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 Front Cover
 Editorial: A letter to chemical...
 Table of Contents
 Classical thermodynamics
 Catalysis and catalytic reaction...
 Parametric pumping
 In memoriam - Hung Tsung Chen
 Molecular thermodynamics and computer...
 Coal liquefaction and desulfur...
 Oil shale char reactions
 Book reviews
 Kinetics and catalysis
 Chemical engineering analysis
 Positions available
 Underground processing
 Polymer processing
 Stirred pots
 Separation processes
 Heterogeneous catalysis
 Book reviews
 The dolphin problem
 In memoriam - Herbert E. Schwe...
 Index: Volumes XI-XV
 Graduate education advertiseme...
 Back Cover








Chemical engineering education
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Title: Chemical engineering education
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Physical Description: v. : ill. ; 22-28 cm.
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Place of Publication: Storrs, Conn
Publication Date: Fall 1981
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Table of Contents
    Front Cover
        Front Cover 1
        Front Cover 2
    Editorial: A letter to chemical engineering seniors
        Page 153
        Page 154
    Table of Contents
        Page 155
    Classical thermodynamics
        Page 156
        Page 157
        Page 158
        Page 159
    Catalysis and catalytic reaction engineering
        Page 160
        Page 161
        Page 162
        Page 163
        Page 164
        Page 165
    Parametric pumping
        Page 166
        Page 167
        Page 168
        Page 169
        Page 170
    In memoriam - Hung Tsung Chen
        Page 171
    Molecular thermodynamics and computer simulation
        Page 172
        Page 173
        Page 174
        Page 175
        Page 176
        Page 177
    Coal liquefaction and desulfurization
        Page 178
        Page 179
        Page 180
        Page 181
        Page 182
        Page 183
    Oil shale char reactions
        Page 184
        Page 185
    Book reviews
        Page 186
        Page 187
    Kinetics and catalysis
        Page 188
        Page 189
        Page 190
        Page 191
    Chemical engineering analysis
        Page 192
        Page 193
        Page 194
        Page 195
        Page 196
    Positions available
        Page 197
    Underground processing
        Page 198
        Page 199
        Page 200
        Page 201
        Page 202
        Page 203
    Polymer processing
        Page 204
        Page 205
        Page 206
    Stirred pots
        Page 207
    Separation processes
        Page 208
        Page 209
        Page 210
        Page 211
        Page 212
        Page 213
    Heterogeneous catalysis
        Page 214
        Page 215
        Page 216
        Page 217
        Page 218
    Book reviews
        Page 219
    The dolphin problem
        Page 220
        Page 221
    In memoriam - Herbert E. Schweyer
        Page 222
    Index: Volumes XI-XV
        Page 223
        Page 224
        Page 225
        Page 226
    Graduate education advertisements
        Page 227
        Page 228
        Page 229
        Page 230
        Page 231
        Page 232
        Page 233
        Page 234
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    Back Cover
        Back Cover 1
        Back Cover 2
Full Text









chemical engineering education


VOLUME XV


NUMBER 4


FALL 1981


GRADUATE EDUCATION ISSUE


Reeatc hac on ...

CLASSICAL THERMODYNAMICS . . .. . . . . . . Abbott

CATALYSIS/CATALYTIC REACTION ENGINEERING . . . But, Kung

PARAMETRIC PUMPING . . . . . . Chen, Kerobo, Holliln, Huang

MOLECULAR THERMODYNAMICS/COMPUTER SIMULATION . Gubbins, Street

COAL LIQUEFACTION AND DESULFURIZATION
Guin, Liu, Curtis, Tarrar, Williams


OIL SHALE TAR REACTIONS


Coamaej in �...

KINETICS AND CATALYSIS . . .

CHEMICAL ENGINEERING ANALYSIS

UNDERGROUND PROCESSING

POLYMER PROCESSING . . . .

SEPARATION PROCESSES . . .
HETEROGENEOUS CATALYSIS


SThomson



S . . . Bartholomew

. . . . . . . . Hauler

. . . . . . . . Miller

. . . . . . . . Soong

. . . . . . . . W nk

. . . . . . . . Wolf


THE DOLPHIN PROBLEM * Levenspiel
HEAT EXCHANGER: THE AGONY AND THE ECSTASY * Barrar
ARIS REVIEWS OMNIBOOK




egCC
achoa/wea d < and fth ank....








3M COMPANY








CHEMICAL BIGINENG EDUCATION
iha d onationbaw o id












A LETTER TO CHEMICAL ENGINEERING SENIORS

As a senior you may be asking some questions about graduate school. In this issue CEE attempts to
assist you in finding answers to them and reports on a survey of industrial needs for Ph.D.'s.


Should you go to graduate school?
Through the papers in this special graduate
education issue, Chemical Engineering Educa-
tion invites you to consider graduate school as
an opportunity to further your professional de-
velopment. We believe that you will find that
graduate work is an exciting and intellectually
satisfying experience. We also feel that graduate
study can provide you with insurance against the
increasing danger of technical obsolescence.
Furthermore, we believe that graduate research
work under the guidance of an inspiring and in-
terested faculty member will be important in
your growth toward confidence, independence,
and maturity.

Is there a need for Ph.D.'s in ChE?
Yes, definitely. A survey conducted by CEE of
ten leading companies indicated that while during
1980-81 they had combined needs for 220 chemi-
cal engineering Ph.D.'s, they were only able to
hire 143. Most companies also indicated that their
1981-82 needs will be as great. In addition, it is
well known that there has been for several years
a great need for additional professors in chemical
engineering departments-a position for which
a Ph.D. is required.

What is taught in graduate school?
In order to familiarize you with the content of
some of the areas of graduate chemical engineer-
ing, we are continuing the practice of featuring
articles on graduate courses as they are taught by
scholars at various universities. We strongly
suggest that you supplement your reading of this
issue by also reading the articles published in pre-
vious years. If your department chairman or pro-
fessors cannot supply you with the latter, we
would be pleased to do so at no charge.

What is the nature of graduate research?
In an effort to acquaint you with some of the


areas of research in chemical engineering, we are
also publishing articles on the research of certain
faculty members. These articles, as well as those
on course work, are only intended to provide
examples of graduate research and course work.
The professors who have written them are by
no means the only authorities in those fields, nor
are their departments the only departments which
emphasize that area of study.

Where should you go to graduate school?
It is common for a student to broaden him-
self by doing graduate work at an institution
other than the one from which he receives his
bachelor's degree. Fortunately there are many fine
chemical engineering departments and each of
these has its own "personality" with special em-
phases and distinctive strengths. For example, in
choosing a graduate school you might first con-
sider which school is most suitable for your own
future plans to teach or to go into industry. If
you have a specific research project in mind, you
might want to attend a university which empha-
sizes that area and where a prominent specialist
is a member of the faculty. On the other hand if
you are unsure of your field of research, you might
consider a department that has a large faculty
with widely diversified interests so as to ensure
for yourself a wide choice of projects. Then again
you might prefer the atmosphere of a department
with a small enrollment of graduate students. In
any case, we suggest that you begin by writing
the schools that have provided information on
their graduate programs in the back of this issue.
You will probably also wish to seek advice from
members of the faculty at your own school.
But wherever you decide to go, we suggest
that you explore the possibility of continuing
your education in graduate school.
Sincerely,
RAY FAHIEN, Editor CEE
University of Florida
Gainesville, FL 32611


FALL 1981







PROCTER & GAMBLE is looking for


in R&D/Product
Development


This organization is responsible for the
creation and improvement of new and
existing products, together with developing
the associated technology advances and
solving technical problems.
While this organization encompasses the full
range of scientific and engineering
backgrounds, the primary need at the BS/MS
level is for Chemical Engineers and
MBAs with a chemical or engineering
undergraduate degree.
Your initial responsibilities in the organization
would be primarily technical, with varying
degrees of interactions with P&G's
Engineering, Manufacturing and Marketing
divisions. As you advance, your career could
evolve along technical and/or management
routes. This evolution will include progressive
assignments, exposure to other divisions, and
in many cases a transfer to another
R&D/Product Development division, or
where appropriate to an Engineering,
Manufacturing or Marketing division.
The R&D/Product Development organization
is headquartered in Cincinnati, consists of
over 20 divisions, focuses on U.S. consumer
and industrial products, conducts P&G's basic
research, and provides technical support for
our international operations and technical
centers. (This technical support includes
international travel by certain of our
U.S.-based division personnel.)


RESPONSIBILITY NOW!
if you are Interested In this area, please send
a resume to:
The Procter & Gamble Company
R&D BS/MS Recruiting Coordination Office
Ivorydale Technical Center
Spring Grove and June Avenues
Cincinnati, Ohio 45217


PROCTER & GAMBLE
AN EOUAL OPPORTUNITY EMPLOYER










EDITORIAL AND BUSINESS ADDRESS
Department of Chemical Engineering
University of Florida
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Editor: Ray Fahien (904) 392-0857
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Chemical Engineering Education


VOLUME XV


NUMBER 4


FALL 1981


RESEARCH ON
156 Classical Thermodynamics, Michael M. Abbott
160 Catalysis and Catalytic Reaction Engineering,
John B. Butt, Harold H. Kung
166 Parametric Pumping, H. T. Chen, C. O. Kerobo,
H. C. Hollein, C. R. Huang
172 Molecular Thermodynamics and Computer
Simulation, Keith E. Gubbins, William B. Street
178 Coal Liquefaction and Desulfurization, J. A. Guin,
Y. A. Liu, C. W. Curtis, A. R. Tarrar,
D. C. Williams
184 Oil Shale Char Reactions, William J. Thomson

COURSES IN
188 Kinetics and Catalysis, C. A. Bartholomew
192 Chemical Engineering Analysis, John C. Hassler
198 Underground Processing, Clarence A. Miller
204 Polymer Processing, David S. Soong
208 Separation Processes, Phillip C. Wankat
214 Heterogeneous Catalysis, Eduardo E. Wolf

DEPARTMENTS
220 Class and Home Problems
The Dolphin Problem, Octave Levenspiel

153 Editorial
171, 222 In Memoriam
Hung Tsung Chen, Herbert E. Schweyer
197 Positions Available
207 Stirred Pots Ellen Barrar
222 Index
186,219 Book Reviews


CHEMICAL ENGINEERING EDUCATION is published quarterly by Chemical
Engineering Division, American Society for Engineering Education. The publication
is edited at the Chemical Engineering Department, University of Florida. Second-class
postage is paid at Gainesville, Florida, and at DeLeon Springs, Florida. Correspondence
regarding editorial matter, circulation and changes of address should be addressed
to the Editor at Gainesville, Florida 32611. Advertising rates and information are
available from the advertising representatives. Plates and other advertising material
may be sent directly to the printer: E. O. Painter Printing Co., P. 0. Box 877,
DeLeon Springs, Florida 32028. Subscription rate U.S., Canada, and Mexico is $15 per
year, $10 per year mailed to members of AIChE and of the ChE Division of ASEE.
Bulk subscription rates to ChE faculty on request. Write for prices on individual
back copies. Copyright ) 1981 Chemical Engineering Division of American Society
for Engineering Education. The statements and opinions expressed in this periodical
are those of the writers and not necessarily those of the ChE Division of the ASEE
which body assumes no responsibility for them. Defective copies replaced if notified
within 120 days.
The International Organization for Standardization has assigned the code US ISSN
0009-2479 for the identification of this periodical.


FALL 1981












CLASSICAL THERMODYNAMICS

CLASSICAL THERMODYNAMICS


MICHAEL M. ABBOTT
Rensselaer Polytechnic Institute
Troy, NY 12181

RESEARCH IN CHEMICAL ENGINEERING thermo-
dynamics is often inspired by the practical
importance of vapor/liquid equilibrium (VLE).
This is certainly true at Rensselaer, where we
specialize in VLE data collection and correlation
for systems at low to moderate pressures. Since
experiment is necessarily conditioned by theory,
we first consider the relevant thermodynamic equa-
tions.

LOW-PRESSURE VLE AND
EXCESS FUNCTIONS
As shown in numerous textbooks, VLE in a
system of uniform T and P requires uniformity of
A
the component fugacity fi of each distributed
species:
A A
f I = fv (1)

This notorious equation, while suitably general, is
not especially useful as it stands. In particular,
one wishes to display explicitly the compositions
x, and yi of the phases. We do this by definition,
through one or the other of two secondary quanti-
A
ties: the component fugacity coefficient i1, or the
activity coefficient yi.
The conventional description of low-pressure
VLE treats the liquid phase through activity co-
efficients, and the vapor phase through fugacity
coefficients. Introducing these quantities, we re-
write Eq. (1) as
A
xiyif� = yi4ip (2)
Here, fi� is the standard-state fugacity of species


Our research program ... initiated
by H. C. Van Ness, is an effort of
some 25 years' standing.

� Copyright ChE Division, ASEE, 1981


i as a liquid, and all quantities are evaluated at
the system T and P. The fugacity coefficients are
determined from an equation of state for the
vapor phase, and the activity coefficients are de-
rived from an expression for the excess Gibbs
function GE for the liquid mixtures. For obvious
reasons, we describe formulations based on Eq.
(2) as "gamma/phi" approaches. ["Gamma/
gamma" and "phi/phi" approaches are also used
for two-phase equilibria, the former for liquid/
liquid equilibria (LLE), and the latter for VLE
at high pressures.]
Equation (2) applies for both subcritical and
supercritical species, provided that appropriate
interpretations are put on yi and fi�. When all
species in a system are subcritical, the state of
pure liquid is accessible for all i, and it is conven-
tional to eliminate each fi� in favor of the vapor/
liquid saturation pressure Pisat of pure i. More-
over, convenience dictates the referral of each
activity coefficient to a fixed reference tempera-
ture T+ and pressure P+. Consistent with these re-
quirements, we may write Eq. (2) in the equiva-
lent form [1]


Xiy 1P sat = ylQIiP


(3a)


where the correction factor Di (a quantity of
order unity) is defined as


A
0i


Here, function Ii depends on liquid properties
only, specifically, on the molar volume of pure i,
and on the partial molar excess functions Hi and
ViE.
Equations (3) find two distinct but comple-
mentary uses: in the reduction of VLE data, the
goal of which is to provide correlations for GE, and
in the computation of VLE, which requires the
availability of appropriate numerical expressions
for GE. In either case, the connection between the
activity coefficient and the excess Gibbs function is
made through the partial-property relationship

yi = exp(GiE/RT) (4)


(3b)


CHEMICAL ENGINEERING EDUCATION








Equation (4) in effect establishes the composition
dependence of GE through reduction of VLE data;
the T and P dependencies are related to HE (the
"heat of mixing") and VE (the "volume change
of mixing") :

HE = GET G (5)
aT
aGE
VE- G (6)
zP
In principle, the T dependence of GE can be de-
termined by analysis of isothermal VLE data
taken at several different temperatures; in
practice, it is far more easily established through
Eq. (5), by use of a single set of isothermal VLE
data and one or more directly measured sets of
data for HE. The volume change of mixing is small
for liquids at low pressure levels and is easily
measured; the correspondingly small effect of P
on GE is always determined through Eq. (6).

DATA COLLECTION AND REDUCTION
O UR RESEARCH PROGRAM IN thermodynamics,
initiated by H. C. Van Ness, is an effort of
some 25 years' standing. The thermodynamics is
"classical," and largely centers on the exploitation
of Eqs. (3) through (5) ; that is, on the measure-
ment, reduction, and correlation of low-pressure
VLE data and of the excess functions, particularly
GE and HE. The immediate goals of our research
are severalfold:
* To derive and expose the classical thermodynamic
theory relating measurable variables to functions
of practical interest.
* To develop the tools (equations of state and ex-
pressions for the excess functions) required for
implementation of technical thermodynamic calcula-
tions.
* To devise experimental methods that are as accurate,
quick, and "technique-proof" as possible, and to
demonstrate their feasibility.
* To produce high-quality data suitable for formula-
tion and testing of theories of solutions.
We regard the last two items as particularly sig-
nificant, and consider them in the following para-
graphs.
Apart from a few special techniques, VLE
data at low pressures (ca. 1 bar or less) are mainly
collected on one of two types of apparatus: dy-
namic circulation stills, and static equilibrium
cells. Because of their simple construction and
ease of operation, we favor the use of static cells.
By this technique, a liquid mixture is charged to


Michael M. Abbott is Associate Professor of Chemical Engineering
at R.P.I., where he has worked since 1969. Prior to that, he was
employed by Esso Research and Engineering. In his research, he
collaborates with H. C. Van Ness on work described in this paper.
His teaching interests are mainly in the thermal sciences and in chemi-
cal process design.

an evacuated cell immersed in a constant-tempera-
ture bath. Equilibration of the phases is brought
about by stirring, and the equilibrium pressure
is read from a high-precision gauge. In an older
design [2], we determined liquid compositions
gravimetrically; with our present equipment [3],
liquids are metered into the cell with calibrated
piston-injectors.
There are two potential problems associated
with static cells: possible errors in measured
pressures because of incomplete degassing of the
liquids before charging, and errors arising from
disturbance of the equilibrium state on withdraw-
ing vapor samples for analysis. We have solved the
first problem by a novel distillation technique
[4]. The second problem is in fact avoidable be-
cause, if an accurate equation of state is available
for the vapor phase (the usual case for low-
pressure VLE), then the vapor compositions
actually represent redundant information. Thus
we measure only P and x, and reduce the data
either by integration of the coexistence equation
[2, 5], or by applying a technique known as
Barker's method [6, 7]. Barker's method presumes
the availability of an expression for GE of sufficient
flexibility to represent the P-x data to within their
precision, and of an efficient computer program
for nonlinear regression. We have built up a
library of such equations and programs, and re-
duction of our VLE data is now normally straight-
forward: we can collect and correlate (via an ex-
pression for GE) VLE data for a binary system
in two to three days, an exercise that at one time
constituted half the effort for a Master's degree.


FALL 1981










It was once hoped ... that thermodynamic
properties of mixtures could somehow be estimated
from properties of the constituent pure species.
This hope has been abandoned and replaced
with a more realistic goal.


Next to GE, the liquid-phase excess function
of major interest is HE, for, by Eq. (5), it es-
tablishes the often significant effect of T on GE, and
is an indispensable tool for computation of isobaric
VLE from isothermal VLE measurements [1].
Moreover, knowing both GE and HE, one can com-
pute the excess entropy and the entropy change of
mixing, quantities of importance to solution
theorists:
SE = (HE - GE/T (7)
AS = SE - RZxiln xi (8)
We measure HE by isothermal dilution calori-
metry, a technique in which amounts of a com-
ponent (or solution) are successively injected into
a vessel containing another component (or solu-
tion), sufficient amounts of heat being added or
extracted in the meantime so as to keep the
contents of the vessel at constant temperature.
The quantitative transfer of heat under these
conditions is an extremely exacting task, subject
to some fairly subtle sources of error, and the
measurement of heats of mixing is thus inherently
more difficult than the taking of isothermal VLE
data. On the other hand, the reduction of the
calorimetric data is trivial-unlike the reduction
of VLE data-because the quantity measured is
directly related to the quantity sought.
Our dilution calorimeters have gone through
several stages of development. The prototype de-
vice of Mrazek and Van Ness [8] demonstrated
the suitability of the technique for producing
high-quality data on endothermic systems, quickly
and with a minimum of effort. The second- and
third-generation designs [9, 10], which followed
closely upon one another, incorporated (then)
state-of-the-art electronics and circuitry, and ac-
commodated exothermic as well as endothermic
systems. These devices have been widely copied
and are thus, directly or indirectly, the source
of many of the world's published heat-of-mixing
data. Inevitably, the most recent electronics revo-
lution has caught up with us, and we recently
[11] constructed and tested a fourth-generation
calorimeter, incorporating the latest in solid-state


microcircuitry. A photograph of the new device
is shown in Figure 1.
As already noted, thermodynamics at R. P. I.
is of the classical variety, directed mainly at the
measurement and empirical description of macro-
scopic properties of solutions. We endeavor, how-
ever, to keep abreast of developments in molecular
thermodynamics, and the tone of our experimental
program reflects and complements trends in this
area. It was once hoped, for example, that thermo-
dynamic properties of mixtures could somehow be
estimated from properties of the constituent pure



I zI


FIGURE 1. The fourth-generation heat-of-mixing calori-
meter.
species. This hope has been abandoned and re-
placed by a more realistic goal: that of predicting
properties of multicomponent mixtures from those
of the constituent binaries, either through models
for GE based on the "local composition" concept
[12, 13, 14], or by "group contribution" techniques
[15, 16]. For such approaches, binary data form the
data base, but multicomponent data are required
for testing and fine-tuning the correlations. The
simplest multicomponent system contains three
chemical species, and thus for the past eight years
we have conducted a program of collecting precise
VLE and HE data for ternary systems and their
constituent binaries. This program is still in pro-
gress. O

REFERENCES
1. Van Ness, H. C., and M. M. Abbott, "Classical
Thermodynamics of Nonelectrolyte Solutions, With
Applications to Phase Equilibria," Ch. 6, McGraw-
Hill, New York (1982).
2. Ljunglin, J. J., and H. C. Van Ness, Chem. Eng. Sci.,
Continued on page 217.


