00001-1

with reversible, complex biochemical or chemical reactions in

1.1 GaseLiquid Reactions

1.1.1 Simultaneous biomolecular reactions and

the drug properties and the physiology of the gastrointestinal

1) release from the food matrix in the lumen,

1.1.1.2 The industrial chemistry and chemical engineering

• The micro model describes the interphase mass transfer be-

Both parts of the overall model may be solved sequentially,

• For packed columns this means, in terms of the Sherwood

Hinterland concept may successfully predict many phenomena

to implement an alternative for the well-known Hinterland

6. Another disadvantage of the Hinterland concept is that it can

conditions, an improvement of the mass transfer (higher kla, for

1.2 The modeling of gaseliquid reactions

1.2.1 Film theory of mass transfer

in which A* is the concentration of dissolved gas at the interface

interfacial area is not generally known! Thus the quantity directly

1.2.2 Surface renewal theory of mass transfer

The form of the surface-renewal model ﬁrst proposed by Hig-

And the rate of transfer of dissolved gas, initial concentration of

Figure 1.1 Schematic of the penetration model.

same rate, and there is not a velocity gradient within the

and the boundary conditions are:

From the above two expressions, the rate of mass transfer at

And the mass transfer coefﬁcient is given by

Thus, from the above equation, the mass transfer coefﬁcient is

1.2.3 Absorption into a quiescent liquid[*1]

Here, x is the distance measured from the surface, where x ¼ 0,

is the error function of x/2O(DAt), and is deﬁned by

Values of the error function may be found in standard math-

1.2.3.1 Absorption accompanied by chemical reactions[*1]

DA v2 a=vx2 ¼ va=vt þ rðx; tÞ (1.16)

1.2.3.2 Irreversible reactions[*1]

þ1 2 expfxOðk1 =DA Þgerfc½x=f2OðDA tÞg þ Oðk1 tÞ

Thus, when k1t is large, the distributions of concentration and

Q z 2A OfðDA t = pÞð1 þ k1 t = 3Þ (1.26)

to within 5% when k1t < 0.5.

where y moles of product arise from the reaction of one mole of

1.2.3.2.2 Instantaneous reactions

The solution of the equations governing this case (and similar

a=A ¼ 0; x > 2bOt (1.29)

b=B0 ¼ ferf½x = 2OðDB teerfðb = ODB Þg=erfcðb = ODB Þ; x > 2bOt

R ¼ fA = erfðb =ODA ÞgOðDA = pÞ ¼ Et A OðDA = pÞ (1.32)

Q ¼ f2A = erfðb =ODA ÞgOðDA t = pÞ ¼ 2Et A OðDA t = pÞ (1.33)

and b is deﬁned by:

= erfcðb =ODA Þexp b = DP

þ1 2 expfxOðk1 =DA Þgerfc½x=f2OðDA tÞg þ Oðk1 tÞ

b=B0 ¼ ferf½x = 2OðDB teerfðb = ODB Þg=erfcðb = ODB Þ; x > 2bOt