CHEMICAL ENGINEERING EDUCATION









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� 1981. The Dow Chemical Company









Research on


CATALYSIS AND

CATALYTIC REACTION ENGINEERING


JOHN B. BUTT AND HAROLD H. KUNG
Northwestern University
Evanston, IL 60201

C ATALYSIS IS A KEY PROCESS in a large share of
the chemical industry and in an even larger
share of the petroleum industry. In addition, im-
portant applications of catalysis are found in en-
vironmental areas, in the pharmaceutical industry,
and in agriculture via fertilizers. Since most
chemical reactions which proceed merely upon
mixing and heating must already have been dis-
covered, the technological importance of catalysis
can only increase with time. Both homogeneous
and heterogeneous catalysis are involved in techno-
logically important processes and it is unlikely
that this situation will change. Each type of
catalysis has its advantages; however, hetero-
geneous catalysis is particularly advantageous in
the important case of large volume operations.
Research in catalysis encompasses a wide
variety of aspects. One is concerned with the basic
chemistry of the catalyst and of the catalytic re-
action, with the kinetics of the reaction, with its
mechanism and the nature of the adsorbed species
which are intermediates in the mechanism, and the
exact structure of the solid catalyst. One is also
concerned with the catalytic reaction engineering
associated with transport effects, reactor design,
catalyst design, and other factors of importance
in technological application. At the other end of
the scale, the relatively new area of surface
chemical physics, which is concerned with the
nature of single crystal surfaces, their interaction
with molecules from the gas phase, and now in-
creasingly with the reactions of adsorbed species
at single crystal planes, is making an ever increas-
ing contribution to the understanding of hetero-
geneous catalysis.
An important result of these very different
aspects of heterogeneous catalysis is that it has
now necessarily become an interdisciplinary area
of research. It is not easy for one person to master

� Copyright ChE Division, ASEE, 1981


John Butt received his B.S. from Clemson University and D.Eng
from Yale. He is a recipient of the Colburn and Professional Progress
Awards from AIChE, and currently is Walter P. Murphy Professor of
Chemical Engineering at Northwestern. (L)
H. Kung received his B.S. from the University of Wisconsin,
Madison, and his Ph.D. from Northwestern University. After a brief stay
at the DuPont Chemical Company as a research scientist, he joined the
Chemical Engineering Department of Northwestern in 1976 where
he is currently associate professor. (R)


the techniques of proper measurement of catalytic
kinetics, methodology of isotopic tracer studies,
handling the rather complicated organic molecules
involved in many catalytic processes, knowledge of
coordination chemistry and organometallic chemis-
try needed to understand reactions at the surfaces
of catalysts, the many techniques of physical
characterization, the methods and interpretation
of electron spectroscopies-and at the same time
be able to master the theory of diffusion and re-
action and be expert in reactor design. Thus while
a very central component of catalysis research at
Northwestern is located in the Chemical Engineer-
ing Department, it will be seen below that sub-
stantial interactions with two other departments
(Chemistry and Materials Science and Engineer-
ing) are involved in the overall program.

CATALYSIS LAB FACILITIES
CURRENTLY IN OUR DEPARTMENT, the effort in
catalysis research involves three post-doctoral
fellows, fifteen Ph.D. students, and four M.S.
students. These students are engaged in over ten


CHEMICAL ENGINEERING EDUCATION








different projects which include studies on
different types of catalysts, as well as studies on
various types of reactions such as hydrogenation,
hydrogenolysis, isomerization, Fischer-Tropsch
synthesis, methanol synthesis, selective oxidation,
total oxidation, and deactivation. In most of the
projects, the objective is to search for funda-
mental chemical principles that govern the cata-
lytic reaction. One particular emphasis being
pursued is to relate the morphology and the com-
position of a catalyst to the kinetics and the
product selectivity of various reactions as well as
to the poisoning resistance characteristics. In
order to accomplish the above objective, it is
necessary to fully characterize the catalysts
chemically and physically. Chemical characteriza-
tion involves the study of reduction, oxidation, and
carefully chosen catalytic probe reactions. Physi-
cal characterization involves measurements of bulk
and surface morphology and composition. There-
fore, as stated above, we attack this combined
material and chemical science problem by ap-
propriate collaboration with faculty in the Ma-
terials Science and Engineering and Chemistry
Departments. Another feature is that we recog-
nize the importance and need to characterize the
catalysts under practical reaction conditions. Thus
as far as possible, spectroscopies capable of in situ
measurements are used. Currently these include
primarily x-ray diffraction and Mossbauer spectro-
scopy. Finally, whenever appropriate, the re-
actions are conducted at elevated pressures.
In other cases where in situ spectroscopic
measurements cannot be conveniently performed,
the catalysts are routinely characterized by various
techniques such as BET surface area measure-
ments, selective chemisorption, temperature pro-
grammed reduction, temperature programmed de-
sorption, and x-ray diffraction. Whenever ap-
propriate, they are also studied with M6ssbauer
spectroscopy, Auger electron spectroscopy, low
energy electron diffraction, and transmission
electron microscopy. While a large number of these
techniques are available in our Department and
many are dedicated to the projects involved, we
also make heavy use of the Materials Science
facilities of the Northwestern Materials Research
Center, and the analytical facility of the Chemis-
try Department. The three Materials Science
facilities most often used are the x-ray facility,
the M6ssbauer facility, and the electron micro-
scopy facility. The x-ray facility houses more than
ten x-ray diffractometers all of which are slaved


to microcomputers. For high intensity measure-
ments there are two rotating anode x-ray sources,
and we have also made use of the Cornell syn-
chrotron center in recent research. In addition to
obtaining the detailed structural information on
metallic catalysts that will be discussed later, the
x-ray facility is routinely used for particle size
determination, single crystal alignment, and struc-
tural identification from diffraction patterns. The
Mossbauer facility is used primarily to character-
ize supported iron, iron alloy, iron carbide and
nitride catalysts. It houses two spectrometers. The
electron microscope facility is used primarily to
characterize supported metal and supported oxide
catalysts by transmission electron microscopy both
in the bright field and the dark field modes.
The Chemistry analytical facilities are being
used currently mostly for the analytical aspects of
catalyst preparation. It houses a wide variety of
spectrometers such as infrared, Fourier trans-
formed infrared, UV-visible, NMR, GC-MS and

An important result of these very
different aspects of heterogeneous catalysis
is that it has now necessarily become an
interdisciplinary area of research.

other spectrometers, as well as a carbon-hydrogen-
nitrogen analysis service; of these, the FTIR is
currently of most use in our catalysis projects. A
C13 high field NMR will be available soon. The
technique of magic angle spinning will permit its
use on solid catalysts, so useful NMR techniques
will become possible.
The Chemical Engineering Department has
two ultra high vacuum chambers for modern
surface analyses. Each chamber is equipped with
a low energy electron diffractometer for the de-
termination of surface atomic crystallography, an
Auger electron spectrometer for surface composi-
tion determination, and a quadrupole mass spectro-
meter for reaction studies; these are dedicated
pieces of equipment. When needed, x-ray and ultra-
violet photoelectron spectrometers (XPS and
UPS) are also available in the Materials Science
surface facility.
The chemical characterizations that we use the
most are adsorption/desorption, reduction and re-
action measurements. Reaction product determina-
tion is often performed by gas chromatography
and mass spectrometry. As far as possible,
routine analyses of the products are performed
by microcomputers. An Apple II Plus and a NU


FALL 1981









Most of the current work is associated with various problems related
to catalyst deactivation, primarily by the mechanism of poisoning-so much so that
Jim Carberry has suggested we dub ourselves the L. Borgia Laboratory of Catalyst Decay


Micro 80 computer are connected to the mass
spectrometers, and recording integrators are used
with gas chromatographs. In the near future, we
expect to see a large increase in the use of micro-
computers to automate data acquisition and pro-
cessing.
When stating the general objective in catalysis
research earlier, we emphasized the need to use
various techniques in materials and chemical
characterization. It is natural then that our re-
search would benefit from scientific exchange and
collaboration with experts in the Materials
Science and Chemistry disciplines. Indeed cross-
disciplinary collaborative research has been a
unique and fruitful experience at Northwestern.
In the past six or seven years, there have been
four extensive projects that involve direct partici-
pation from faculty and students in Chemistry
and/or Materials Sciences. Three of these will be
discussed in greater detail later. In addition to
these formal collaborations, there are countless in-
formal discussions and consultations. For example,
neither of us has formal training in the area of
ultra high vacuum surface science. Thus when
we set up the surface analytical tools, the task
was made much easier when Professor Peter Stair
of Chemistry and Professor Yip-Wa Chung of
Materials Sciences offered to share their wisdom
and experience.

CATALYTIC REACTION ENGINEERING

CATALYTIC REACTION ENGINEERING has had a
rather long history in our department and
names of faculty both past and present who have
contributed research in this area include J. S.
Dranoff, H. M. Hulburt, Y. G. Kim, J. M. Smith,
and G. Thodos. Over the years this work has en-
compassed a wide variety of interests including
kinetic studies, pore diffusion problems, catalytic
reactor design and analysis, photocatalytic re-
actions, and catalyst deactivation. Most of the
current work is associated with various problems
related to catalyst deactivation, primarily by the
mechanism of poisoning-so much so that Jim
Carberry has suggested we dub ourselves the L.
Borgia Laboratory of Catalyst Decay.
Many of the techniques and approaches that


we have mentioned in the previous section carry
over directly to the work in catalyst deactivation.
To this we may add one special type of "spectro-
scopy": the fixed bed reactor or single catalyst
particle undergoing catalyst decay. Our particular
interests have been in how catalyst poisoning or
coke formation influences the dynamics of parti-
cles or reactors. These effects manifest themselves
in two ways; first, the existence of deactivation
itself means that our familiar steady-state
problems become unsteady-state ones (with vastly
differing time scales) and, second, the dynamics
of partially deactivated systems to perturbations
in concentration or temperature are different from
those of undeactivated systems.
Another aspect that is somewhat unique to
these "spectroscopies" is the fact that they are
completely tied in with the measurement of
gradients. Thus, rather than gradientless reactors,
we have "grandientfull" ones, and much of our
work has dealt with the reconciliation of theoreti-
cal models of varying degrees of complexity to ex-
perimental data on the motion of thermal waves
within fixed bed reactors or individual catalyst
particles.
Some of our more recent work on poisoning
has a clear interrelation with the catalysis
studies of supported metals. In that work (de-
scribed in more detail below) a major interest is
in the relationship between the morphology of a
supported metal crystallite, in particular size, and
its catalytic properties. It has been shown that for
certain reactions the specific activity of an in-
dividual metal atom depends upon the size of the
crystallite in which it is found; in such instances
the reaction is termed "structure sensitive." It
stands to reason that it is possible that the poison-
ing of such metal crystallites could also be struc-
ture sensitive, and if so, one might use some good
catalytic reaction engineering to try to tailor the
catalyst for maximum resistance to poisoning.
Systems such as carbon monoxide on platinum are
being investigated in this work and, since there
is a considerable amount of information available
from surface chemical physics studies on such
systems, the additional hope is that we can effect
some bridging of results from the two types of
experiments.


CHEMICAL ENGINEERING EDUCATION









OUR CLUB: THE CATALYSIS, ENGINEERING AND
SURFACE SCIENCE SEMINAR

T HE INTENSE INTEREST IN catalysis and catalytic
reaction engineering, and the extensive in-
volvement among various faculty in different de-
partments result in a core group of over thirty-
five graduate students working in these areas.
This large number of students enables us to have
a weekly seminar group. The participants in the
seminars are both graduate students and faculty,
and topics span a wide range from surface chemi-
cal physics calculations and measurements to
surface organometallic chemistry, to reaction
kinetics and mechanisms, and to catalyst deactiva-
tion engineering. The students are therefore being
exposed to a broad view. Visitors often inject new
ideas and approaches also.
While we enjoy and benefit from the collabora-
tive atmosphere among people in various disci-
plines, graduate students in our department also
receive a coordinated introduction to catalysis re-
search through a series of courses. Currently,
there are three courses on this subject in our de-
partment. One course surveys the various spectro-
scopic methods currently used in catalysis; one
surveys the modern theory and current research;
one surveys the industrial and processing aspects
of catalysis. In addition, students commonly take
courses in advanced kinetics, x-ray diffraction,
electron microscopy and others. In the reaction
engineering area, in addition to an entry level
graduate course in kinetics and reactor design, an
advanced reactor course is offered covering gas-
liquid, multiphase, chromatographic, and fluidized
bed design and analysis. In recent years we have
also been offering a course on reactor stability in
alternate years. Our modest goal in both catalysis
and reaction engineering is to make our students
as broadly-based and as knowledgeable as possible.

SOME EXAMPLES

T HUS FAR WE HAVE HIGHLIGHTED the special
features of our research efforts in general
terms. Now we discuss as examples three projects
to illustrate in detail some of these features.

Fischer-Tropsch Catalysis
The catalytic production of higher hydro-
carbons from CO and H2 is known as the Fischer-
Tropsch process. The possible change of the source
of raw material from crude oil to other fossil fuel


has renewed interest in the study of this process.
We are studying this on iron, promoted iron, and
iron alloy catalysts to determine how the proper-
ties of iron and the chemical nature of the catalysts
are being affected by the alloying agents and
promoters, and what their relationship is to the
activity and product selectivity. One of us (JBB)
in collaboration with Professor L. Schwartz in
Materials Science (who provides expertise in
Mbssbauer spectroscopy and electron microscopy)
began this project by studying supported iron
catalysts. Starting with a calcined supported iron
oxide, the reduction of the oxide to metal can be

1.002

.J r^-^A-r


.986
.978


.970

.994
.986
.978

S.970

1.002
3 .994

.986
.978
.970
1.000
.996


.992


.988 [
.984

-9 -6 -3 0 3 6 9
VELOCITY (r/sec)

FIGURE 1. Identification of oxidation-reduction for a
5% (wt) Fe/SiO2 catalyst via Mossbauer
spectroscopy. (a) calcined sample, (b) re,
duced in H2 for 12 h, (c) Spectrum of (b)
after exposure to 02 at room temperature,
(d) Reduced in H2 at 425 oC for 24 h in a
differential reactor.


FALL 1981










1.000

.992
.984
.976

.968

1.000
.992
.984
.976
.968


1.000
.996


.992 ' , VU
.988
.984

-9 -6 -3 0 3 .6 9
VELOCITY (mm/sec)
FIGURE 2. Identification of the carburization of a 5%
(wt) Fe/SiO2 catalyst via Mossbauer spectro-
scopy. (a) Carburized by 1:3 CO in H2 at
250 �C for 6 h, (b) Spectrum of (a) at liquid
N2 temperature, (c) Carburized by 1:3 CO
in H2 at 255 �C for 1.5 h in a differential
reactor.

easily monitored by M6ssbauer spectroscopy (Fig.
1). However the reduced metal is not very active
for the FT reaction. Instead, the activity slowly in-
creases with time on stream. Simultaneously the
M6ssbauer pattern slowly converts into one
characteristic of iron carbide (Fig. 2), which is
then the active phase. The reduction behavior of
the iron oxides is found to depend on the mode of
preparation. While attempting to interpret this
by the different crystallite sizes, we discovered
that x-ray line broadening and Mossbauer adsorp-
tion analysis gave misleading results on the
crystallite sizes of the iron particles on the support.
What happened was that both of these techniques
give sizes of the crystallites that are atomically
well ordered. Yet they cannot distinguish whether
these crystallites are physically separated from


each other, or clumped together to form a big
cluster. Transmission electron microscopy which
sees crystallites directly can easily distinguish
these possibilities. Indeed depending on the de-
tails in the catalyst pretreatment, different de-
grees of clustering can be obtained.
The type of information obtained for the
supported iron catalyst can likewise be obtained
for the promoted and alloyed catalysts. Coupling
Missbauer, kinetics and reduction measurements,
we found that some promoters affect the carbiding
of the catalysts, some affect the activity and se-
lectivity, while some affect stability of the cata-
lysts. Thus much richer information has been
obtained using this multi-technique approach
than would be possible with only some of these
techniques. It is clear that both the students in-
volved and the scientific understanding benefit
from the collaborative effort.


Supported Noble Metal Catalysis

Noble metal catalysts highly dispersed on an
inert support have long been a subject of research.
However, only recently have there been developed
techniques that permit us physically to probe
these metal clusters of only a small number of
atoms. Analysis of diffuse x-ray scattering now
can provide information on the average size, the
size distribution, the degree of perfection, and
crystallographic orientation of these crystallites.
This makes possible a very meaningful study that
involves a careful, well documented preparation
of these catalysts, x-ray characterization, and
chemical characterization by chemisorption,
deuterium isotope exchange reaction, hydrogena-
tion, isomerization and hydrogenolysis reactions.
This extensive program involves the participation
of three faculty: John Butt, R. L. Burwell, Jr. of
Chemistry, and J. B. Cohen of Materials Sciences.
An interesting result of this work is that it has
been found that the small noble metal crystallites
are crystallographically perfect down to as small
as two nanometers in diameter. Furthermore the
activity and selectivity in the test reactions vary
by less than a factor of five when the metal
crystallite sizes change from less than two nano-
meters to over fifteen nanometers. Pretreatment
conditions have a much more profound effect than
particle size alone.
Another study that was made possible by this
collaboration was the in situ x-ray characteriza-
tion of supported Pd catalysts. Fig. 3 shows some


CHEMICAL ENGINEERING EDUCATION-








of the findings in which a Pd/SiOz catalyst was
being exposed to a reaction mixture of hydrogen
and methylcyclopropane. If the starting catalyst
was Pd, the reaction mixture results in the forma-
tion of a mixture Pd metal and Pd hydride at
steady state. If the starting catalyst was Pd
hydride, the steady state of the catalyst was also
a mixture of Pd metal and hydride but of a
different proportion. We think this is the first
report of multiple steady states of a working
catalyst obtained by direct observation.

Mixed Oxide Catalysis
Almost all commercial oxide catalysts are
multicomponent, and it is of interest to understand
how these different components affect each other
catalytically. In particular, some of these com-
ponents in industrial catalysts are added as
promoters and their functions are not fully under-
stood. Our effort in this area has been to elucidate



DIFFRACTrION PEAK,
P STARTING CATALYST 100% Pd
Pd



AFTER 16:1::MCP:H2, 00C,10 MIN
70% Pd, 30% PdHg.7


PdHO,7


DIFFRACTION PEAK
S TARTING CATALYST 10% Pd, 90% PdH0.7






AFTER 16:1::MCP:H2, 0, 6 AND 13 MIN
107, pd, 90% PdHO.7
Pd

TWO THETA ANGLE
FIGURE 3. The multiple steady states of a Pd/Si02
catalyst in the hydrogenolysis of methyl-
cyclopropane at 0 �C. (a) Starting with
100% Pd, steady state catalyst is 70%
metal, 30% hydride, (b) Starting with 10%
metal and 90% hydride, steady state
catalyst is unchanged.


One is also concerned with the
catalytic reaction engineering associated with
transport effects, reactor design, catalyst design ...

the effect of these promoters on bulk structural
stabilization, reducibility, and activity and se-
lectivity. The catalytic system being investigated
is the selective oxidative dehydrogenation of
butene to butadiene over ferrite catalysts promoted
by zinc and/or chromium. To achieve our objec-
tive, the surface and the bulk of the catalysts
must be well characterized. This would involve in
addition to catalytic measurements, measurements
of surface composition, bulk structure, reduction
behavior and chemisorption. H. Kung, in col-
laboration with Professor Y. W. Chung of Ma-
terials Science and Professor P. Stair of Chemis-
try, has measured quantitatively the surface
density of iron even though the samples are
electrically insulating. Temperature programmed
reduction and reaction further suggest that the
reducibility of the oxide greatly affects the se-
lectivity of the reaction. In particular, the carbon
dioxide production is reduced on catalysts more re-
sistant to reduction. These and other observations
allow us to conclude that the Zn and Cr additives
act as structural promoters by stabilizing the bulk
against reduction and structural transformation.
They also stabilize-the surface against reduction
which leads to enhanced selectivity. Finally, they
affect the active sites through long range
electronic interaction which results in enhanced
activity by lowering the activation energy of the
reaction.

Concluding Statement

T HE EXAMPLES ABOVE SERVE TO illustrate the
emphasis and the approach in most of our
catalytic research effort. To reiterate, we aim at
fundamental understanding of catalytic reactions
through detailed studies of the solid and the re-
action. A very special feature is that we try to
involve workers in other disciplines who bring in
a wide spectrum of expertise. This allows us to
make use of the fullest potential of many physical
and chemical techniques in a manner that would
be impossible for a single worker. Thus the re-
search problem can be more satisfactorily solved.
The collaboration also benefits the graduate
students by broadening their experience and
knowledge. We might add that the same state-
ment pertains to the faculty. 5


FALL 1981










Redea4ch on


PARAMETRIC PUMPING


H. T. CHEN (deceased), C. O. KEROBO,
H. C. HOLLEIN and C. R. HUANG
New Jersey Institute of Technology
Newark, NY 07102

PARAMETRIC PUMPING IS A new separation
technique that should rightfully take its place
alongside other chemical engineering unit opera-
tions. Parametric pumping is a cyclic separation
process characterized by flow reversal coupled to
a change in a thermodynamic variable. The
change in the intensive variable induces separa-
tion of the components of a fluid mixture in a two-
phase system consisting of one mobile and one
immobile phase (gas-solid, liquid-solid, or liquid-
liquid). The oscillating direction of fluid flow
enhances the separation normally achieved in ad-
sorption-desorption or liquid-liquid extraction pro-
cesses. Parametric pumping has received con-
siderable attention in recent years.
Parapumping represents a new development
in separation science, both because of its novelty
and because of its adaptability to techniques
commonly used in the separation of fluid mix-
tures, i.e., adsorption, extraction, affinity chroma-
tography, and ion-exchange chromatography. The
adaptation can be made in principle to any system
where alteration of an applicable intensive vari-
able, such as temperature, pressure, pH, ionic
strength, or electric field, results in a differential
shift in the distribution of solutes between the
mobile and immobile phases.
The new separation technique has the follow-
ing features:

1) Batch chromatographic separations can be made
semi-continuous or continuous; continuous opera-


A similar process which utilizes
cyclic variation of an intensive variable,
but no change in flow direction, called "cycling
zone adsorption," was developed by
Pigford and co-workers.


tion minimizes processing time (thereby reducing
degradation of sensitive substances like proteins)
and maximizes production rate.
2) The semi-continuous or continuous process, when
optimized, has a high separation capability, and
the solutes can be concentrated to certain desired
levels by setting the relative volumes of the ap-
propriate product streams.
3) No regeneration chemicals are needed to clean the
adsorbent, so chemical contamination of the
product streams is eliminated.
The late Wilhelm and co-workers [1] invented
the batch parapump and introduced a semi-
continuous parapumping process in 1966. Since
that time, a pre-existing industrial process, known
as "pressure swing adsorption," has been identi-
fied as operating on the parametric-pumping
principle [2, 3]. A similar process which utilizes
cyclic variation of an intensive variable, but no
change in flow direction, called "cycling zone ad-
sorption," was developed by Pigford and co-work-
ers in 1969 [4]. A number of review papers are
available: Sweed, 1971 and 1972 [5, 6]; Wankat,
1974 and 1978 [7, 8]; Rice, 1976 [9]; and Chen,
1979 [10]. We intend to concentrate this discussion
on the parametric pumping research work done in
our laboratories.

PARAPUMPING RESEARCH AT N.J.I.T.
A N EXTENSIVE AMOUNT OF work has been done
by Chen and co-workers using temperature and
pH as the intensive variables for parametric
pumping separations. Other intensive variables
under investigation are pressure, ionic strength,
and electric field. The overall objective of these
research projects is to demonstrate that para-
metric pumping is a feasible process for the sepa-
ration of fluid mixtures commonly found in life
sciences, and in chemical and pharmaceutical
industries. The research is oriented towards the
development of sound experimental programs and
suitable mathematical models for design, scale-up,
and optimization of the processes. Following is a
brief review of these research projects.


� Copyright ChE Division, ASEE, 1981

CHEMICAL ENGINEERING EDUCATION




















Hung-Tsung Chen was Professor of Chemical Engineering and
Assistant Chairman of the Graduate Program. He taught at N.J.I.T.
from 1966 until his death in 1981. He received his B.S. degree from
National Taiwan University in 1958 and his M.S. and Ph.D. degrees
from the Polytechnic Institute of New York in 1962 and 1964. He
was the author of a number of publications in the fields of para-
metric pumping and photopolymerization reactor design, and held
grants from the National Science Foundation for fundamental research
in these areas. (L)
Charles Kerobo has been a Research Associate at N.J.I.T. in the
field of parametric pumping since 1975. He received his B.S.Ch.E. and
M.S.Ch.E. degrees from N.J.I.T. in 1976 and 1979, respectively. He is
currently a Ph.D. candidate, and his parametric pumping research ex-
perience includes pressure-, pH-, and temperature-driven parapump
systems. (LC)


Helen Hollein has been an Adjunct Professor at N.J.I.T. since
1978. She received her B.S.Ch.E. degree from the University of South
Carolina in 1965, and worked for Exxon Research and Engineering
Company following graduation. She earned her M.S. degree at
N.J.I.T. in 1979 and is currently a Ph.D. candidate working on protein
separations via parametric pumping. (RC)
Ching-Rong Huang came to N.J.I.T. in 1966 and is currently Pro-
fessor of Chemical Engineering and Assistant Chairman for the
Graduate Program of the Department. He received his chemical engi-
neering degrees from National Taiwan University (B.S., 1954), Massa-
chusetts Institute of Technology (M.S., 1958), and the University of
Michigan (Ph.D., 1966). He also earned an M.S. in mathematics at the
University of Michigan in 1965. His research interests are in the areas
of rheology, transport phenomena, and mathematical modeling. (R)


THERMAL PARAMETRIC PUMPING
Chen and Hill [11] introduced the first com-
pletely continuous parametric pumping process in
1971. Five different versions of the thermal para-
pump (two continuous, two semi-continuous, and
the batch pump) were analyzed in terms of the
equilibrium theory and the appropriate mass
transport equations. The mathematical model
indicates that, under certain operating conditions,
the batch pump and pumps with feed at the en-
riched end have the capacity for complete removal
of a solute from one product fraction and for
arbitrarily large enrichment of that solute in the
other fraction. Separation factors and enrichment
are modest for pumps with feed at the depleted
end. Experimental verifications of these models
for the system toluene-n-heptane on silica gel have
been subsequently presented [12, 13, 14].
Continuous thermal parametric pumping was
extended to the separation of multicomponent mix-
tures. The model system used was toluene, aniline,
and n-heptane on silica gel [15]. A simple method
for predicting multicomponent separations was
developed. This method invokes the assumption
that a multicomponent mixture contains a series
of pseudo-binary systems. Each binary system
consists of one solute (toluene or aniline) plus
the common inert solvent (n-heptane). Experi-
mental data agreed reasonably well with the


analytical predictions.
The multicomponent system, glucose-fructose-
water on a cation exchanger (Bio-Rad AG50W-X4,
calcium form) was also studied [16]. Agreement
between experiment and theory was roughly
equivalent to that obtained above. Earlier studies
on the glucose-fructose-water system used fuller's
earth (LVM 16-30 Mesh) and activated carbon
as the adsorbent [17, 18].
Mathematical expressions for determining
optimal performance of equilibrium pumps were
derived, based on the separation of NaNOa from
water via an ion-retardation resin [19]. Emphasis
was placed on the operating conditions necessary
for achieving high separation factors with maxi-
mum yield.
The performance of non-equilibrium continu-
ous pumps for the case of NaCI separation from
water via an ion-retardation resin was also studied
[20]. The criterion for approach to equilibrium
operation was established for the cases where
large separations were deemed possible.
A scale-up of the continuous thermal para-
pumping system was made and the design equa-
tions were developed [21]. Proposals were out-
lined for the construction and operation of the
parapump assembly; the auxiliary equipment and
the instrumentation were also outlined. The com-
mercial parapump assumes the configuration of


FALL 1981









Parametric pumping is
a cyclic separation process characterized
by flow reversal coupled to a change
in a thermodynamic variable.


multiple parallel tubes in a heat exchanger shell;
this design facilitates direct thermal mode opera-
tion. The energy requirements were shown to be
of the same order of magnitude as that for distilla-
tion.
All of the thermal processes investigated by
Chen and co-workers were operated in the so-
called direct mode, i.e., the intensive variable is
applied instantaneously over the entire bed. This
is the more common method of operation for
thermal parametric pumping [7, 8]. Rice and Foo
[22] have recently carried out a direct-mode pro-
cess for the continuous desalination of water,
using a dual-column system.

pH PARAMETRIC PUMPING

PARAMETRIC PUMPING PROCESSES which are
based on pH variation are usually operated in
the so-called recuperative mode, i.e., the intensive
variable is set at a different level in the streams
entering either end of the bed. In this mode, the
pH change moves across the bed as the entering
streams penetrate the chromatographic column.
Sabadell and Sweed [23] developed pH para-
metric pumping in 1970 for the separation of
aqueous solutions of K+ and Na+ on a cation ex-
change resin. In 1975, Shaffer and Hamrin [24] re-
ported a pH parapumping process for trypsin re-
moval from an enzyme mixture (a -chymotrypsin
plus trypsin) using a Sepharose type ion ex-
changer. Since then, Chen and co-workers have
researched protein separations via pH parametric
pumping, with emphasis on maximum separation
and continuous operation.
A semi-continuous pH parametric pump was
experimentally investigated using the model
system of the two arbitrarily mixed proteins,
human serum albumin and human hemoglobin in
aqueous solution on Sephadex cation exchanger
[25, 26]. These two proteins have different iso-
electric points, and the processes developed for
the model system may be applied to any mixture
of proteins having different isoelectric points.
Proteins carry a net positive charge and will ad-
sorb on a cation exchanger at pH's below their
isoelectric points; proteins carry a net negative


charge at pH's above their isoelectric points. The
semi-continuous pump, which had a center feed
between an enriching column and a stripping
column, was operated batchwise during upflow and
continuously during downflow. Two pH levels were
imposed periodically on the system. Various
factors affecting the separation were examined,
including pH levels and ionic strength of the
protein solutions, reservoir displacement, and
product flow rate. Hemoglobin was stripped from
the top stream and enriched in the bottom stream;
the separation factor for hemoglobin reached a
limit of six in the best run. The albumin con-
centration remains unchanged in this process,
but removal of hemoglobin from the top stream
leaves the top product relatively richer (by weight
fraction) in albumin.
A "continuous" pH parametric pump was used
to separate the model system hemoglobin-
albumin on CM Sepharose cation exchanger [27].
This pump configuration had protein feed solu-
tions at low pH and at high pH (relative to the
isoelectric point of hemoglobin) introduced re-
spectively to the bottom and top of a chroma-
tographic column. It was shown that increasing
the volume of the top product to some optimum
level relative to the volume of the bottom product
gave the pump the capacity for large enrichment
of hemoglobin in the bottom product stream. Note
that this system is currently considered to be
"semi-continuous," because each cycle contains
two stages where product is not withdrawn. A
completely continuous parapumping process for
protein separations is being developed.
A mathematical model with finite mass trans-
fer was developed for the model system hemo-
globin-albumin on CM Sepharose [28]. This model
agrees quite well with the experimental data.
Various factors affecting the separation were
examined, including the addition of recycle stages
to the one-column process.
An equilibrium theory was used in a theo-
retical analysis of the batch single-column and
multi-column pH parametric pump [29]. Simple
grapl ical procedures for predicting separation
showed that a parapump consisting of a series of
columns packed alternately with cation and anion
exchangers is capable of yielding very high
separation factors. Experimental results, based on
a comparison of albumin enrichment in one-column
and two-column systems packed with CM and
DEAE Sepharose, were shown to support the
theory.


CHEMICAL ENGINEERING EDUCATION








Fractionation of multicomponent protein mix-
tures by multi-column pH parametric pumping
was investigated theoretically and experiment-
ally [30]. The parapump consists of a series of
chromatographic columns packed alternately with
cation and anion exchangers. Separation of a mix-
ture of n proteins requires a parametric pumping
system consisting of n columns and n+2 reser-
voirs. Various methods of operation of the para-
pump were discussed. Preliminary experimental
data was shown in this paper for the two-column
batch separation of the model system hemoglobin-
albumin on CM and DEAE Sepharose, and this
data was in qualitative agreement with the calcu-
lated results. Optimization of the batch two-
column system has been recently completed and
separation factors as large as twenty-five were
obtained for the mixture [31]. The semicontinuous
multicolumn data is being currently obtained.

PRESSURE PARAMETRIC PUMPING
P PRELIMINARY WORK HAS BEEN done on the
separation of gas mixtures. An equilibrium
plug-flow model for the batch isothermal system
(propane-argon on activated carbon) was studied
using pressure swing adsorption [32]. Effects of
temperature, pressure, and concentration were
investigated. A continuous pressure parapump
was studied for the model system carbon dioxide-
helium on silica gel [33]. The experimental results
were analyzed by means of an equilibrium theory,
and the various operating parameters necessary
for the complete removal of the solute (CO2) were
investigated.
The continuous process was extended to the
separation of a ternary mixture, propylene-
carbon dioxide-helium on silica gel [34]. Various
performance characteristics were examined.
Using the same model system, an experimental
and theoretical study was done based on a non-
equilibrium theory and linear adsorption iso-
therms [35]. A comparison was made for the
binary and ternary gas mixtures, and the condi-
tions necessary for the separation of the multi-
component mixtures were established.

SCOPE OF CURRENT RESEARCH

E EXPERIMENTAL STUDIES ARE currently in pro-
gress on two pressure swing systems: one for
the removal of organic from hydrogen streams
and one for the separation of hydrogen isotopes.
Although pressure swing adsorption is a common


industrial process, fundamental studies are limited
in the open literature [36]. The separation of
hydrogen isotopes on vanadium hydride was re-
cently reported by Wong, Hill and Chan [37].
The purification of the enzyme (alkaline phos-
phatese) by parametric pumping with pH and
ionic strength has been investigated using a semi-
continuous process [38]. Alkaline phosphatese, ex-
tracted from the human placenta, contains some
undesired proteins which have isoelectric points
approximately equal to that of the enzyme; hence,
the additional intensive variable (ionic strength)
is required. This new process is the first one re-
ported which uses ionic strength as the intensive
variable for parametric pumping. Comparison of
enzyme purification by parametric pumping and
cycling zone adsorption shows that the former


A new semi-continuous parapumping
process based on cyclic variation of pH
and electric field has been shown to be
capable of splitting two proteins
in a mixture from each other...


process has a higher purification factor and larger
% enzyme activity recovered, while the latter
process has a higher rate of production. Optimiza-
tion studies on the enzyme system indicate that
a parapump operation with the proper combina-
tion of the two intensive variables, pH and ionic
strength, is superior to a parapump system based
on only pH or ionic strength [39]. A comparison
of the purification of alkaline phosphatese via
parametric pumping to the purification which can
be obtained via a conventional process, such as
polyacrylamide gel electrophoresis, is nearly com-
pleted.
A new semi-continuous parapumping process
based on cyclic variation of pH and electric field
has been shown to be capable of splitting two
proteins in a mixture from each other, using a
single-column set-up [40]. The same model system
was used as in previous protein separation studies,
i.e., hemoglobin and albumin in aqueous solution
on CM Sepharose cation exchanger. The separation
obtained in the single-column, semi-continuous
pH parametric pumping process is enhanced by
inducing an electric field across the chromato-
graphic column during certain stages of the pro-
cess. Separation factors as high as 120 are re-
ported for the mixture. Mathematical analysis of
this system is currently underway. Separation, re-


FALL 1981








cover and production rate for this system will
be compared to the multicolumn pH system, when
the semi-continuous multicolumn data is available.
Other researchers have shown electrochemical
parapumping to be potentially useful for desali-
nation of water [41, 42].
Separation of protein mixtures by multi-
affinity chromatography combined with cyclic
operation is being investigated [43]. The system
consists of a series of columns packed alternately
with anion and cation exchangers (Sephadex
(G150) and Sepharose (4B)). Two cyclic methods
are being considered: semi-continuous parametric
pumping and continuous simulated moving bed
operation. This process is being adapted for the
separation of lectine mixtures, such as Convalin
A and Ricinus Communis Agglutinin I.
A staged sequence multicolumn cyclic process
is being developed for the separation of liquid
mixtures. This continuous process eliminates the
mixed reservoirs normally used in parametric
pumping. (Note that reservoir mixing tends to
reduce separation [22].) Separation of a mixture
of n solutes by the direct-mode of operation re-
quires a set-up with n+1 columns and n driving
forces. The feed and product ports are fixed in
the staged sequence process, but different com-
ponents can be directed to exit from specified
ports by synchronizing the feed and product
positions with the appropriate intensive variable.
Preliminary experimental results for semi-
continuous operation in a one-column system are
being extended to the continuous multicolumn
system. A mathematical model which fits the one-
column data is being modified to predict the
continuous separation.
From the discussion of active research areas,
it is evident that parametric pumping is a very
useful and versatile process in separation tech-
nology. It is our belief that commercialization of
some of these parapumping systems would be
economically feasible.


ACKNOWLEDGEMENT

Portions of this research were supported by
the National Science Foundation under Grants
ENG 77-04129 and CPE 79-10540. O


POSTSCRIPT
This article was initiated by Dr. Chen at the
request of CEE, prior to the tragic automobile


accident which ended his life on April 21, 1981,
and completed by his co-workers in his memory.

REFERENCES
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Eng. Chem. Fund., 5, 141 (1966).
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(Eds.), "Progress in Separation and Purification,"
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in Separation Science," Vol. 1, Chemical Rubber Co.,
Cleveland (1972).
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ings of the NATO Advanced Study Institute on
Percolation Processes," Espinho, Portugal (July,
1968).
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of Separation Techniques for Chemical Engineers,"
McGraw-Hill, New York (1979).
11. Chen, H. T. and F. B. Hill, Separation Science, 6,
411 (1971).
12. Chen, H. T., J. L. Rak, J. D. Stokes and F. B. Hill,
AIChE Journal, 19, 356 (1972).
13. Chen, H. T., E. H. Reiss, J. D. Stokes and F. B. Hill,
AIChE Journal, 19, 589 (1973).
14. Chen, H. T., J. A. Park and J. L. Rak, Separation
Science, 9, 35 (1974).
15. Chen, H. T., W. W. Lin, J. D. Stokes and W. R.
Fabrisiak, AIChE Journal, 20, 306 (1974).
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813 (1975).
17. Chen, H. T., J. Jaferi and J. D. Stokes, paper 9e pre-
sented at 73rd AIChE National Meeting, Minneapolis,
MN (August, 1972).
18. Ahmed, Z. M., paper F2-2 AIChE-GVC joint meeting,
Vol. IV of preprints, Munich, Germany (September,
1974).
19. Chen, H. T. and J. A. Manganaro, AIChE Journal,
20, 1020 (1974).
20. Chen, H. T., A. K. Rastogi, C. Y. Kim and J. L. Rak,
Separation Science, 11, 335 (1976).
21. Stokes, J. D. and H. T. Chen, Ind. Eng. Chem. Process
Des. Dev., 18, 147 (1979).
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150 (1981).
23. Sabadell, J. E. and N. H. Sweed, Separation Science,
5, 171 (1970).
24. Shaffer, A. G. and C. E. Hamrin, AIChE Journal,
21, 782 (1975).
25. Chen, H. T., D. I. Cho, J. Dell'Osso and P. Falcon,
paper 34b presented at 82nd AIChE National Meet-
ing, Atlantic City, NJ (August, 1976).
26. Chen, H. T., T. K. Hsieh, H. C. Lee and F. B. Hill,
AIChE Journal, 23, 695 (1977).


CHEMICAL ENGINEERING EDUCATION









27. Chen, H. T., Y. W. Wong and S. Wu, AIChE Journal,
25, 320 (1979).
28. Chen, H. T., W. T. Yang, C. M. Wu, C. O. Kerobo and
V. Jajalla, Separat. Sci. and Tech., 16, 43 (1981).
29. Chen, H. T., U. Pancharoen, W. T. Yang, C. O. Kerobo
and R. J. Parisi, Separat. Sci. and Tech., a5, 1377
(1980).
30. Chen, H. T., W. T. Yang, U. Pancharoen and R. J.
Parisi, AIChE Journal, 26, 839 (1980).
31. Chen, H. T., D. Hanesian and A. Allentuch, "Separa-
tion and Purification of Proteins via Continuous Para-
metric Pumping," N. S. F. Report (March 25, 1981).
32. Lopez, J. G., M. S. Thesis, New Jersey Institute of
Technology (1973).
33. Weingartner, P. F., M. S. Thesis, New Jersey Insti-
tute of Technology (1973).
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Technology (1977).
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Technology (1977).
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Eng. Sci., 86, 243 (1981).
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Sci. and Tech., 15, 423 (1980).
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Chem. Fund., 20, 171 (1981).
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tute of Technology (1981).
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be presented at 2nd World Congress of Chemical
Engineering, Montreal (October, 1981).
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Engr., 52, 345 (1974).
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869 (1978).
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paper to be presented at AIChE New Orleans Meet-
ing (November, 1981).


9#t Memo&ia#K

HUNG TSUNG CHEN
Hung Tsung Chen was killed in an auto acci-
dent on April 21, 1981. His numerous students,
faculty colleagues, and members of the New Jersey
Institute of Technology community will miss him
a great deal. The work he did in the area of para-
metric pumping and polymer engineering was
exemplary and he is irreplaceable. We all extend
our sympathies to his wife Vera, his son, Andrew,
and his daughter, Carol.
Dr. Chen was born in Taiwan, Republic of
China, on August 23, 1935. He attended the
National Taiwan University and obtained his BS
degree in chemical engineering in 1958. He came
to the United States and received both the MS
(1962) and PhD (1964) in chemical engineering
from Brooklyn Polytechnic Institute. He worked
under the supervision of Dr. Othmer.
Following his graduate studies he worked for
FMC Corporation. In 1966, he joined the faculty
of the Department of Chemical Engineering and
Chemistry at New Jersey Institute of Technology
where he worked until his untimely death. Dr.
Chen was a Full Professor and Assistant Chair-
man of the Graduate Program. He has served as a
consultant for numerous companies including
Bookhaven National Laboratory. He was an ex-
cellent undergraduate and graduate teacher and
was highly admired by his students. He worked in
the area of parametric pumping and had developed
into one of the leading international authorities on


the subject. He had more than 20 graduate
students working with him in this area and poly-
merization reactor technology. Dr. Chen, a prolific
publisher, had more than 40 publications. He also
contributed to Handbook of Separation Techniques
for Chemical Engineers. One publication in the
AIChE Journal was accepted without any revision
needed. The Editor called this a "first."
He served the department and Institute on
many committees. He was an active member of
AIChE, Sigma Xi, Omega Chi Epsilon and was a
registered professional engineer.
Dr. Chen was an invited speaker at the Gordon
Conference (1980), had numerous NSF grants,
was named "Outstanding Educator of America,"
was listed in Who's Who in the East, American
Men of Science, Community Leaders and Note-
worthy Americans, Directory of International
Biography, and Men of Achievement.
On May 28, 1981, at our Institute's Centennial
Year Commencement exercise, Dr. Chen received
(posthumously) the first Harlan J. Perlis Award
for Excellence in Research given by our Institute.
The award was received by his wife, Vera, with a
standing ovation.
Dr. Chen can never be forgotten. He is irre-
placeable and future generations of chemical en-
gineering students have been deprived of his atten-
tion by our great loss. Dr. Chen will always be
with us, and will represent a standard of high
achievement and excellence. He will be missed
very much by our chemical engineering profession.

Deran Hanesian
Angelo Perna


FALL 1981










ReeaiAc on


MOLECULAR THERMODYNAMICS

AND COMPUTER SIMULATION


KEITH E. GUBBINS
WILLIAM B. STREET
Cornell University
Ithaca, NY 14853

T HE FOUNDATIONS OF MOLECULAR thermo-
dynamics were laid about 100 years ago by
J. D. van der Waals working in Amsterdam and
J. Willard Gibbs at Yale University. The first
realistic equation of state, and also the principle
of corresponding states, were proposed by van der
Waals, and led to a flourishing Dutch school of
thermodynamics (Roozeboom, Schreinemakers,
Buchner, Kuenen, and others) and extensive
studies of binary phase equilibria. Gibbs intro-
duced the phase rule and provided the basis for
all modern work on both classical chemical thermo-
dynamics and statistical mechanics.
From its beginnings chemical engineering has
included classical thermodynamics as an important
branch of the subject. Classical thermodynamics
tells us how to carry out calculations given the
necessary property data, but tells us nothing
about how to predict the data needed for design
or operation of chemical processes. For this we
must turn to statistical mechanics, the science
that connects the properties of interest to the
underlying intermolecular forces. Over the past
25 years chemical engineers have increasingly
used statistical mechanics as a starting point for
predictive techniques and correlations. Notable
successes that have been thoroughly integrated
into industrial use include the calculations of heats
and free energies of formation of gases and


The three approaches of
experiment, theory, and computer simulation
are complementary and are most powerful
when combined in a comprehensive
study of particular liquids
and liquid mixtures.


� Copyright ChE Division, ASEE, 1981


solids [1], the virial equation of state for com-
pressed gases [2], and a variety of corresponding
states methods [2, 3]. Among the more difficult
problems have been the prediction of thermo-
dynamic and interfacial properties of liquids.
Some chemical engineering problems of current
interest that call for further research on liquid
properties include:
* The need for experimental studies and prediction
methods for new fuel technologies, including coal
liquefaction and gasification, the conversion of methanol
to gasoline, hydrogen-energy technology, processing
liquefied natural and synthetic gas, and the production
of ethanol. Existing prediction methods were developed
for hydrocarbon mixtures, and often fail for synthetic
fuels.
* Prediction of solvent effects on reaction rates and
equilibrium yields.
* The design of high pressure separations equipment
and multiphase reactors.
* The role of surface properties (surface tension,
molecular alignment, diffusion rates, etc.) in the use
of surfactants in modifying emulsions and oil recovery,
interfacial transfer rates in extraction equipment,
nucleation, lubrication, liquid-phase reactions at a solid
surface, adsorption and chromatography, crystalliza-
tion, and the design of artificial organs for the body.
The most significant advances that have oc-
curred in molecular thermodynamics of liquids in
the past decade have been: (a) the development
of new prediction methods for polar (and other)
liquids of industrial interest, based on perturba-
tion theory, (b) the rapid development of com-
puter simulation techniques for such liquids, in
which the properties of precisely defined model
fluids are evaluated by using the computer to
calculate molecular motions and configurations,
(c) experimental studies of phase equilibria and
critical phenomena in highly nonideal mixtures
over wide ranges of pressure and temperature, and
(d) the study of interfacial properties by both
theory and simulation. The three approaches of
experiment, theory, and computer simulation are
complementary (Figure 1) and are most powerful
when combined in a comprehensive study of par-
ticular liquids and liquid mixtures. A program


CHEMICAL ENGINEERING EDUCATION








combining these three methods was initiated in
the School of Chemical Engineering at Cornell
University in 1977.


EXPERIMENTAL STUDIES OF FLUIDS

E EXPERIMENTAL THERMODYNAMICS AT Cornell
currently includes measurements of phase
equilibria, PVT properties, and heats of mixing.
The phase equilibria and PVT studies are carried
out over wide ranges of pressure and temperature
(0-10,000 atm, 70-500K) to provide extensive
data for testing and refining the predictions of
theories based in molecular physics and statistical
mechanics. Mixtures for study are chosen mainly
on the basis of the types of molecules (spherical,
diatomic, triatomic, etc.) and intermolecular forces
(dipolar, quadrupolar, hydrogen-bonded, etc.) to
provide examples of several classes of industrially
important mixtures. Recent phase equilibrium ex-
periments for binary mixtures include: simple
nonpolar systems, such as krypton/xenon, kryp-
ton/methane, and krypton/ethane; systems con-
taining polar liquids such as carbon dioxide/
dimethyl ether [4] and methanol/dimethyl ether;
and a family of hydrogen binary mixtures includ-
ing hydrogen/nitrogen [5], hydrogen/methane [6],
hydrogen/carbon monixide [7], and hydrogen/
carbon dioxide [8]. The hydrogen/X phase dia-
grams have been studied at pressures up to about
1500 atm. Together with earlier studies of helium/
X and neon/X systems carried out at pressures
as high as 10,000 atm [5], they provide a compre-
hensive picture of fluid phase behavior in binary
systems in which one pure component is a highly
supercritical gas and the other a liquid.
The experimental apparatus used in this work
includes a vapor-recirculating equilibrium system,
in which the vapor phase is continuously recircu-


TEST OF
MODEL,


TEST OF
\THEORY


I TEST of MODETHEORY
EXPERIMENT TEST TEORMY THEORY

FIGURE 1. Three methods of studying properties, and
the interaction between them. 'Model'
refers to the intermolecular force law.


Keith E. Gubbins is currently the Thomas R. Briggs Professor of
Engineering at Cornell University. He received his B.S. and Ph.D.
degrees at the University of London, and was on the staff at the
University of Florida from 1962-1976, when he moved to Cornell. He
has held visiting appointments at Imperial College, London, Oxford
University, the University of Kent, and the University of Guelph,
and has coauthored two books, Applied Statistical Mechanics (Reed
and Gubbins) and Theory of Molecular Liquids (Gray and Gubbins-
to appear in 1982). (L)
William B. Street is Professor of Chemical Engineering at Cornell
University, where he has been a member of the faculty since 1978.
He received a B.S. degree from West Point and a Ph.D. in mechanical
engineering from the University of Michigan. He spent 23 years in
the Army, mainly at West Point where he was the founder and first
Director of the Science Research Laboratory. His research interests
are in experimental thermodynamics of fluids and computer simulation
studies of molecular liquids. He was awarded a Guggenheim Fellow-
ship in 1974. (R)


lated through a closed loop of high pressure tubing
by means of a magnetically operated pump, and
bubbled through the liquid phase [4, 5]. After
equilibrium is established at fixed P and T, samples
of the two phases are withdrawn through stainless
steel capillary lines and analyzed by means of a
thermal conductivity detector or gas chromato-
graph.
Recent experiments have shown that there are
continuous transitions at high pressures between
phase separations of the gas-liquid, liquid-liquid,
and so-called "gas-gas" types [9, 10]. An example
of such a high pressure phase diagram produced
by our experiments is shown in Figure 2. These
diagrams are often found in mixtures of highly
dissimilar molecules, in which the critical tempera-
tures of the pure components are far apart.
Examples include He/CH4 [11], He-Xe [12], and
He-C02 [13]; experimental data for the He/CH,
system, for example, cover temperatures from 95
to 290 K, and pressures to 10,000 atm. A gaseous
mixture of 75 mole % helium in methane, com-
pressed isothermally at 20�C, separates into two


FALL 1981








fluid phases at about 8000 atm; at 10,000 atm the
light phase contains about 95% helium and the
dense! phase about 45% helium. (A temperature


FIGURE 2. Schematic three-dimensional phase dia-
gram for a binary system that exhibits gas-
gas equilibrium. Lines AC and AD, in the
near P-T face of the diagram, are the vapor
pressure and melting curves of the pure
heavy component. The critical temperature
of the light component lies well below the
triple point A, out of the range of the
diagram. The planes T, - T, are isotherms
and P1 - P2 are isobars, in which the
shaded areas are regions of phase separa-
tion. The curved boundaries of these areas
are lines cut by planes of constant T or P
in the pairs of surfaces that describe the
equilibrium between two phases. The mix-
ture critical line, CC', begins at the critical
point, C, of the pure heavy component,
and rises to higher temperature at higher
pressures. Thus isotherms T2 and T3 repre-
sent phase separations at temperatures
above the critical temperatures of both pure
components-the phenomenon commonly
known as gas-gas equilibrium. The shaded
surface AFGBEA describes a region of
equilibrium between three phases: a solid
phase represented by AE, a liquid phase
AB, and gas phase AFG. At low pressures
this region terminates in the triple point,
A, of the pure heavy component.


of 20�C corresponds roughly to T, in Figure 2).
Accurate prediction of thermo-physical properties
under these extreme conditions poses a severe test
for any prediction method.

THEORY OF LIQUID MIXTURES

T HE METHODS CURRENTLY USED BY chemical
engineers to predict liquid properties are
based largely on theories developed before 1970;
these theories assume the molecules are roughly
spherical and interact rather weakly. They are
satisfactory for near-ideal solutions, but perform
poorly for mixtures involving polar or super-
critical fluids, or when liquid-liquid immiscibility
occurs [14].
Since 1972 interest has turned to theories for
liquids composed of nonspherical molecules, in
which the intermolecular forces are strongly
orientation-dependent, and include long-range
(e.g. dispersion, electrostatic) and short-range
(repulsion, hydrogen-bond, etc.) contributions. At
the present stage of development the theory is
capable of predicting the thermodynamics of fluids
of fairly small polar and quadrupolar molecules,
such as HC1, C02, HO0, lower molecular weight
alcohols, hydrocarbons, etc. The most successful
approach for thermodynamic properties is pertur-
bation theory, in which the properties of the fluid
of interest are related to those of a reference fluid
with simpler intermolecular forces. The properties
of the two fluids are connected via an expansion
in powers of the perturbing force or potential.
For the Helmholtz free energy A, for example,
we have
A = Ao + A, + A2 + As +...
where Ao is the reference fluid free energy, Ai is
the first order perturbation term, and so on. Ex-
pressions for the perturbation terms involve
reference fluid properties, and are obtained from
the expressions of statistical mechanics. Recent
advances in such theoretical equations of state
have come from the improved understanding of
suitable reference fluids, and from the use of
standard mathematical methods (e.g. Pad6 ap-
proximants) to accelerate series convergence. Such
perturbation expansions are more powerful than
the traditional corresponding states methods, since
they can be applied to mixtures of constituents
that obey different intermolecular force laws (e.g.
hydrocarbons with alcohols, as occurs often in
coal-derived synthetic fuels). In the most widely
studied form of the theory, the reference fluid is


CHEMICAL ENGINEERING EDUCATION









Classical thermodynamics tells us how to carry out calculations given
the necessary property data but tells us nothing about how to predict the data needed for
design or operation of chemical processes. For this we must turn to statistical mechanics, the
science that connects the properties of interest to the underlying intermolecular forces.


taken to be one of spherical or near spherical
molecules, and the perturbation terms then ac-
count for the nonspherical force contributions due
to dipoles, nonspherical shape, etc. [15]. This
method is superior to the existing chemical engi-
neering prediction methods for mixtures that
involve polar liquids or are otherwise highly non-
ideal [6, 15-21]. A comparison of theory and ex-
periment is shown in Figure 3 for H2/CH4 [6], a
highly nonideal system with a three-dimensional
PTx phase diagram of the form shown in Figure
2. In this case H2 is supercritical, and quantum
effects are important.
Much remains to be done to develop these
methods for hydrogen-bonded liquids, dilute solu-
tions, liquid-liquid immiscible systems, synthetic
fuel mixtures, supercritical extraction, etc. The
further development of theoretical equations of
state will be aided by combining theoretical work
with computer simulation studies and experimen-
tation.

COMPUTER SIMULATION
IN COMPUTER SIMULATION THE fluid is repre-
sented by a small sample containing a hundred
to a few thousand molecules [22]. The equation de-
scribing the intermolecular forces is precisely
specified, and surface effects are minimized by the
use of periodic boundary conditions, in which the
basic cell containing the sample is surrounded by
replicas of itself. Such small samples have been
found to faithfully represent macroscopic systems
except for fluids with quantum effects or near criti-
cal points. Two simulation procedures have been
used-the Monte Carlo (MC) and molecular
dynamics (MD) techniques, both introduced in the
1950's. In the MC method the many-dimensional
integrals that arise in statistical mechanics are
evaluated by sampling using random numbers. In
the MD method the Newtonian equations of
motion are solved numerically for each molecule in
the sample, keeping the system energy, volume and
number of molecules fixed. The molecular motions
are followed for a period of the order of 10-9 sec.,
and averages over these motions are then taken
to obtain the thermodynamics, diffusion co-


efficient, molecular distributions, etc. MD has the
advantage that transport properties can be studied,
whereas in MC calculations only the equilibrium
properties are obtained. However in MC the
energy and volume need not be kept constant; this
is an advantage in many applications of interest
to chemical engineers, e.g. the study of phase
equilibria.
At Cornell these studies are carried out on a
dedicated PDP 11/70 computer, and on a Floating
Point Systems array processor. Research problems
in this area include:

* Studies of activity coefficients in liquid mixtures
containing polar and supercritical components, and the
development of better equations to describe them.
* Studies of gases dissolved in liquids and systems used
in supercritical extraction (solids or liquids dissolved in
compressed gases). A recent result for such a study of
the Henry's constant in simple liquid mixtures [23] is
shown in Figure 4.
* Development of computer graphics techniques for the
display of molecular motions and orientation in liquid
mixtures and at surfaces, and for displaying three
dimensional phase diagrams and projections of these.


1000


800


* 600


400


200


0.2 0.4 0.6 0.8 1.0


FIGURE 3. VLE for H2/CH, at 100K from experiment
(points), perturbation theory (solid line) and
Redlich-Kwong equation (dashed line)
[from ref. 6].


FALL 1981


I!

i a


0

0
r

0
/



to

-


I I I








* Nucleation studies, where nucleation rates are
controlled by poorly understood surface effects.
* Molecular diffusion and orientation at gas-liquid, liquid-
liquid, solid-liquid, and solid-gas interfaces.
* Behavior of surfactants at interfaces.
* Droplet properties-surface tension, diffusion, etc.

SURFACE PROPERTIES

T HE INTERFACE BETWEEN TWO phases is an in-
homogeneous layer that is usually only two
or three molecules thick. The interfacial proper-
ties (diffusion rates, molecular orientation,
surface tension, pressure tensor, adsorption, etc.)
play a crucial and often poorly understood role
in many chemical engineering processes-in
separations, oil recovery, heterogeneous reactions,
etc. Because of the thinness of the interface, ex-
perimental studies are fraught with difficulty.
Relatively sophisticated particle beam scattering
experiments can be carried out on solid surfaces,
but cannot be used for liquid surfaces because
they require a vacuum above the liquid. Computer
simulation and theoretical studies therefore play
a particularly important role [24, 25]. The first
simulations of gas-liquid interfaces were carried
out in the mid-1970's, and are now being extended
to solid-liquid interfaces and polar liquids. In addi-
tion to the perturbation theory approach described

5.



o % Vca Vcb


.S -5 -
-s-s


-10 -


0 0.5 1.0 1.5 2.0
(Tca/Tcb)'2
FIGURE 4. The Henry constant K, for solute a in solvent
b as a function of (Tea/Teb) for a mixture of
simple spherical molecules from MC simula-
tion (points, solid line) and two current
theories (dashed line = expansion about
pure solvent, dotted line = Mansoori-
Leland approximation). Here T, , V, are criti-
cal temperature and volume, v is molar
volume of solvent (from ref. 23).


A great variety of surface effects
of practical interest remain to be studied ...


above for bulk liquids, an alternative approach
known as integral equation theory seems promis-
ing for surface properties. A great variety of
surface effects of practical interest remain to be
studied, some of which have been listed under
computer simulation above. Others include the de-
velopment of predictive methods for calculating
surface tensions, adsorption at interfaces, dif-
fusion rates across and through the surface
layer, and nucleation rates.

CONCLUSION
AFTER A PERIOD OF CONSOLIDATION in the 1960's,
molecular thermodynamics has in the last six
or seven years entered a period in which there
have been dramatic developments in both experi-
mental studies of phase behavior, and in the
techniques of theory and simulation. In parallel
with these developments, chemical engineers have
been faced with challenging thermodynamics
problems in new processes for synthetic fuels, oil
recovery, and new separations techniques. The
most profitable line of approach will involve care-
fully planned studies that combine the techniques
of experiment, theory and simulation. E

ACKNOWLEDGMENTS
It is a pleasure to thank the National Science
Foundation, the Gas Research Institute, and the
Donors of the Petroleum Research Fund of the
American Chemical Society for continued support
of this research. We thank Katherine Shing for
permission to reproduce Figure 4.

REFERENCES
1. JANAF Thermochemical Tables, Nat. Stand. Ref.
Data Series, Nat. Bur. Stand. 37, U.S. Department
of Commerce (1971); F. D. Rossini et al., "Selected
Values of Chemical Thermodynamic Properties," Nat.
Bur. Stand. Circular 500 (1952).
2. T. M. Reed and K. E. Gubbins, "Applied Statistical
Mechanics," McGraw-Hill, New York (1973), Chap.
7, 11; J. M. Prausnitz, "Molecular Thermodynamics
of Fluid Phase Equilibria," Prentice-Hall, Englewood
Cliffs (1969), Chap. 4, 5.
3. R. C. Reid, J. M. Prausnitz and T. K. Sherwood, "The
Properties of Gases and Liquids," 3rd edition,
McGraw-Hill, New York (1977), particularly Chap.
Continued on page 197.


CHEMICAL ENGINEERING EDUCATION









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COAL LIQUEFACTION AND DESULFURIZATION


J. A. GUIN, Y. A. LIU, C. W. CURTIS,
A. R. TARRER AND D. C. WILLIAMS
Auburn University
Auburn, AL 36849

A LABAMA IS A SIGNIFICANT producer of coal in
the United States, particularly in the Gulf
province. There are large reserves of coal in Ala-
bama; 35 billion tons lie in the northern and
central counties, enough for hundreds of years at
our present rate of production. Lignite deposits
in southern Alabama counties await the technology
to properly realize their value. Thus, a strong
recommendation of a statewide conference on
"Energy and the Future of Alabama" sponsored
by Auburn University in 1972 was for "research,
development and technical liaison in the areas of
coal production, coal processing and coal usage."
Auburn University acted upon this recommenda-
tion, and with major support from the National
Science Foundation (NSF), established the Au-
burn Coal Conversion Research Laboratory in
the Department of Chemical Engineering in 1973.
Subsequently, with additional support from NSF
in 1975, Auburn University established a Coal
Preparation Research Laboratory. Since their
initiation, the Auburn Coal Research Laboratories
have been heavily involved in the graduate train-
ing of selected M.S. and Ph.D. students in the areas
of coal conversion and utilization. A major thrust
of the recent and ongoing research has been
placed on coal liquefaction and desulfurization.
The program is presently the largest university-
based coal research program in the Southeastern
region, and current support for the program is at
a level of about $450,000 annually. Recent and
current sponsors of the program, summarized in
Table 1, have included many industrial organiza-
tions. Of particular significance is the fact that
the Southern Company Services, Inc., which is
widely recognized in the area of coal conversion
technology and applications of coal-derived fuels,
has continued since 1973 to actively support many

� Copyright ChE Division, ASEE, 1981


The program is presently the
largest university-based coal research
program in the Southeastern region, and current
support is ... about $450,000 annually.


aspects of the Auburn coal liquefaction research
program. It has made available its resources and
facilities at the 6 tons/day solvent-refined-coal
(SRC) pilot plant located at Wilsonville, Alabama
(90 miles from Auburn) for support of the super-
vised internship and hands-on research training of
the Auburn program. The largest utility coal user
in the Northeast, the New England Electric
System, has also actively participated in the Au-
burn coal desulfurization research since 1978.

COAL RESEARCH FACULTY AND FACILITIES
The Auburn coal liquefaction research program
is presently being directed by a number of
chemical engineering faculty, including Drs. J. A.
Guin, A. R. Tarrer, C. W. Curtis and D. C.
Williams. These individuals have had extensive
coal liquefaction research experience, particularly
related to the aspects of transport phenomena,
reaction engineering, analytical chemistry, applied

TABLE 1
Recent Sponsors of the Auburn Coal Research Program
Disposable catalysts for coal liquefaction:
Air Products and Chemicals, Inc.
Corrosion by coal liquids: Catalytic, Inc.
Catalyst deactivation in coal liquefaction:
Cities Service Research and Development
Two-stage coal liquefaction: Electric Power Research
Institute
Visual reactor studies of coal dissolution:
Gulf Research and Development Company
Magnetofluidized beds and coal desulfurization:
New England Power Service Company
Magnetic beneficiation of coal: Union Carbide Corporation
Graduate training in coal conversion and utilization:
U.S. Department of Education
Solvent refining of coal: U.S. Department of Energy
Dry coal desulfurization: U.S. Department of Energy


CHEMICAL ENGINEERING EDUCATION









catalysis and separation processes. Both Drs.
Guin and Tarrer have served as project managers
for the Fossil Energy Program of the U. S. De-
partment of Energy, providing the Auburn Labo-
ratories with unique and practical insights to the
ongoing coal conversion research in the country.
In addition, Dr. S. C. Worley of the Department
of Chemistry and Dr. B. Tatarchuk, a new chemi-
cal engineering faculty in the Fall, 1981, are di-
recting fundamental research related to catalysis
in coal liquefaction; and Dr. R. B. Cook of the
Department of Geology is directing the geological
aspects of coal conversion processes. The Auburn
coal desulfurization research program is currently
being directed by Dr. Y. A. Liu, a chemical engi-
neering faculty member.
During the past few years, the Auburn coal
research faculty has become nationally and inter-
nationally recognized for its research as well as
its scholastic and professional contributions re-
lated to coal liquefaction and desulfurization, and
magnetic separation applied to coal preparation.
The research results obtained in the last few years
have been widely publicized through publication
of three books, two patents, and over 150 articles,
presentations and seminars. Further, the Auburn
Laboratories have organized and chaired two
international conferences on coal desulfurization
and magnetic separation (B8, B9), and one
national conference on the future of coal. A list of


Y. A. Liu received his B.S. from National Taiwan University, M.S.
from Tufts University and Ph.D. from Princeton University in 1974. He
is presently an alumni associate professor of Chemical Engineering at
Auburn University. (L)
James A. Guin is a professor of chemical engineering at Auburn
University. He received his B.S. and M.S. from the University of
Alabama and Ph.D. from the University of Texas at Austin. His re-
search interests include coal liquefaction, reactor design, and catalytic
upgrading of coal liquids. (LC)
Authur R. Tarrer is an associate professor of chemical engineering
at Auburn University. He received his B.S. from Auburn University and
M.S. and Ph.D. from Purdue University. His research interests include


selected recent publications and theses from the
Auburn coal research program is given at the end
of this article.
Laboratories containing approximately 4000
ft2 in the Department of Chemical Engineering
have been equipped for coal conversion and
utilization studies. Complete laboratory facilities
for high-pressure coal conversion, coal crushing
and grinding, instrumental analysis, wet chemical
analysis and coal preparation research are avail-
able. Complete analytical equipment for standard
analyses of coal and coal-derived products is also
available in the laboratories. In addition,
specialized research equipment such as a Fourier
Transform Infrared Spectrophotometer, an X-ray
Fluorescence Spectrometer, a CHONS analyzer
and a superconducting high-intensity magnetic
separator are available in the laboratories.

COAL LIQUEFACTION RESEARCH
Chemistry and Technology of Coal Liquefaction
In order to better appreciate the research
being conducted in coal liquefaction, a brief look
at coal liquefaction chemistry and technology
is desirable. Coal may be viewed as a large,
organic, amorphous, polymeric-like structure
consisting of condensed polynuclear aromatic
systems coupled by methylene-bridge groups, or
heteroatom linkages such as ether or sulfide















coal liquefaction, solids/liquid separation, process dynamics and
control, and catalysis. (C)
Christine W. Curtis is a research associate in chemical engineering
at Auburn University. She received her B.S. from Mercer University and
M.S. and Ph.D. from Florida State University. Her research interests
include coal liquefaction, catalytic upgrading and analysis of coal
liquids. (RC)
Dennis C. Williams is an assistant professor of chemical engineer-
ing at Auburn University. He received his Ph.D. in chemical engineer-
ing from Princeton University in 1980. His research interests include
process control, process synthesis, reactor modelling, phase behavior
effects in coal liquefaction, and numerical methods. (R)


FALL 1981









groups. Nitrogen is also a significant heteroatom
component of the coal structure. The liquefaction
of coal is thought to begin with the thermal rup-
ture of scissile linkages at temperatures around
375�C with the resulting formation of a large
number of free radical species. The key to the
liquefaction process is to "cap off" these free
radicals by hydrogen addition before they can
recombine with large coal fragments to form a
high-molecular-weight structure. This "donor"
hydrogen usually comes primarily from a "donor"
solvent; however, it may also arise from gas-
phase hydrogen or hydroaromatic portions of the
coal itself. The effective "capping" of these free
radicals leads to the formation of products of
lower molecular weight. If the reaction conditions
are severe enough, a liquid product is formed. A


cnl


CH'--CH '* TetrallnH2
* U 2 (Donor Molecule)
CH2
oaol
Froment




Naphtholene
(Spent Solvent)


CH
Stabilization / I

CH3-C CH Naphthalene
I C3 (Spent Solvent)
CH3
Stabilized
Molecule


Regenerotion


H2
Tetralln2
(Donor Molecule)


FIGURE 1. Hypothetical stabilization of coal fragment
by donor solvent and regeneration of
solvent in coal liquefaction.


simple diagram of this process is shown in Figure
1, using a model donor solvent, tetrahydronaphtha-
lene (tetralin). The "spent" donor, naphthalene,
can be hydrogenated to regenerate the donor. In
an actual process, the donor recycle solvent is a
complex mixture of condensed aromatic com-
pounds derived from the coal itself. A more de-
tailed investigation of factors affecting coal lique-
faction has been presented elsewhere (Al). A
good introduction to coal technology can be found
in Berkowitz (A2).
A diagram of a typical coal liquefaction plant
is shown in Figure 2. The raw coal is liquefied in
the presence of a coal-derived recycle solvent and
hydrogen gas at about 2000 psig and 4250C. A
catalyst can be used in the reactor if desired. The
mineral matter indigenous to the coal together
with any undissolved coal are physically removed
following the reaction. The coal liquids are then


available for subsequent separation and process-
ing into the desired clean fuels. A commercial coal
liquefaction plant would process about 30,000
tons/day of raw coal. The only commercial opera-
tion of this magnitude today is in South Africa
where large quantities of liquid fuels are produced
via coal gasification and catalytic Fischer-Tropsch
technology (A3). The direct production of liquid
fuels from coal by solvent extraction-hydrogena-
tion avoids the gasification step and offers the po-
tential of a more thermally efficient process. A
survey of different coal liquefaction processes
being developed in this country can be found in
the excellent surveys by Klass (A4) and Perry
(A5).

Current Scope and Accomplishments

Coal liquefaction research at Auburn centers
on the production of clean liquid and solid fuels
from coal. At the present time, processes to per-
form these operations are not economically com-
petitive with the use of petroleum. The objective
of the Auburn research program is to investigate
the effects of process operating conditions, equip-
ment configurations, and nature of raw materials
upon the kinetics and mechanisms of coal lique-
faction. Included within the framework are the
hydrogenation, cracking and heteroatom (N, O, S)
removal reactions which are essential to convert-
ing coal to clean liquid fuels. By obtaining a
better understanding of coal liquefaction chemis-
try, guidelines and recommendations for improve-
ments in liquefaction technology can be developed,
thus leading to more competitive processes.
The coal liquefaction research thus far has re-
sulted in findings which may point the way to im-
provements in several areas of coal liquefaction
technology.
* Solids Removal. Because of the large quantities
involved, the high solution viscosity, and the micron-
sized particles, the removal of coal mineral matter
and undissolved coal from the reactor effluent is a
costly and difficult job. Current research has shown
that analysis of particle size distribution in the
filter feed stream can provide an indication of the
difficulty of downstream filterability and filter cake
resistance (Bl).
* Coal Properties. It has been determined that various
coals, e.g., Kentucky, Pittsburgh, Illinois, Wyoming,
respond quite differently to the liquefaction process.
Attempts are being made to correlate their diverse
behavior with the coal properties.
* Solvent Composition. The quantity and composi-
tion of the recycle solvent are key variables in any
coal liquefaction operation. Using IR and NMR


CHEMICAL ENGINEERING EDUCATION









spectroscopies, it has been found that the hydro-
aromaticity of the recycle solvent is closely related
to its effectiveness for coal liquefaction (B7).
* Sulfur Removal. In certain coal liquefaction pro-
cesses, e.g., the SRC process, the primary objective is
to remove sulfur from the coal to produce a non-
polluting, clean burning product. By introducing
certain sulfur scavenging agents, e.g., Fe2O3, into
the liquefaction reactor, it has been found possible
to significantly reduce the sulfur content of the
SRC product (B5).
* Coal Pretreatment. The oxidation of coal has been
found to reduce significantly the liquid yield from
processing. This factor has stimulated considerable
interest in the protocol used to store, grind, and
dry the fresh coal prior to liquefaction.
* Coal Mineral Catalysis. It has been established that
coal minerals, notably pyrite, act as weak catalysts
for hydrogenation and heteroatom removal reactions
in the liquefaction process (B2, B4). This catalysis
can be used to improve hydrogen usage selectivity
and to lower the yield of non-desirable products,
e.g., light hydrocarbon gases (B6). The regenera-
tion of mineral residue from the reactor to produce
an active catalyst is an item of current research,
as are the kinetics of the catalytic reactions.
* Product Characterization. The chemical nature of
coal liquefaction products, e.g., asphaltenes, SRC,
etc., is vastly complex. Inroads are being made in
this area using a variety of separation techniques
such as high performance liquid chromatography
coupled with a number of spectroscopic techniques
including Fourier transform infrared spectro-
photometer, nuclear magnetic resonance and mass
spectroscopy (B3).

Work related to the above areas is now ongoing
as part of the current coal liquefaction program
at Auburn. Some typical current research topics
on which graduate students are now working in-
clude:

* A critical evaluation of mass transfer effects in
coal liquefaction
* Solvent characterization using chromatographic
separation with 1H and 13C NMR


Cool Feed Liquefaction Gases
Reactor _ Solids
400OC, 2000 psig Separatlon
Coal Liquids

Minerals
Undissolved Cool Recycle
, " Solvent


solvent
Hydrosgenation Gsf Ash
(op iona) Gasiser As

SHydrogen

FIGURE 2. A schematic diagram of a typical coal lique-
faction process (adapted from A8).


The objective of the ... program
is to investigate the effects of process
operating conditions, equipment configurations,
and nature of raw materials upon
the kinetics and mechanisms
of coal liquefaction.



* Catalyst deactivation in upgrading of crude coal
liquids
* Kinetics and mechanism of hydrogen shuttling in
coal liquefaction
* Tailoring of coal recycle solvent for more effective
liquefaction
* Catalyst poisoning by heteroatom compounds in
coal derived liquids

COAL DESULFURIZATION RESEARCH

Physics and Technology of Coal Desulfurization

Physical coal desulfurization (cleaning or
beneficiation) methods are based upon the differ-
ences in the physical characteristics that affect
the separation of sulfur-bearing and ash-form-
ing minerals from the pulverized, coal. Typical
physical characteristics utilized in these methods
include specific gravity, electric conductivity,
magnetic susceptibility and surface properties.
In some of the new methods being developed,
chemical pretreatment is used to enhance the
difference in physical characteristics to facilitate
the physical separation of mineral impurities from
the pulverized coal (A6). An excellent survey of
the present and developing physical coal desulfuri-
zation processes can be found in Berry (A7), and
an in-depth review of much of the new methods
and developments of physical coal desulfuriza-
tion technology will soon be published (B10).
A relatively well-established technology which
has been proposed for coal desulfurization applica-
tions is the magnetic separation technique. Pre-
vious investigators have indicated that most of
the mineral impurities which contribute to coal's
sulfur and ash contents are weakly magnetic,
whereas coal is nonmagnetic (BS). During the
past few years, the magnetic desulfurization of
coal has been given new impetus with the introduc-
tion of the high gradient magnetic separation
(HGMS) technology (B9). The latter utilizes the
modern large-capacity magnetic separation equip-
ment of an intense field intensity and a large field
gradient, coupled with the latest magnetic pro-
cessing know-how such as the control of retention


FALL 1981








time for reducing the fluid drag force and im-
proving the separation efficiency.

Current Scope and Accomplishments

Since 1975, the Auburn Coal Preparation
Laboratory has been actively involved in both
basic and applied research in physical coal de-
sulfurization, emphasizing the development and
demonstration of HGMS processes. Major results
from this research have included:

* The pilot-scale demonstration of the technical
feasibility of magnetic separation of mineral resi-
due from liquefied coal (B11);
* The computer development and experimental verifi-
cation of a practical model for predicting the
technical performance of HGMS for the removal
of sulfur and ash from coal/water slurries (B12);
and
* The experimental development of the patented
Auburn fluidized-bed HGMS process for desulfuriza-
tion of dry pulverized coal (B13).

The recent and current emphasis of the Auburn
coal desulfurization research has been placed on
the continued development and demonstration of
the patented fluidized-bed HGMS process for de-
sulfurization of utility boiler feed coals. In par-
ticular, a pilot-scale superconducting fluidized-
bed HGMS process development unit (PDU) has
been successfully designed, constructed and tested.
The available experimental results have shown
that the new fluidized-bed magnetic process can
reduce the sulfur emission level (lb S per million
BTU) of several pulverized Eastern coals (70 to
80% minus 200-mesh) by 55-70% and achieve
an average BTU recovery of 85-95% (B14). Work
is continuing on the automation and optimization
of the continuous PDU in order to provide the
necessary data for assessing the economics of the
new dry magnetic process for coal desulfurization.
Another emphasis of the Auburn current research
is the fundamental studies of magnetofluidized
beds as a new gas-solid contacting technology for
reaction, separation and filtration applications. A
novel concept of using a packed fluidized-bed in a
magnetic field for the removal of sulfur and ash
from pulverized coal invented in the Auburn
Laboratories has been described in a recent
patent (B13). O

A. LITERATURE CITED
Al. Guin, J. A., A. R. Tarrer, Z. L. Taylor, Jr., J. W.
Prather and S. Green, "Mechanisms of Coal Particle


Dissolution," I & EC Process Des. and Develop., 17,
490 (1976).
A2. Berkowitz, N., An Introduction to Coal Technology,
Academic Press, New York (1979).
A3. Heylin, M., "South Africa Commits to Oil from
Coal Process," Chem. and Eng. News, p. 13, Sept.
17 (1979).
A4. Klass, D. L., "Synthetic Crude Oil from Shale and
Coal," Chemtech., p. 499, Aug. (1975).
A5. Perry, H., "Coal Conversion Technology, Chem.
Eng., p. 88, July 22 (1980).
A6. Leonard, J. W., Editor, Coal Preparation, Soc.
Mining Engrs., Denver (1979).
A7. Berry, R. L., "Guide to Coal-Cleaning Methods,"
Chem. Eng., p. 47, Jan. 26 (1981).


B. SELECTED RECENT PUBLICATIONS FROM THE
AUBURN COAL RESEARCH PROGRAM
Bl. Curtis, C. W., A. R. Tarrer and J. A. Guin, "Particle
Size Variation in the Solvent Refined Coal Process,"
I & EC Process Des. and Develop., 18, 377 (1979).
B2. Guin, J. A., A. R. Tarrer, J. M. Lee, H. F. Van-
Brackle and C. W. Curtis, "Further Studies of
Catalytic Activity of Coal Minerals in Coal Lique-
faction: 1. Verification of Catalytic Activity of
Mineral Matter by Model Compound Studies, and
2. Performance of Iron and SRC Mineral Residue
as Catalysts and Sulfur Scavengers," I & EC Pro-
cess Des. and Develop., 18, 371 and 631 (1979).
B3. C. W. Curtis, C. D. Hathaway, J. A. Guin, and
A. R. Tarrer, "Spectroscopic Investigation of Sol-
vent Refined Coal Fractions," Fuel, 59, 575 (1980).
B4. Guin, J. A., J. M. Lee, C. W. Fan, C. W. Curtis, J. L.
Lloyd and A. R. Tarrer, "The Pyrite Catalyzed
Hydrogenolysis of Benzothiophene at Coal Lique-
faction Conditions," I & EC Process Des. and
Develop., 19, 440 (1980).
B5. Garg, D., A. R. Tarrer, J. A. Guin, C. W. Curtis
and J. . Clinton, "The Selective Action of Hema-
tite in Coal Desulfurization," I & EC Process Des.
and Develop., 19, 572 (1980).
B6. Garg, D., A. R. Tarrer, J. A. Guin, C. W. Curtis,
J. H. Clinton and S. M. Paranjape, "Selectivity Im-
provement in the Solvent Refined Coal Process. 1.
Detailed First-Stage Reaction Studies: Coal Mineral
Catalysis; and 2. Detailed Second-Stage Reaction
Studies: Hydrotreating of Coal Liquids," Fuel Pro-
cess Technol., 3, 245 and 263 (1980).
B7. Curtis, C. W., J. A. Guin, J. F. Jeng and A. R.
Tarrer, "Coal Solvolysis with a Series of Coal-
Derived Liquids," Fuel, in press (1981).
B8. Liu, Y. A., Editor, Proceedings of Magnetic De-
sulfurization of Coal Symposium, Special Issue on
Magnetic Separation, IEEE Trans. on Magn., MAG-
12, 423-551 (1976).
B9. Liu, Y. A., Editor, Industrial Applications of Mag-
netic Separation, 206 pages, IEEE Publication No.
78CH1447-2 MAG, Institute of Electric and
Electronic Engineers, Inc., New York (1979).
B10. Liu, Y. A., Editor, Physical Cleaning of Coal:
Continued on page 213.


CHEMICAL ENGINEERING EDUCATION









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OIL SHALE CHAR REACTIONS

WILLIAM J. THOMSON
Washington State University
Pullman, WA 99164


WITH THE RE-EMERGENCE OF an oil shale in-
dustry in the United States, most chemical
engineers have become acquainted with the pyro-
lytic requirements to decompose the kerogen
contained in the raw shale; namely, temperatures
of 725 - 800 K and a sweep gas to remove the
pyrolysis products. However, what is often over-
looked is the fraction of the organic carbon which
remains behind on the spent shale as a carbona-
ceous char. As Dockter [1] has shown, there is
more than enough energy in the residual char to
supply the pyrolysis heat requirements for shales
assayed at greater than 20 gal/ton (GPT). Al-
though first generation surface retorting pro-
cesses will not utilize this char (TOSCO II,
UNION RETORT B), there is general agreement
that energy efficiency considerations will dictate its
exploitation in all future process schemes.
In discussing oil shale char, distinction must
be made between the western shales of the Green
River formation and the so-called black shales
which are found in the eastern United States (in
a north-south belt from Michigan to Texas). De-
pending on retorting conditions and assay, the
char remaining on spent western shale is 2-5 % of
the raw shale weight. On the other hand, whereas
the organic carbon content of the black shales is
similar to that of the western shales, the oil yield
is typically a factor of three lower. Thus the char
content here is substantially greater, undoubtedly
due to the higher degree of aromaticity in the
black shale kerogen [2].
The author has been involved in research on
the reactions and the associated kinetics of oil
shale char for the past six years. The ultimate
goal of the research is to develop quantitative rate
expressions for these reactions in support of
modeling efforts for both in-situ and surface re-
torting processes. Since any char utilization
scheme will necessarily involve at least partial

� Copyright ChE Division, ASEE, 1981


William J. Thomson is professor and chair of Chemical Engineering
at Washington State University. Prior to assuming these duties in
January, 1981, he taught at the University of Idaho for 11 years. He
holds degrees from Pratt Institute (B.Ch.E.), Stanford University (M.S.)
and the University of Idaho (Ph.D.). His research interests are in oil
shale processing as well as applied kinetics and catalysis.

combustion, temperatures will be high (950-1200
K), and a significant fraction of the mineral
matter in the shale will also react. Because a
number of these inorganic constituents can also
act as catalysts for the char reactions, there is no
way to ignore their behavior. We discovered this
early in our work and although it made our task
more difficult, it led to a number of interesting ob-
servations. The pertinent mineral reactions which
take place in western shale and the char reactions
we have studied are shown in Table 1.

EXPERIMENTAL APPROACH

ALL OF OUR WORK TO DATE has been conducted on
western oil shale; specifically on samples taken
from the Parachute Creek member near Rifle,
Colorado. The raw shale samples, assayed at 15 to
50 GPT, were retorted under various conditions,
crushed to about 100 mesh and placed in a thermal
gravimetric analysis (TGA) system. Continuous
gravimetric measurements together with on-line
chromatographic analyses of the exit gas allowed
us to follow each of the reactions and to obtain
quantitative rate data. Details of the experimental
system and a discussion of its limitations have
been given in previous publications [3, 4].


CHEMICAL ENGINEERING EDUCATION








CHAR OXIDATION


A S PART OF OUR STUDIES OF char oxidation we
included an evaluation of the effects of assay
and retorting conditions on the resultant char
activity. We found no dependence on assay and
only when the retorting rate was less than 1 K/
min and the sweep gas velocity was less than 0.05
m/min was there any effect on char activity. In
this case the quantity of char produced was in-
creased and its activity was 50 % lower. As Camp-
bell et al. [5] have suggested, the additional char
is probably due to the coking of the product oils.
Equation (9) gives the reaction rate expression
obtained at temperatures below 900 K where Ce
is the char concentration (moles/g shale)
97200
ro, = 1.41 x 103 exp [ RT ] Po, C (9)

with RT in joules/mole, Po2 in kPa, rox expressed
in moles/sec-g shale. It should also be pointed
out that, unlike coal combustion, the activity
does not change with fraction combusted (other
than the first order dependence on Ce). Variable
coal activity is generally attributed to changes
in pore size distribution during combustion
whereas oil shale char is distributed rather uni-
formly throughout an established inorganic
matrix. At temperatures greater than 900 K the
mineral reactions given in Table 1 begin to take
place and there is positive evidence [4] that the
CaO produced by reaction (7) catalyzes the char
oxidation. The effect is at least an order of magni-
tude increase in the activity but this has never
been quantified as a function of the CaO con-


The ultimate goal of the
research is to develop quantitative
rate expressions for these reactions in support of
modeling efforts for both in-situ and
surface retorting processes.


centration.
Both inter- and intra-particle mass transport
resistances are expected to be significant during
char combustion. Measurements of the effective
diffusivities for diffusion paths parallel and per-
pendicular to the bedding plane give values of
30 x 10-6 and 12 x 10-6 m2/sec, respectively. These,
together with estimates of gas-solid mass transfer
coefficients, were used to show that both forms of
mass transport were equally significant during the
consumption of the initial 40% of the char for a
typical in-situ burn [6].

CO, GASIFICATION

D DURING HIGH TEMPERATURE OIL shale processing,
the reaction between CO2 and carbon can be
an important part of the overall gasification
scheme. This is because of the large volumes of
CO2 liberated due to combustion and mineral de-
composition. In fact, the simultaneous occurrence
of these reactions is just what makes CO2 gasifica-
tion so difficult to isolate and analyze. As a result
it was necessary to develop a careful procedure to
study this reaction [7] and we were necessarily
limited to a rather narrow temperature range
(975 - 1050 K). The kinetic data were fit to the
types of rate expressions derived from the coal


TABLE 1
Char and Mineral Reactions (Western Shale)


INITIATION
TEMPERATURE
(�K)


WGSR
4) CO + H2O -> CO, + H2
Mineral
5) CaMg(CO3), -> CaCO, + MgO + CO2
6) CaFe(CO3), -> CaCO, + FeO + CO2
7) CaCO,3 CaO + CO2
8) 2CaCO, + SiO2 -> Ca2SiO4 + 2CO,


COMMENTS


Strong CO inhibition
Catalyzed by CaO

Catalyzed by iron

Difficult to separate from reaction (7)

Reversible
Slow


REACTION


Char
1)
2)
3)


C + 02 -> CO2
C + CO, -> 2CO
C + H20 -> H2 + CO


FALL 1981








literature, resulting in equation (10). The numer-
ical values in equation (10) are similar to those
found in

k0 Pco2 Ce
roo2 - 1+ KPoo, + KPco (10)
ke = 7.83 x 104 exp [-184000/RT]
(kPa-sec) -1
k, = 0.0495 (kPa)-1
k2 = 5.0 (kPa)-1
the coal literature except that the inhibiting effect
of CO is ten times greater.

STEAM GASIFICATION

S TEAM GASIFICATION ALSO PROVED difficult to
isolate since the CO formed by reaction (3)
was found to react very rapidly via the water gas
shift reaction (WGSR), reaction (4). The CO.
formed in that reaction then competes with H20
for the available carbon. In fact the net effect of
steam gasification is to produce H2 and CO2 and,
after CO, scrubbing, the H2 could be used to offset
hydrotreating requirements for the raw shale oil.
We were able to circumvent these interactions by
taking initial rate data [7] and the rate expression
is given in equation (11).
k. Po20
rH20 = (11)
1 + Ks PH'o + K, PH2
k, = 6.62 exp [-100700/RT] (kPa-sec)-1
K� = 0.20 exp [-17000/RT] (kPa)-1
K4 = 0.15 (kPa)-1

CATALYTIC EFFECTS
OVER THE YEARS THERE HAS been a continuing
interest in alkali promoted catalysis of coal
gasification and, more recently, of biomass py-
rolysis. In both of these applications an alkali
salt must be added to the fuel, either by im-
pregnation or by admixing. However, with oil
shale we already have many of these elements in
place. It is not surprising then that CaO was
found to catalyze char combustion and, later, to
catalyze steam gasification [7]. Recall that iron is
also present in the shale, either in the form of
ankerite (Table 1) or pyrite. In either case, oxida-
tion and its associated high temperatures result
in producing one or more of the oxidation states
of iron (FeO, Fe2O,, FeO,). We have studied
the WGSR over shale ash [7] and not only is it
catalyzed by iron, but the iron oxidation state
changes as the surrounding gas composition
changes. Again, as in the case of CaO, we have a
variable catalyst concentration and the dependence


of activity as a function of catalyst concentration
has yet to be quantified.

CONCLUSIONS
As is the case with most complex mixtures,
the study of oil shale and its reactions is a
challenging subject. Whereas we have managed
some success with the obvious, the subtle and vary-
ing catalytic effects of the inorganic matrix is still
in the early stages of investigation. It is likely
that we will discover more interesting catalytic
properties of shale ash as we continue our
studies. O

REFERENCES
1. Dockter, L., AIChE SYMP. SER., 72, 24 (1976).
2. Miknis, F. P. and Macill, G. E., presented at 14th Oil
Shale Symposium, Golden, CO, 22-24 April 1981.
3. Soni, Y. and Thomson, W. J., Proceedings of the 11th
Oil Shale Symposium, Colorado School of Mines
Press, p. 364 (1978).
4. Soni, Y. and Thomson, W. J., I&EC Proc. Des. and
Dev., 18, p. 661 (1979).
5. Campbell, J. H., Koskinas, G. H. and Stout, N. D.,
IN-SITU, 2, p. 1 (1978).
6. Thomson, W. J. and Soni, Y., IN-SITU, 4, p. 61
(1980).
7. Thomson, W. J., Gerber, M. A., Hatter, M. A. and
Oakes, D. G., to be published in, "Oil Shale, Tar Sands
and Related Materials," ACS SYMP. SER. (1981).


' book reviews

COAL AND MODERN COAL PROCESSING:
AN INTRODUCTION

By G. J. Pitt and G. R. Millward
Academic Press, New York, 1979

Reviewed by T. D. Wheelock
Iowa State University
A number of books dealing with the properties
of coal and methods of utilizing this complex and
interesting material have recently appeared. Not
least among them is this volume of lectures pre-
sented during the 1976-77 session of the University
College of Wales to commemorate a British coal
scientist Dr. Walter Idris Jones. These lectures
were presented by various technical experts from
the National Coal Board in England and edited by
G. J. Pitt, one of the lectures, and G. R. Millward
who was with the University at the time.
Continued on page 219.


CHEMICAL ENGINEERING EDUCATION












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FALL 1981














KINETICS AND CATALYSIS


C. H. BARTHOLOMEW
Brigham Young University
Provo, UT 84602

C ATALYSIS IS A DEVELOPING SCIENCE which plays
a critically important role in the petroleum,
chemical, and emerging energy industries. It com-
bines principles from somewhat diverse disciplines
of kinetics, chemistry, material science, surface
science and reaction engineering.
The subjects of kinetics and catalysis are very
basic to graduate curriculums in Chemical Engi-
neering and Chemistry. Yet because of the de-
manding nature of graduate curriculum require-
ments, few departments can afford the luxury of
offering and/or requiring more than one intro-
ductory course treating a combination of these
two subjects.

THE CHALLENGE
The challenge at BYU is to combine the funda-
mentals of kinetics and scientific/engineering
principles of heterogeneous catalysis into a single-


Calvin H. Bartholomew received his B.S. degree in Chemical Engi-
neering from Brigham Young University and his M.S. and Ph.D. de-
grees in Chemical Engineering from Stanford University. He spent a
year at Corning Glass Works as a Senior Chemical Engineer in
Surface Chemistry Research. In 1973 he joined the Chemical Engi-
neering Department at Brigham Young University and is currently
associate professor. His major research interests are heterogeneous
catalysis (adsorption, kinetics and catalyst characterization), Moess-
bauer spectroscopy and air pollution chemistry.


The challenge ... is to combine the
fundamentals of kinetics and scientific engineering
principles of heterogeneous catalysis into
a single-semester, 3-credit course
suitable for chemical engineering
and chemistry graduate students.

semester, 3-credit course suitable for chemical
engineering and chemistry graduate students. A
typical class consists of 15-20 students, most of
which are M.S. and Ph.D. bound chemical engi-
neers, the remainder consisting of 1-2 chemistry
majors and 1-2 chemical engineering seniors. The
obvious diversity in class makeup and subject
matter requires (i) review of some basic kinetic
and chemical principles and (ii) a careful com-
promise between depth and breadth in course
topics. Accordingly the course is divided into eight
topics covered in 35 50-minute lectures (see Table
1). In addition, three special lectures and three
demonstrations (see Table 2) and a term paper
based on study of the literature add spice and
flavor to the course.
Another challenge which faces instructors of
kinetics and catalysis is that of finding suitable
text materials. There is, in fact, no single text
which covers this subject matter as outlined in
Table 1. Our solution to this dilemma is to use
portions of J. M. Smith's book on "Chemical Engi-
neering Kinetics" (the only required text) supple-
mented with 4 chapters from Boudart's "Kinetics
of Chemical Processes" (out of print and used by
permission from the author), reference books on
library reserve and papers from the literature
(see References).

COURSE ORGANIZATION

T HE COURSE BEGINS WITH A brief but enthusi-
astic introduction to the world of catalysis and
the basic concepts, rules and definitions of
kinetics. The foundation for understanding and
predicting reaction rates is next laid through 6

0 Copyright ChE Division, ASEE, 1981


CHEMICAL ENGINEERING EDUCATION









TABLE 1: Course Outline


I. INTRODUCTION AND DEFINITIONS
(two lectures)
A. Past, present and future of catalysis
B. Basic kinetic concepts and definitions
II. KINETIC THEORY
(six lectures)
A. Collision theory
B. Transition state theory
C. The H2 - 12 reaction, a case study
D. Thermodynamic formulation of rates
III. CONCEPTS, METHODS, AND TOOLS OF
KINETICS (three lectures)
A. Elementary steps/active centers and catalysis
B. Catalysis and the steady state approximation
C. Concept of the rate determining step
IV. ADSORPTION (four lectures)
A. Adsorption processes and types
B. Adsorption Isotherms
1. Langmuir
2. Others (Freundlich, Tempkin and BET)
C. Chemisorption
1. Measurement of Active metal surface area
2. Calculations of dispersion and crystallite
size
3. Heterogeneity and particle size effects
V. KINETICS OF SURFACE REACTIONS
A. Unimolecular and bimolecular surface reactions


lectures on kinetic theory using the magnificent
work of John H. Sullivan on H2 + 21 -> HI as
our classic case study. The student is next fitted
with the basic tools of kinetics in three lectures
dealing with elementary steps, the steady state
approximation and the concept of rate determin-
ing step. Here the methanation of CO serves
as our model reaction. The foundation and tools
are now used to erect the course framework
consisting of four lectures on adsorption and
surface reactions, the most basic processes in
catalysis. Two lectures on methods and materials
in catalysis provide an interesting diversion while
introducing the knowledge of catalyst structure
needed to tackle the meaty subjects of diffusion
and mass transfer. We concentrate on these latter
subjects in some depth (seven lectures) and in a
way which prepares the student for the ultimate
engineering problem of designing fixed bed
catalytic reactors. Again methanation is used as
our model reaction.

LEARNING FROM EXPERIMENTS AND LITERATURE

A MOST ENJOYABLE PART of the course involves
special lectures, experimental demonstrations
(see Table 2) and the study of papers from the
literature. The oscillating reaction is clearly our


B. Kinetics of heterogeneous catalytic reactions
1. Definitions of rate, activity, selectivity, and
turnover number
2. Facile and demanding reactions
VI. METHODS AND MATERIALS IN CATALYSIS
(two lectures)
A. Catalyst properties and materials
B. Catalyst selection and testing
C. Catalysts characterization-tools of the trade
VII. DIFFUSION AND MASS TRANSPORT IN
CATALYSIS (seven lectures)
A. Diffusion in porous catalytic solids
1. Overall rates and resistances
2. Effects of pore diffusion on rate-models
and equations
3. Pore resistance criteria
B. Film mass transfer
1. Model and correlations
2. Calculation of km
3. Mass transfer criteria
C. Nonisothermal heat effects
VIII. REACTOR DESIGN IN HETEROGENEOUS
CATALYSIS (eight lectures)
A. Review of ideal reactors
B. Material and energy balances for fixed beds
C. Laboratory and industrial reactors
D. Case study: reactor design of a methanator


most dazzling demonstration; although the simple
study of water level recession rates in a tank with
the exiting tube either verticle or horizontal pro-
vides a rewarding kinetic analogy in connection
with Bernoulli's equation. The very exothermic
oxidation of ammonia on thin (brightly) hot Pt
and Cu wires provides a fascinating but straight-
forward demonstration of the role of heat transfer
in catalysis.
Because catalysis is in large part an experi-
mental science, several class assignments are di-
rected at understanding basic experimental
techniques, methods of analyzing data, and ele-
ments of reactor design (including the design of
a recycle methanator). Most of our weekly as-

TABLE 2

Special Lectures and Demonstrations
SPECIAL LECTURES
1. Kinetic Analogies
2. Oscillating reactions and auto catalysis
3. Catalytic petroleum refining processes
DEMONSTRATIONS
1. Kinetic analogy: Water level in a tank with outlet
2. Oscillating reactions
3. Hot wire ammonia oxidation


FALL 1981









signments include the reading of a carefully se-
lected journal article (see References). One of
the assignments is to critically review one of these
articles, a task which stimulates the thinking of
the best students and makes for interesting class
discussion. However, the assignment that appears
to have the greatest learning impact is the prepa-
ration of a literature review paper on a topic of
the students' choice, typically a catalytic reaction
or process. O


ACKNOWLEDGMENTS

The author acknowledges the excellent
examples of former teachers and stimulating con-
versation with colleagues of the present who have
influenced his thinking and provided ideas leading
to the demonstrations and special lectures, in-
cluding Michel Boudart (Stanford U.), Duane
Horton (formerly BYU), Douglas Bennion (BYU,
who has shared in the teaching of this course) and
James Christensen (BYU).


REFERENCES

Texts
1. Smith, J. M., "Chemical Engineering Kinetics," 3rd
Ed., McGraw-Hill, N.Y., 1980.
2. M. Boudart, "Kinetics of Chemical Processes,"
Prentice Hall, 1968, Chapters 1-4. (Out of print, use
by permission of author).

Background Readings
1. Anderson, R. B., "Experimental Methods in Catalytic
Research," Academic Press, N.Y., 1968.
2. Benson, S. W., "Foundations of Chemical Kinetics,"
McGraw-Hill, 1960.
3. Carberry, J. J., "Chemical and Catalytic Reaction
Engineering," McGraw-Hill, N.Y., 1976.
4. Denbigh, K. G. and Turner, J. C. R., "Chemical Re-
actor Theory," 2nd Edition, Cambridge, 1971.
5. Hill, C. G., "An Introduction to Chemical Engineering
Kinetics and Reactor Design," John Wiley, 1977.
6. Laidler, K. J., "Chemical Kinetics," 2nd Edition,
McGraw-Hill, 1965.
7. Moore, W. J., "Physical Chemistry," 3rd Edition,
Prentice-Hall, N.Y. 1962.
8. Glasstone, S., Laidler, K. J., and Eyring, H., "Theory
of Rate Processes," McGraw-Hill, 1941.
9. Satterfield, C. N., "Mass Transfer in Heterogeneous
Systems," MIT Press, 1970.
10. Satterfield, C. N., "Heterogeneous Catalysis in
Practice," McGraw-Hill, N.Y., 1980.
11. Thomas, C. L., "Catalytic Processes and Proven
Catalysts," Academic Press, N.Y., 1970.
12. Bond, G. C., "Heterogeneous Catalysis," Oxford
Press, 1979.


Topical Journal Articles
1. Sullivan, J. H., "Mechanism of the "Bimolecular"
Hydrogen-Iodine Reaction," J. Chem. Physics 46, 73
(1967). (Also see C & EN, Jan. 16, 1967, p. 40).
2. Boudart, M., "Catalysis by Supported Metals," Ad-
vances in Catalysis 20, 153 (1969).
3. Yates, J. T., Jr., "Catalysis, Insights From New
Technique and Theory," C. & EN, Aug. 26, 1974, p. 19.
4. Butt, J. B., "Progress Toward the a Priori Determina-
tion of Catalytic Properties," A.I.Ch.E. Journal 22,
1 (1976).
5. Sinfelt, J. H., Carter, J. L., and Yates, D. J. C.,
"Catalytic Hydrogenolysis and Dehydrogenation over
Copper Nickel Alloys," J. Catal. 24, 283 (1972).
6. Sinfelt, J. H., "Ru/Cu Bimetallic Clusters," J. Catal.
29, 308 (1973).
7. Boudart, M., "Two Step Catalytic Reactions,"
A.I.Ch.E. Journal 18, 465 (1972).
8. Dalla Betta, R. A., Piken, A. G., and Shelef, M.,
"Heterogeneous Methanation: Steady-State Rate of
CO Hydrogenation on Supported Ruthenium, Nickel
and Rhenium," J. Catal. 40, 173 (1975).
9. Vannice, M. A., "The Catalytic Synthesis of Hydro-
carbons from H2/CO Mixtures Over the Group VIII
Metals," J. Catal. 37, 449 (1975).
10. Wentrcek, P. R., Wood, B. J., and Wise, H., "The
Role of Surface Carbon in Catalytic Methanation,"
J. Catal. 43, 363 (1976).
11. Bartholomew, C. H., and Farrauto, R. J., "Chemistry
of Nickel-Alumina Catalysts," J. Catal. 45, 41 (1976).
12. Taylor, K. C., "Determination of Ruthenium Surface
Areas by Hydrogen and Oxygen Chemisorption," J.
Catal. 38, 299 (1975).
13. Mustard, D. G., and Bartholomew, C. H., "Determi-
nation of Crystallite Size and Morphology in Sup-
ported Nickel Catalysts," J. Catal. 67, 186 (1981).
14. Dumesic, J. A., Topsoe, H., Khammouma, S., and
Boudart, M., "Catalytic and Magnetic Properties of
Small Iron Particles, II Structure Sensitivity of
Ammonia Synthesis," J. Catal. 37, 503 (1975).
15. Bartholomew, C. H., Pannell, R. B., and Butler, J. L.,
"Support and Crystallite Size Effects in CO Hydro-
genation on Nickel," J. Catal. 65, 335 (1980).
16. Mears, D. E., "Tests for Transport Limitations in
Experimental Catalytic Reactors," Ind. Eng. Chem.
Process Des. Devel., 10, 541 (1971).
17. Carberry, J. J., and Butt, J. B., "On the Status of
Catalytic Reaction Engineering," Cat. Rev.-Sci. Eng.
10, 221 (1974).
18. Field, R. J., "A Reaction Periodic in Time and
Space," J. Chem. Ed. 49, 309 (1972).
19. Lefelhocz, "The Color Blind Traffic Light," J. Chem.
Ed. 49, 313 (1972).
20. Butt, J. B., and Weekman, V. W., Jr., "The Determina-
tion of Catalyst Properties," CEP 71, 33 (1975).
21. Carberry, J. J., "Designing Laboratory Catalytic Re-
actors," Ind. & Eng. Chem. 56, 39 (1964).
22. Weekman, V. W., A.I.Ch.E. Journal, 1974.
23. Conn, A. L., "Developments in Refining Processes
for Fuels," CEP 69, 11 (1973).
24. D. P. Burke, "Catalysts," Chemical Week, Nov. 1,
1972, p. 23.


CHEMICAL ENGINEERING EDUCATION









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FALL 1981


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4f ac^Ai in


CHEMICAL ENGINEERING ANALYSIS

JOHN C. HASSLER
University of Maine at Orono
Orono, ME 04469


O NE OF THE MOST IMPORTANT changes in chemi-
cal engineering over the last several years has
been the rapid increase in the availability of a
rather vaguely defined resource which I will call
"computing power." In fact, mathematical
modeling has reached a level of sophistication and
reliability sufficient to allow it to replace some
or all of the "pilot plant" part of designing a
process. Further, the rate of increase of comput-
ing power availability shows no sign of decreas-
ing. This all serves to emphasize the importance
of the teaching of effective use of computers in
chemical engineering education.
Though few would disagree with these state-
ments, there is an important difficulty which I
have observed in myself and others. Most of our
faculty learned computing in the days of cards,
batch submission of programs, and expensive com-
puter time. Now, students have access to fully in-
teractive terminals, and computer time is
virtually free, compared to an engineer's time.
This requires a completely different attitude
toward computer use, especially in regard to the
efficiency of programs and algorithms, than most
of us are accustomed to. "Quick and dirty" solu-
tions to problems may be perfectly acceptable;
sloppy thinking never is. It is sometimes difficult
for the students to grasp the distinction, so I
return to this idea several times during the se-
mester in connection with various other topics.
This article describes a 3-hour, one semester
graduate course called "ChE Analysis." It is a re-
quired course, generally taken during the first


In fact, mathematical modeling has
reached a level of sophistication and reliability
sufficient to allow it to replace some
or all of the "pilot plant" part
of designing a process.


� Copyright ChE Division, ASEE. 1981


John C. Hassler is currently an Associate Professor of Chemical
Engineering at the University of Maine at Orono. His degrees are in
physical chemistry from Kansas State University. He spent several
years in the "post-doc. holding pattern", including four years in the
Electrical Engineering Department at the University of Illinois, working
on lasers. He joined the Chemical Engineering faculty at Virginia
Polytechnic Institute and State University in Blacksburg, Virginia in
1972, and moved to Maine in 1977. His research interests are process
instrumentation, modeling, and control, with an emphasis on the
hardware and software involved in the application of computers to
real-time problems.

semester in residence, along with courses in ad-
vanced thermodynamics and unit operations. The
prerequisites are the usual undergraduate courses
in ChE, and the ability to program a computer.
Our students invariably use FORTRAN or a
structured version of FORTRAN (e.g., WATFIV-
S), though other languages could be used.
The purpose of the course is to provide a
"toolkit" of numerical methods and modeling
techniques sufficient to handle most of the
problems that are likely to occur in further
courses, or in engineering practice. Since most of
our students are M.S. candidates, the course is
strongly "applied" in nature. The emphasis is on
simple methods which usually work and which re-
quire no detailed knowledge in their application,
so that the student will be able to apply them even
after disuse has left them a bit rusty. This is
different from the usual graduate "Analysis"
course in that the emphasis is on applications
rather than on advanced mathematics.
This course was first taught in 1975 at VPI
in Blacksburg, VA, as a special one quarter


CHEMICAL ENGINEERING EDUCATION








remedial FORTRAN course for a class of in-
coming graduate students. Since they were able
to learn the actual programming fairly quickly, I
spent most of the quarter on numerical methods
and modeling. The course filled an obvious need,
and was offered the next year without the
FORTRAN. In 1977, it was brought to UMO,
expanded to a semester, and made a required
graduate course. The content has been remarkably
stable over the years, though there has been a
gradual drift of the material from the first part
of the course into the undergraduate level. I
expect this to continue, which will allow the
introduction of more new mathematical material,
such a matrix theory, at the graduate level.

COURSE FORMAT

T HIS IS A ONE SEMESTER, three credit hour
graduate course. The grading is based entirely
upon a series of problem sets of increasing
difficulty. There are no examinations. All of the
problems involve computer use, and the results
are submitted in the form of informal reports. The
students are explicitly permitted to discuss the
problems among themselves, but are told to do
their own actual work. Though there is a potential
for abuse, we have had no real difficulties with this
policy.
The only real problems that I have ever had in
teaching the course resulted from a leniency in
enforcing due-dates for problems. The less fore-
sighted students suddenly found themselves at the
end of the semester with several (long) problems
to work, just at the time when access to the com-
puter is the most difficult to get. This resulted in
a very stressful couple of weeks for all concerned.
Since then I have been quite adamant about dead-
lines, with stiff penalties for lateness.

COURSE DESCRIPTION

T HE MATERIAL BREAKS INTO three roughly equal
(five week) segments. The first covers basic
numerical techniques, the second applies these to
modeling problems, and the last picks up topics
which I think are important, but which are less
likely to be immediately useful to a M.S. engineer.
Since each class progresses at a somewhat
different speed, it is usually necessary to choose
some subset of the matrix operations to fill out the
semester.
The text is Carnahan, Luther, and Wilkes
(CLW) [1]. Most students also have Luyben [2]


from undergraduate process control, and Franks
[3] is recommended as a reference. I also refer to
journal articles when appropriate, especially for
problems.
The following is an outline of the course, with
some comments. Most of the numerical methods
material comes directly from CLW, so I will not
comment on the methods themselves. Instead, I will
present the rationale for choosing the particular
topics which are covered.

SECTION I-The tool kit
Interpolation
This is used only as a background for the other
methods, and as an introduction to finite differ-
ences. There is really very little need for inter-
polation itself, since the advent of powerful calcu-
lators. For example, I find it easier to get values
of the error integral by direct integration on a


"Quick and dirty" solutions to problems
may be perfectly acceptable; sloppy thinking
never is. It is sometimes difficult for
the students to grasp the distinction,
so I return to this idea several
times during the semester...


programmable calculator than to use interpola-
tion in a table. This is another example of the
change in approach from when I was a student.

Integration
The methods considered are rectangular,
trapezoidal, and Simpson's rule. Gaussian methods
are described, but not covered in any detail. The
first homework assignment is to use numerical
integration to find the value of the error function
at x = 1, using each of the three methods mentioned
above, and to note the number of intervals re-
quired to get six figure accuracy. Students are
duly impressed by the difference between
Simpson's rule (a few intervals) and the trape-
zoid rule (a few tens of intervals), but are
astonished to find that the rectangular integra-
tion to the specified accuracy is impossible. Since
many tens of thousands of intervals would be re-
quired to reduce the truncation error to the desired
value, round off error builds up and overtakes it
before the required accuracy is reached. The few
clever students who figure this out and try to use
double precision arithmetic discover that the time


FALL 1981









. . we again discuss the trade off between engineering time and computer time, and try to decide
when it is appropriate to use crude algorithms to minimize programming time.


allowed for a single run on a student computer
account is insufficient for the required number of
calculations. At this point, the ideas of round-
off and truncation errors are discussed in the
lecture.

Equation roots
These are covered from the "fixed point" ap-
proach [4]. Functional iteration, the secant
method ("false position"), and the Newton-
Raphson methods are discussed and shown to be
closely related. I recommend that they use either
Newton-Raphson or the secant method, depend-
ing on the difficulty of taking the derivative of the
equation. The standard polynomial root sub-
routines available on the computer are also dis-
cussed at this point.
Convergence criteria, and the use of iteration
counters to catch divergent cases, are discussed
next. The use of the programmer as the con-
vergence test is also discussed. It is often useful
in "quick and dirty" problems to just dump the
successive iterations to an interactive terminal and
let the programmer decide when to quit. As
pointed out above, this is a different way of using
the computer than those of us who grew up in the
days of "batch submission" are used to. However,
modern students seem to use it naturally, so we
spend a little class time discussing the good and
bad points. (The major bad point, incidentally, is
simply the danger that a casual approach to pro-
gramming can lead to a casual approach to think-
ing through the problem.)

Simultaneous linear equations
These are handled by Gauss-Jordan reduction
with pivoting. Since subroutines for linear systems
are readily available, very little time is spent on
this topic. Factorization schemes such as Grout's
or Doolittle's are mentioned but not covered, and
iterative methods are deferred until the next
topic.

Simultaneous non-linear equations
These are treated by analogy with the "fixed
-point" methods for a single equation. The Gauss-
Seidel method is recommended unless the Jacobian


is easily calculated, in which case the Newton
method is preferred. Some special methods for
very large or sparse systems are discussed briefly
[5], but not covered in any depth. Relaxation
methods, and the "damped Newton" method [4]
are also presented at this time.

Ordinary differential equations (ODE)
Here, I first derive Euler's method in three
ways, from a truncated Taylor's series, from finite
differences, and intuitively, from the current point
and the slope of the approximating straight line.
Then I show that the Euler method is closely re-
lated to rectangular integration. The students
readily recognize the accuracy problems by
analogy with their earlier integration problem. At
this point, we again discuss the trade off between
engineering time and computer time, and try to
decide when it is appropriate to use crude
algorithms to minimize programming time.
The "cannon problem," which is the calcula-
tion of a ballistic trajectory in the presence of a
velocity-dependent drag, is now used to introduce
several important concepts. These include modular
program design using subroutines (or "remote
blocks" for those using a structured FORTRAN),
modular testing, and program testing by the use
of limiting cases. For example, the case of zero
drag can be solved analytically, and the cor-
responding limiting case of a very low drag co-
efficient should approach this analytical solution.
The Modified and Improved Euler methods
are used to introduce Runge-Kutta methods. The
standard Runge-Kutta subroutine is described, and
the principle reason for its use is discussed, i.e.,
that it is readily available and familiar. Predictor-
corrector methods are also described, and the
standard Hamming subroutine is presented.
The origins of and problems inherent in "stiff
equations" are covered in detail. The usual method
of attack ("brute force"; a small step size, and
hang the computer time) is discussed, along with
a reiteration of the computer time vs. engineering
time trade off. Implicit methods are introduced
using the Backwards Euler method as an example,
and we demonstrate that what we have done is
replace the problem of a small step size with the
problem of solving a set of nonlinear simultaneous


CHEMICAL ENGINEERING EDUCATION








equations to high accuracy. The standard Gear [6]
subroutines are described, but not covered in any
detail.

SECTION II-Modeling
At this point, about five weeks into the se-
mester, the students have sufficient tools available
to attack an impressive array of modeling
problems. They have, however, only been given
some highly structured and relatively easy problem
sets, and they are beginning to become compla-
cent. I repeat the warnings given at the beginning
of the semester about falling behind, and tell them
that things are now going to become much more
interesting.

Preliminaries
One class period is spent on various pre-
liminaries. I make extensive use of the informa-
tion flow diagrams given by Franks [3] in the
modeling part of the course. Though they are
helpful in general, they are the best method that
I have found to teach the modeling of staged
operations. I also present a number of little
aphorisms, such as, "Two small problems are
easier than one big one," or "Divide and conquer,"
or "KISS-Keep It Simple, Stupid." I then indicate
in a general way how one goes about breaking a
big problem into managable parts, and also bring
in the ideas from structured programming (fa-
miliar to some of our students) of "psychological
chunking," "reducing connectivity," etc., and how
these apply to modeling problems. This is all il-
lustrated with a sequence of simple examples,
following Franks [3], and culminating in the single
component boiler example [2, 3].

Applications to problems
For the first real modeling problem, the
students are asked to model an unstable CSTR
with a proportional controller (adapted from
Luyben [2]), and to use the model to determine
various stability limits, such as the minimum
value of the controller constant, the minimum
and maximum allowable feed temperatures, etc.
This is just a somewhat messy ODE problem, and
the first part is very well defined, so most students
get it easily. I also ask them to devise a start-up
procedure that they could use on a real system,
and test it with their model. With the problem as
stated (no external heating of the reactor-only


cooling) the only way is to start with the re-
actor full of heated pure solvent, and then start
the reactor flows. (The first several years that I
gave this course, there would be only one or two
students in a class who would get this part. Now,
they all do. Either they're getting smarter, or the
word is getting around.)
While the students are working the CSTR
problem, the lectures are leading up to a non-ideal
batch distillation problem. Though most of the
students are taking advanced thermodynamics
concurrently with the modeling course, they have
not reached the vapor-liquid equilibrium (VLE)
section yet, so I spend about one period covering
non-ideal VLE, the Margules and van Laar equa-
tions, and the like. They then solve a batch dis-
tillation problem, which is basically another ODE
problem, but with an "inner loop" of simultaneous
equations which must be solved to get the activity
coefficients.
The next problem is a single-effect evaporator.
It is not difficult, being somewhat similar to the

I also present a number of
little aphorisms, such as, "Two small
problems are easier than one big one," or
"divide and conquer," or "KISS-Keep
It Simple, Stupid."

batch distillation, but it is a preliminary to the
triple effect evaporator, which follows.
A triple effect evaporator is used for the staged
operation problem. The students are guided
through the setting up of the information flow
diagrams, and warned that the last effect is some-
what different than the first (n-1) effects. This is
easily seen from the information flow diagrams,
because the externally fixed parameters are
different for the two cases. The resulting set of
equations and flow diagrams is rather awesome.
However, we note that if we use forward integra-
tion methods for the ODE parts, then we can solve
all of the integration blocks at time t to get the
outputs of these at time t+dt. We then erase the
integration blocks, and solve the resulting alge-
braic network at the new time t+dt. Then we
simply repeat these steps. The Franks 13] informa-
tion flow diagrams get this across very easily. No
other teaching method that I have tried has re-
sulted in as rapid or as complete an understand-
ing of what is really being done in the solution of
dynamic models.
It should be noted that although the problems


FALL 1981








are easily described, this is actually the most
difficult part of the course. Five to six weeks are
usually spent on this section.

SECTION III-More numerical methods
The students have now seen the application of
their "toolkit" of methods to some moderately
difficult problems, so we now add a few more
"tools."

Optimization
The basic theory of optimization, and gradient
methods in general, are briefly touched upon. We
cover the "Sequential Simplex" method of Nelder
and Meade [7] in detail. I have found this to be
an easily understood and programmed method,
which works reasonably efficiently in practice.
Penalty functions [7] are suggested for con-
strained optimization, but no problems are
assigned.

Statistics
Some topics in statistics, taken from Himmel-
blau [8], are covered next, for two reasons. First,
our students have no idea of what is involved in
statistical analysis beyond the blind application
of "least squares," and second, it gives a play-
ground for applications of optimization methods.
Most of the students have had the experience of
trying to apply "least squares" to some problem
for which the normal equations turned out to be
impractical to solve. We discuss the use of opti-
mization methods to "minimize the squared
error," but we also give some thought as to what,
if anything, this really tells us. The students seem
to enjoy this section very much, gleefully fitting
arbitrary functions to random collections of points.
(In fact, I've done some of it myself, but I called
it "research.")
The last two topics are not very demanding,
and are given at this time partly to let the students
catch up on their modeling problems. The next two
sections are again fairly difficult.

Partial differential equations (PDE)
PDE are covered directly from the text [1]. I
preceded the text material by a short review of the
theory of PDE, and of the resulting types of
boundary conditions, and add a brief section on
hyperbolic PDE (which are not covered in the
text). The problems assigned include the steady
state temperature distribution in a cooling fin,


and the fearsome "ice problem," in which the
students model the freezing of a lake. This is a
moving interface problem, and is reasonably
difficult.

Matrix theory
By this time, we are near the end of the se-
mester, so I can cover only a little matrix theory.
We always cover the basic operations, and usually
manage an introduction to eigenvalues and eigen-
vectors, but only rarely do we have time to cover
similarity transformations. Although I regret this,
since my major interest is in control theory, the
other topics seem more directly useful to students
at this level.
A FEW GENERAL COMMENTS

T HERE ARE SEVERAL POTENTIAL problems in the
teaching of this course. For example, grading
can be difficult. If an answer is incorrect, it can
be very time consuming to decide whether it is
due to a lack of understanding or simply to a
trivial error in programming. I have not had much
success in trying to get the students to verify
their answers, either. They treat this as "just an-
other course," and expect me to tell them if they
are right or wrong. The only remedy I have found
is to require complete documentation, of the
algorithm as well as the program, along with the
problem solution. Since our students don't write
any better than anyone else's, this is also good
practice for them. (The students themselves com-
plain bitterly about all the writing. They would
rather spend 10 hours at a terminal than 10
minutes writing about what they have done.)
Another difficulty lies in the distribution of
work during the semester. The first half of the
course is really very easy, and doesn't require
much outside effort. The second half becomes
suddenly very demanding, and the students are
caught off guard no matter how often I have
warned them of what was coming. The only
remedy is to be completely rigid in the deadlines
for problems. This may result in some students
losing a lot of points for lateness, but I think
that it is preferable to allowing the student to
get hopelessly behind.
A final difficulty is keeping the problems fresh
and challenging. Even though the students don't
seem to copy old solutions, the approach to
specific problems seems to become part of the "con-
ventional wisdom" after a few years. For this
reason, I have given up using a distillation


CHEMICAL ENGINEERING EDUCATION









column for the staged operation problem, and
substituted the triple effect evaporator. This
should be good for another year or so, and then I
will have to find something else. Another example
is the ice problem. Last year, I substituted the
"mirror fog" problem [9] as a moving boundary
example. Although the solution is obvious almost
by inspection, the requirement that the students
actually solve the PDE does result in a meaning-
ful problem.
To conclude on a positive note, when we were
revising the graduate curriculum a few years ago,
the graduate students recommended that this
course be kept unchanged. Also, several of my
former students have told me that this is one of
the most directly useful of the courses that they
have taken. It seems to fulfill its purpose of pro-
viding the tools needed to use a computer to solve
problems, and it gives the student a feeling for
how to approach even a very large modeling
problem. And perhaps the most important of all,
it is fun to teach. OE

REFERENCES
1. Carnahan, B., H. A. Luther, and J. O. Wilkes,
"Applied Numerical Methods," Wiley (1969).
2. Luyben, W. L., "Process Modeling, Simulation, and
Control for Chemical Engineers," McGraw-Hill
(1973).
3. Franks, R. G. E., "Modeling and Simulation in
Chemical Engineering," Wiley Interscience (1972).
4. Conte, S. D., and C. deBoor, "Elementary Numerical
Analysis," McGraw-Hill (1980).
5. Westerberg, A. W., H. P. Hutchison, R. L. Motard, and
P. Winter, "Process Flowsheeting," Cambridge Uni-
versity Press (1979).
6. Gear, C. W., "Numerical Initial Value Problems in
Ordinary Differential Equations," Prentice-Hall
(1971).
7. Beveridge, G. S. G., and R. S. Schecter, "Optimiza-
tion: Theory and Practice," McGraw-Hill (1970).
8. Himmelblau, D. M., "Process Analysis by Statistical
Methods," Wiley (1970).
9. Kabel, R. L., "The Mirror Fog Problem," Chem. Eng.
Education 18 No. 4 (1970) 155.


MOLECULAR THERMODYNAMICS
Continued from page 176.
3, 5, and 8.
4. C. Y. Tsang and W. B. Street, J. Chem. Eng. Data,
26, 155 (1981).
5. W. B. Street and J. C. G. Calado, J. Chem. Thermo.,
10, 1089 (1978).
6. C. Y. Tsang, P. Clancy, J. C. G. Calado and W. B.
Street, Chem. Eng. Commun., 6, 365 (1980).
7. C. Y. Tsang and W. B. Street, Fluid Phase Equi-


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UNIVERSITY OF TEXAS AT AUSTIN
ASSISTANT PROFESSOR OF CHEMICAL ENGI-
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Responsible for teaching undergraduate and graduate
courses, supervising graduate research. Send resume, three
references, transcripts, and statement of interest to: Dr.
D. R. Paul, Chairman, Department of Chemical Engineer-
ing, The University of Texas at Austin, Austin, TX
78712-1165. Affirmative Action/Equal Opportunity Em-
ployer.

libria, 6, 261 (1981).
8. C. Y. Tsang and W. B. Street, Chem. Eng. Sci., 86,
993 (1981).
9. G. Schneider, in "Chemical Thermodynamics, Vol. 2,"
Specialist Periodical Reports, The Chemical Society,
London, 1978, Chap. 4.
10. W. B. Street, Can. J. Chem. Eng., 52, 92 (1974).
11. W. B. Street, A. L. Erickson and J. L. E. Hill, Phys.
Earth Planet. Interiors, 6, 69 (1972).
12. J. de Swaan Arons and G. A. M. Diepen, J. Chem.
Phys., 44, 2322 (1966).
13. D. S. Tsiklis, Doklady Akad. Nauk S.S.S.R., 86,
1159 (1952).
14. For a review of the earlier theories see: K. E.
Gubbins, AIChEJ, 19, 684 (1973).
15. A review of theory and applications is given in:
K. E. Gubbins and C. H. Twu, Chem. Eng. Science,
33, 863, 879 (1978).
16. G. M. Gibbs, D. Phil. Thesis, University of Oxford
(1979).
17. K. P. Shukla and Y. Singh, J. Chem. Phys., 72, 2719
(1980).
18. P. Clancy, K. E. Gubbins and C. G. Gray, Disc.
Faraday Soc., 66, 116 (1978).
19. K. E. Gubbins, C. G. Gray and J. R. S. Machado,
Molec. Phys., 42, 817 (1981).
20. B. Moser, K. Lucas and K. E. Gubbins, Fluid Phase
Equilibria, in press (1981).
21. K. E. Gubbins, Proc. Second Internat. Conf. Phase
Equilibria and Fluid Props. in the Chem. Industry,
Berlin, Dechema, Frankfurt (1980), p. 621.
22. For reviews see: W. B. Street and K. E. Gubbins,
Ann. Rev. Phys. Chem., 28, 373 (1977); J. M. Haile,
K. E. Gubbins and W. B. Street, Proc. 7th Symp.
Thermophys. Properties, Amer. Soc. Mech. Engr.,
New York (1977), p. 421.
23. D. A. Jonah, K. S. Shing and K. E. Gubbins, Proc. 8th
Symp. Thermophys. Properties, Amer. Soc. Mech.
Engr., New York (1981).
24. K. E. Gubbins and J. M. Haile, in "Oil Recovery by
Surfactant and Polymer Flooding," ed. D. O. Shah
and R. S. Schechter, Academic Press, New York
(1977), p. 119.
25. S. M. Thompson and K. E. Gubbins, J. Chem. Phys.,
74, 6467 (1981).


FALL 1981








7 Goane 0o1



UNDERGROUND PROCESSING

CLARENCE A. MILLER*
Carnegie-Mellon University
Pittsburgh, PA 15213


THE EVENTS OF RECENT YEARS have brought in-
creased attention to processes for recovering
fossil fuels and minerals from underground forma-
tions. Higher prices for petroleum have caused
the industry to give serious attention to more
sophisticated recovery processes involving not just
flow, as in conventional processes, but also heat
and mass transport, various phase changes, chemi-
cal reactions, and interfacial phenomena. Under-
ground coal gasification seems promising for the
future. Research has increased on in situ process-
ing to recover oil from oil shale and tar sands.
Solution mining of uranium has begun in some
locations.
The number of engineers working on such
processes has increased rapidly in recent years,
especially in research. As more extensive field ap-
plications develop, additional engineers will be re-
quired to design processes applicable to specific
locations and to supervise production operations.
Because flow, transport, and chemical reaction are
involved in most of the processes, chemical engi-
neers are well suited for this work and should be
much in demand.
STo acquaint chemical engineering students with
this rapidly growing field and to provide them
with pertinent fundamental information not
ordinarily covered in a chemical engineering cur-
riculum, I have developed a one-semester course in
"Underground Processing." Although basically a
graduate course, it is open to interested under-
graduates who have had courses in fluid mechanics,
transport phenomena, and thermodynamics.

GEOLOGICAL BACKGROUND

T ABLE 1 IS AN OUTLINE of the course. The first
section deals with geological background ma-
terial.-In contrast to the usual situation in a
chemical plant, the "reactor" for an underground
process is not built to the designer's specification
*Present address: Rice University, Houston, TX 77001.


Clarence A. Miller received his B.A. and B.S. Degrees in chemical
engineering from Rice University in 1961. After spending four years
as an engineer with the Navy's nuclear power program in Washing-
ton, D.C., he undertook graduate studies at the University of Min-
nesota, receiving his Ph.D. Degree in 1969. He spent twelve years
on the chemical engineering faculty at Carnegie-Mellon University and
joined Rice University in September, 1981, as a Professor of Chemical
Engineering. For the last several years his major research interest has
been investigation of interfacial phenomena in enhanced oil recovery
processes.

but is provided by nature. It is usually the result
of geological processes which have occurred over
periods of tens to hundreds of millions of years.
As it is accessible only through a few widely
spaced wells, details of how its physical structure
and chemical composition vary with position are
not known. Some understanding of its geological
origin is useful in determining how effective
various processes might be.
The difference in pore structure between sand-
stones and limestones, the two most common reser-
voir rocks for petroleum, provides an example of
the importance of geology to an engineer. The
pore space in a sandstone is basically that origin-
ally present between the individual sand grains
just after deposition, although some decrease in
pore size occurs over time due to compaction as
the deposit is buried and due to precipitation of
silica, calcium carbonate, or other substances on
the surfaces of the grains and at their junctions.
Also called cementation, the precipitation at
junctions serves to bind the individual grains to-
( Copyright ChE Division, ASEE, 1981


CHEMICAL ENGINEERING EDUCATION









gether to form a rock.
The situation is quite different for limestone
rocks which, in the first place, are often formed by
deposition of rather irregularly shaped particles
consisting of shells or skeletal fragments of
various marine creatures. Then too, some re-
crystallation after deposition is common in car-
bonate rocks. Since a density change is involved,
porosity and pore structure are affected. Pore
structure changes are also caused by cementation,
which can be extensive, by dissolution of material
in water flowing through the rock, and by fractur-
ing, which occurs more easily than for sandstones.
The overall result is a pore space much less regu-
lar than in a sandstone. Differences in pore size

TABLE 1
Course Outline for Underground Processing
A. GEOLOGICAL BACKGROUND
1. General geology
a. Plate tectonics theory
b. Formation and characteristics of sedimentary
rocks
c. Age of rocks and the geological time scale
2. Formation of fossil fuel and mineral deposits
a. Origin of hydrocarbons in shale deposits
b. Relation to formation of other fossil fuels
c. Migration of petroleum from source rocks to
traps
d. Formation of petroleum traps-sedimentary
basins
e. Formation of mineral deposits by hydrothermal
processes
f. Relation between plate tectonics and sites of
fossil fuel and mineral deposits
B. FLOW, TRANSPORT, AND INTERFACIAL
PHENOMENA IN POROUS MEDIA
1. Basic interfacial phenomena-interfacial tension,
contact angles
2. Interfacial phenomena in porous media-capillary
pressure
3. Single-phase flow in porous media-Darcy's Law
4. Relative permeabilities and two-phase flow
5. Conditions for trapping or mobilizing a residual
phase
6. Heat transport in porous media
7. Mass transport, hydrodynamic dispersion
8. Chromatographic transport
9. Stability of displacement fronts in porous media
C. DESCRIPTION OF UNDERGROUND PROCESSES
1. Petroleum recovery
a. Immiscible displacement, waterflooding
b. Polymer and surfactant flooding
c. Miscible displacement, carbon dioxide injection
d. Thermal recovery processes
2. Underground coal gasification
3. In situ processes for oil shale and tar sands
4. Solution mining of uranium


Because flow, transport, and chemical reaction
are involved in most of the processes, chemical
engineers are well suited for this work
and should be much in demand.

and shape between rocks have a significant effect
on displacement of one fluid by another, e.g., of oil
by water, and are thus of great importance to the
engineer.
Even when consideration is restricted to sand-
stone rocks, relatively minor differences in com-
position can be important for performance of
certain processes. For instance, most sandstones
contain some clay minerals although their primary
component is silica. Clays can adsorb surfactant
molecules and they can serve as sites of cation ex-
change between liquids in the pore space and the
rock surface. Both these properties have a signifi-
cant influence on enhanced oil recovery processes
which employ surfactants. Indeed, failure to
properly account for ion-exchange effects is be-
lieved to be the main reason for poor performance
of at least one field test of the surfactant process.
Thus, the amount of clay originally deposited with
the sand is significant.
Finally, variation in depositional conditions
with position and time can cause significant
permeability variations within a petroleum-
containing rock. Injected fluids prefer to flow
through high-permeability regions, largely by-
passing regions of low permeability. In an extreme
case, permeability barriers may exist between
nearby wells in a formation, so that flow between
the wells is minimal. Such a situation was found
in a recent field test of an enhanced oil recovery
process. Fortunately, it was discovered during
preparations for the test, and process adjustments
were made before the test was begun.
A brief overview of plate tectonics theory
begins the course. Only some fifteen years old in
its modern form, this theory has been the most
exciting development in geology in decades be-
cause it has provided a unifying framework re-
lating diverse results from many fields of geology.
Then a rather extensive discussion of rock forma-
tion is given with emphasis on sedimentary rocks
where oil, oil shale, and tar sands were formed
and where they are found.
The next major topic is formation of fossil
fuel and mineral deposits. As the result of ex-
tensive work by petroleum geologists and geo-
chemists during the past thirty years, much has
been learned about the origin of petroleum. Shale


rALL 1981









In contrast to the usual situation in a chemical plant,
the "reactor" for an underground process is not built to the designer's specification
but is provided by nature. It is usually the result of geological processes
which have occurred over periods of tens to
hundreds of millions of years.


is a sedimentary rock consisting mainly of small
particles of clay minerals and other inorganic ma-
terials but also containing a few percent of organic
material. If the original deposit forms under
anaerobic conditions, the organic material is pre-
served and, on burial, undergoes chemical reaction
to form a complex polymeric material known as
kerogen. As burial depth increases, the tempera-
ture rises until, at some point, further reactions
take place in which the kerogen releases hydro-
carbon molecules in order to form a more compact
structure consisting largely of multiple aromatic
rings. Hydrocarbons so produced are the con-
stitutents of petroleum.
With modern analytical techniques such as gas
chromatography, the composition of organic ma-
terial in shale has been measured as a function
of depth in several locations. Such work has
allowed the course of the reactions which generate
hydrocarbons in shale to be followed. It has also
shown that the same basic chemical process is re-
sponsible for formation of petroleum, coal, and oil
shale. Differences in these materials are the result
of differences in composition of the initial deposits.
Oil shale is richer in organic material than most
petroleum source rocks while coal forms from
deposits which are primarily organic with only
a few percent of inorganic material, just the op-
posite of shales. The differences in composition
between the terrestrial organic material which
forms coal and the marine organic material which
is the source of most oil also lead to major differ-
ences in the distribution of reaction products,
e.g., to generation of more methane and fewer
longer-chain hydrocarbons in coal. Oil shales have
never been subjected to temperatures high enough
to cause appreciable hydrocarbon release. Effect-
ing such release is the chief objective of oil shale
processing. Two excellent summaries of current
knowledge of fossil fuel formation are the recent
books by Tissot and Welte [1] and Hunt [2].
Also covered in the course are "primary" mi-
gration of hydrocarbons from the shales where
they form to nearby sandstones or limestones, a
process which remains poorly understood, and
"secondary" migration of oil within the reservoir


rocks. Generally speaking, oil travels upward
owing to gravitational effects until it reaches a
"trap" where a low-permeability shale or some
other permeability barrier precludes further up-
ward movement. Several geological structures
which can cause trapping are considered. So are
salt dome formation and other geological condi-
tions which can cause these structures to form.
Some comments are made on the emerging picture
of the connection between plate tectonics and oil
formation.
Tar sands are oils which have been degraded
after trapping by exposure to ground waters
containing bacteria. The bacteria preferentially
consume short-chain and paraffinic compounds.
Depending on the amount of degradation, the re-
maining oil may be only slightly more viscous than
the original oil, or it may be a "tar" with a vis-
cosity of tens of thousands of centipoise or more.
Student assignments for this part of the course
consist of: 1) a set of simple problems, which
provide a feeling for the magnitude of such quanti-
ties as the rate of plate motion over the earth's
surface, the heat flux from the earth's surface,
and the amount of water needed to increase the
porosity of a limestone rock by dissolution, and
2) a short paper on some aspect of the geological
part of the course. Topics selected by the students
have ranged from discussion of certain geophysi-
cal and geochemical methods for locating oil and
mineral deposits to a summary of the arguments
given by the few geologists who have yet to accept
plate tectonics theory. Most of the papers, how-
ever, have dealt with some aspect of the formation
of fossil fuels in more detail than the class notes
and lectures.
In summary, some knowledge of geology is
essential to those working in underground pro-
cessing. Experience has shown that the more one
knows about formation properties, the better the
chances of process success. Although engineers
naturally interact with geologists, who have a
detailed understanding of depositional conditions,
in developing formation descriptions, the inter-
action is more productive if the engineer has some
background in geology.


CHEMICAL ENGINEERING EDUCATION








INTERFACIAL PHENOMENA, FLOW, AND
TRANSPORT IN POROUS MEDIA

A ALTHOUGH THE FORMATIONS which serve as sites
for underground processes vary widely in
structure and composition, they may all be con-
sidered porous media. Since interfacial phenomena
control the distribution of immiscible fluids such
as oil and water within a porous medium at the
low flow rates common in oil recovery processes,
the first step is a thorough discussion of interfacial
tension and contact angles. A brief account of
surfactants and their properties is included as
well to provide a background for later considera-
tion of surfactant processes for enhanced oil re-
covery.
In porous media interfacial phenomena are
responsible for the pressure difference or "capil-
lary" pressure between immiscible fluids. Varia-
tion of capillary pressure during slow displace-
ment of one fluid by another is described. Empha-
sis is given to interfacial instabilities which lead
to "Haines jumps," the rapid and irreversible
final stage of displacement occurring in individual
pores even when the overall rate of displacement
is slow. As a result of these instabilities, capillary
pressure behavior exhibits hysteresis, i.e., capil-
lary pressure variation when water displaces oil
is not simply the reverse of that when oil dis-
places water.
Next, single-phase and two-phase flow in porous
media are discussed. Consideration is restricted to
low flow rates where Darcy's Law applies, the
usual situation in underground processing. An
important topic is the mechanism of trapping of a
residual phase when one fluid displaces another.
Because of such trapping, water is usually able to
displace only about half the oil originally present
in a reservoir. Obviously, the conditions required
to prevent trapping are of great interest. These
amount to a sufficiently large ratio of viscous to
interfacial forces, i.e., a sufficiently large value
of the dimensionless capillary number (tv/y4)),
where I and v are continuous phase viscosity and
superficial velocity, y is the interfacial tension
between fluid phases, and 0 is porosity.
After some coverage of heat and mass trans-
port in porous media and hydrodynamic dis-
persion, chromatographic transport in porous
media is considered. Introduction of the methods
of chromatographic analysis is a key part of the
course since they are used later in the analysis of
oil recovery processes. The presentation consists


of a sequence of examples of ever increasing
difficulty, ranging from simple adsorption of a
solute or its partitioning into a trapped fluid
phase to immiscible displacement of one fluid by
another (Buckley-Leverett analysis) to ion ex-
change phenomena to two-phase displacement pro-
cesses with partitioning of various components
between phases. The method of characteristics is
used to solve the simpler examples and to illustrate
how traveling concentration waves develop. Then
the more complicated examples are treated by
Helfferich's general scheme [3], which begins with
the assumption that concentration waves occur.
Winding up this portion of the course is a dis-
cussion of the stability of displacement fronts in
porous media. No matter how well a fluid can dis-
place another from an individual pore, its effective-
ness in a large-scale process is limited if the macro-



... the study of flow, transport, reaction,
and interfacial phenomena in porous media is an
excellent application of basic chemical engineering
principles and one that has utility far
beyond underground processing.


scopic front between displacing and displaced
fluids is unstable. For in this case the injected
fluid travels through the reservoir in channels,
completely bypassing many pores containing the
oil or other fluid originally present.
The lectures here deal first with instability
in the form of viscous fingering which occurs, for
example, during waterflooding of high viscosity
oils. Then transport effects are discussed with
stress given to their importance in thermal pro-
cesses for oil recovery and in underground coal
gasification.
Homework problems are assigned frequently
throughout this part of the course as the basic ma-
terial is by nature more quantitative than in the
geological background section.

PROCESSES FOR FOSSIL FUEL RECOVERY
SN THE LAST PART OF THE course the major
underground processes in use or being developed
are described. More attention is given to petroleum
recovery than to other processes, primarily be-
cause more is known about it. Waterflooding is
considered first. Then polymer flooding, surfactant
flooding, and miscible displacement, e.g., with high


FALL 1981








pressure carbon dioxide, are discussed. Basic
physical mechanisms are stressed in lieu of details
of processes performance. Simplified analyses
using chromatographic transport methods are used
to illustrate the main features of each process.
Because the chromatographic analyses em-
ployed assume that phase equilibrium and chemi-
cal reaction equilibrium are reached instantane-
ously, other methods are used for analysis of
thermal oil recovery processes such as steam drive
and underground combustion. In these processes
the rate of heat transport from the reservoir to
the surrounding formations is of great importance,
and heat conduction terms must be included in
the analysis.
Finite rates of chemical reaction are important
in other types of processes. Examples are the use
of acids to dissolve some of the rock near a well,
thereby increasing permeability, and reverse com-
bustion processes which are used in the initial
stages of underground coal gasification and which
are potentially of use in in-situ tar sand recovery.
Some aspects of a process are more important
in underground than in ordinary processing.
Clearly one highly desirable feature of an under-
ground process is relative insensitivity to varia-
tions in formation properties since, as indicated
above, detailed knowledge of such properties at all
points in a formation cannot be obtained.
The linked-vertical-well method of under-
ground coal gasification is used as an example to
illustrate this point. Reverse combustion is used
to "link" injection and production wells, i.e., to
provide a high-permeability path between them.
Once the link is complete air or oxygen can be
injected at relatively low pressure with a high de-
gree of assurance that, whatever the flow proper-
ties of the original coal, most of the injected gas
will travel along the link where resistance to flow
is low. This behavior has the highly desirable
results that most injected gas participates in the
main gasification reaction and that only a small
amount leaks away to surrounding areas where
its presence could be undesirable from an environ-
mental point of view.
Student assignments here consist of some
homework problems on waterflooding and sur-
factant flooding and a project involving a short
paper on some feature of a particular underground
process of interest to the student. Some of these
papers have been basically literature surveys,
while others have been analyses of certain pro-
cesses using chromatographic transport methods.


CONCLUDING REMARKS
N O EXISTING TEXTBOOK IS suitable for the entire
course. As a result, I have prepared notes for
most parts. Some books and articles which have
proved useful in this task and which are sources
of further information for students are listed
below [1-12]. The last part of the course on the
processes themselves is, except for the discussion
of waterflooding, based largely on journal articles
which have appeared during the past few years.
In summary, the course provides an introduc-
tion to underground processing to acquaint
students with opportunities in this area and with
pertinent fundamental knowledge. The geological
background material has been emphasized to a
greater extent in this article than in the course
itself because of its novelty and because the
author believes that interaction between chemical
engineering and geology may be fruitful in
generating research ideas beyond the present topic.
From a more traditional chemical engineering
view, however, the study of flow, transport, re-
action, and interfacial phenomena in porous
media is an excellent application of basic chemical
engineering principles and one that has utility far
beyond underground processing. 0
REFERENCES
1. Tissot, B. P. and D. H. Welte, Petroleum Formation
and Occurrence, Berlin, Springer Verlag, 1978.
2. Hunt, J. M., Petroleum Geochemistry and Geology,
San Francisco, W. H. Freeman, 1979.
3. Helfferich, F., Soc. Petrol. Eng. J., 21, 51-62 (1981).
"Theory of multicomponent, multiphase displacement
in porous media."
4. Barnes, H. L. (ed.), Geochemistry of Hydrothermal
Ore Deposits, 2nd ed., New York, Wiley, 1979.
5. Selley, R. C., An Introduction to Sedimentology, New
York, Academic Press, 1976.
6. Press, F. and R. Siever, Earth, San Francisco, W. H.
Freeman, 1974.
7. Scheidegger, A. E., The Physics of Flow Through
Porous Media, 3rd ed., University of Toronto Press,
1974.
8. Dullien, F. A. L., Porous Media-Fluid Transport
and Pore Structure, New York, Academic Press,
1979.
9. Muskat, M., Physical Principles of Oil Production,
New York, McGraw-Hill, 1949.
10. Craig, F. F., Jr., The Reservoir Engineering Aspects
of Waterflooding, Dallas, Society of Petroleum Engi-
neers of AIME, 1971.
11. Craft, B. C. and M. F. Hawkins, Applied Petroleum
Reservoir Engineering, Englewood Cliffs, N.J.,
Prentice-Hall, 1959.
12. Aris, R. and N. R. Amundson, Mathematical Methods
in Chemical Engineering, Vol. 2, Englewood Cliffs,
N. J., Prentice-Hall, 1973.


CHEMICAL ENGINEERING JPVCATIQN










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FALL 1981










44%c4"e in


POLYMER PROCESSING


DAVID S. SOONG
University of California
Berkeley, CA 94720


IN VIEW OF THE ever-increasing trend of polymer
utilization, there exists a need for a rigorous
course in polymer rheology and melt processing at
the graduate level. This led to a decision by the
faculty of chemical engineering at Berkeley to
develop two courses in polymer processing and re-
action engineering, which can be taken successively
or individually. When the first of the two-course
sequence was recently offered in the form of ChE
295N, Special Topics in Polymers, the emphasis
was placed on polymer dynamics, rheology and
processing.
Major references for the lecture materials of
ChE 295N included Middleman's "Fundamentals
of Polymer Processing" [1] and Bird et al's "Dy-
namics of Polymeric Liquids" [2, 3].
A survey of the various kinds of polymer pro-
cessing operations was given at the beginning of
the course, introducing the students to the di-
versity of this field. The importance of the rheo-
logical properties of polymers in affecting the
process characteristics was stressed at this early
stage, which prompted subsequent review of the
continuum mechanics and molecular approaches to
describe the behavior of polymeric fluids. Selected
processes, such as extrusion, calendering, injection
molding and fiber spinning, were then separately
discussed. In each case the general transport equa-
tions were first set up and boundary conditions
stipulated. Simplifying assumptions were made to
facilitate solution of the equations. Constitutive
equations for purely viscous materials (both
Newtonian and non-Newtonian) were used to
obtain model predictions before the complication
of viscoelasticity was introduced. This progressive
increase in the degree of sophistication allowed
the students to appreciate the critical considera-
tions in designing and operating processes handl-
ing viscoelastic materials. Results for viscoelastic

� Copyright ChE Division, ASEE, 1981


David Soong obtained his B.S. in Chemistry from National Taiwan
University in 1973. Upon arrival in the United States in 1975, he
pursued graduate work in Chemical Engineering at the University of
California at Berkeley, receiving his M.S. in 1977 and Ph.D. in 1978
under Mitchel Shen. Since 1979 he has been an Assistant Professor of
Chemical Engineering at Berkeley. His major research interests are
theological properties of polymers, polymer reaction engineering,
plasma-initiated polymerization and related microelectronics applica-
tions. He is a member of the Society of Rheology, Sigma Xi, AIChE and
ACS.

models were compared with those of the purely
viscous cases.
With the above brief introduction to the origin
and nature of this course, we are now in a posi-
tion to discuss various aspects of the course, such
as objectives, detailed content, teaching strategies
and, most importantly, observations and ex-
periences from its first offering.

COURSE OBJECTIVES
THE COURSE SERVED A number of functions and
carried multiple objectives. For example, a
variety of important process operations commonly
encountered in industry were examined. Basic
mechanical components and associated geometries
determining the critical flow field and state of
deformation of process fluids were depicted and
analyzed in depth. Much effort was devoted to
developing the ability to set up equations of con-
tinuity and motion to describe the processes under
consideration. For nonisothermal and/or reacting
systems, heat and mass transport equations were


CHEMICAL ENGINEERING EDUCATION








invoked. These dynamic equations and related
boundary/initial conditions were independent of
the material being treated. The latter affected the
processes through the use of constitutive equa-
tions. These in turn were merely mathematical
representations (or rather approximations) of the
inherently complicated responses of the fluids to
the imposed flow field. The importance of ma-
terial properties in affecting polymer processing
was illustrated by several examples. A representa-
tive one involved laminar pressure flow in a
cylindrical conduit of constant cross-section.
Newtonian behavior, power-law fluid, and a hypo-
thetical system obeying Maxwell equation with
constant viscosity and relaxation time were
examined successively. In the first two cases sig-
nificant differences in the volumetric flowrate
were predicted at a given pressure gradient. When
the pressure gradient was suddenly varied, the
new steady state was rapidly reached for these
purely viscous fluids. The viscoelastic model gave
similar steady-state results, depending on model
parameters. However, when the pressure gradient
became a function of time, marked transient be-
havior was observed, even if uniform shear rate
in the radial direction was assumed at all time
(an idealized situation considering the finite rate
of momentum transfer).
Polymers, being viscoelastic and exhibiting
quite "peculiar" behaviors, are, in principle, amen-
able to systematic mathematical description. The
actual analytic/numerical manipulations involved
may be vastly greater than those for simpler
(viscous) fluids. Still, chemical engineers with a
sound training in transport phenomena coupled
with some knowledge of material properties of
polymers, should be capable of comprehending and
analyzing these polymer processes. Hence, this
course dispels certain "mystique" surrounding
polymers, viscoelasticity and the related processes.
In addition, an important concept emerged from
the repeated use of the series of constitutive equa-
tions to different processes. It was realized that
viscoelasticity is a generality rather than a
specialty, as purely viscous responses can be de-
rived from a viscoelastic equation by neglecting
certain terms, and Newtonian fluid represents
nothing more than a limiting behavior.
This course seeks to enhance the ability of
the students to apply transport principles to
situations where the fluid properties as well as
flow kinematics are both quite complicated. Solu-
tion of the simultaneous equations describing the


The first phase is a brief review of the
various common polymer processes, familiarizing the
students with the breadth of the subject and
illustrating the importance of modeling and
application of transport equations.

processes by either making simplifying assump-
tions or resorting to numerical methods is another
major objective. The relative merits and limita-
tions of either approach can thus be ascertained.

COURSE CONTENT

T HE COURSE CONSISTS OF three phases. The first
phase is a brief review of the various common
polymer processes, familiarizing the students
with the breadth of the subject and illustrating
the importance of modeling and application of
transport equations. Simple model flows (e.g.,
pressure and couette flow in parallel plates,
rectangular channels and concentric cylinders
executing axial and transverse motions) are then
analyzed in preparation for the more complicated
actual processes where the different modes of
simple flows frequently occur simultaneously.
Next the problem of describing theological proper-
ties of polymers is addressed. Experimental results
on two major flows (simple shear and uniaxial
elongation) are discussed extensively. Constitu-
tive equations of different levels of approxima-
tion, such as Newtonian, power-law and other
nonNewtonian functions, and several selected
viscoelastic models, are developed for obtaining
model predictions in later stages of the course.
Finally, individual processes are analyzed in detail.
In each case the applicable dynamic equations
and the appropriate boundary conditions are es-
tablished, thus forming the mathematical frame-
work of the model. Constitutive equations de-
veloped previously are then substituted into the
set of dynamic equations to yield predictions.
Table 1 outlines the course content.
As Table 1 indicates, ample opportunities for
modeling studies were provided in this program.
Couette and pressure flows in simple geometries
were thoroughly examined for Newtonian and
power-law fluids. The effects of combining two
or more simple flows for these purely viscous
fluids were also presented. These simple model
flows formed the basis for later development of
processes involving viscoelastic materials in com-
plex geometries.
Development of viscoelastic constitutive equa-


FALL 1981


205









tions was preceded by a brief review of various
empirical nonNewtonian functions for rate-de-
pendent viscosity. Elastic phenomena exhibited by
polymers and their influence on processing were
then discussed, justifying the use of viscoelastic
models under certain operating conditions. A
critical consideration here is the ease of applica-
tion of these models to engineering flow calcula-
tions. Unfortunately, most continuum models and
molecular theories developed to date [2, 3] to de-
scribe theological properties of concentrated solu-
tions and polymer melts are so mathematically
complex as to render their direct application to
actual process design impractical. This prompted
the adoption of the contravariant Oldroyd form of
the Maxwell equation [2, 3].
8T
r + X- = 71y (1)


TABLE 1
Course Outline

1. INTRODUCTION AND FUNDAMENTALS
Introduction to Polymer Processing
Modeling Philosophy
Review of General Transport Equations
* Equations of Continuity
* Equations of Motion (Dynamic Equations)
* Heat and Mass Transport Equations
Kinematics and Dynamics
Boundary and Initial Conditions
Simple Model Flow Analysis
Combined Flow Analysis
2. DEVELOPMENT OF CONSTITUTIVE EQUATIONS
FOR POLYMERS
Rheological Properties of Polymers-Experimental
Results
Continuum Mechanics and Molecular Models
Constitutive Equations for Purely Viscous Materials
Constitutive Equations for Viscoelastic Materials
Theories for Polymer Melts
3. DISCUSSION OF INDIVIDUAL POLYMER
PROCESSES
Extrusion * Newtonian and NonNewtonian Fluids
* Isothermal and Nonisothermal Analyses
Calendering * Newtonian and NonNewtonian Fluids
* Lubrication Approximation
* Normal Stresses and Viscoelasticity
Fiber Spinning * Newtonian, NonNewtonian and
Viscoelastic Fluids
Injection Molding * Isothermal and Nonisothermal
Analyses for Viscous Fluids
* Pressure-Dependent Viscosity
Polymerization Reaction * Constitutive equations for
Diffusion and Generation
* Dimensional Analysis of a
Tubular Reactor


... the course dispels a certain
"mystique" surrounding polymers, viscoelasticity
and the related processes.


where T and y are the stress and rate-of-deforma-
tion tensors, 8/8t is the Oldroyd contravariant de-
rivative, and X and 47 are the Maxwell relaxa-
tion time and viscosity of the fluid. Due to the
incorporation of this equation, the process models
now possess a unique set of transient responses.
However, Equation 1 is only qualitatively correct,
thus necessitating further improvement without
undue increase in mathematical tractability. One
such remedy is achieved by introducing certain
structure-property relationships into the original
formulation, i.e., making X and 1 structure-
dependent and thus time-dependent [4, 5]. Al-
though this approach is still in its infancy, the
resulting equation has proved useful [5] and is
mathematically simple so as to be practical for
engineering calculations. Throughout the balance
of this course, the original and the modified
Maxwell equations are used extensively.

COURSE REQUIREMENT AND
TEACHING STRATEGIES
A LIST OF TERM PROBLEMS was given to the
class, from which every member chose one for
an in-depth literature search and analytical/
numerical solution. Time was set aside at the
end of the course for student presentations of
their work. This was a successful endeavor in that
it encouraged much effort in problem solving and
stimulated active post-presentation discussions.
The complete sequence of identifying a research
problem, pursuing its solution, presenting the find-
ings and generating new ideas was experienced
through the term assignment, which was con-
ducted with minimal supervision. Research inde-
pendence was encouraged in the process.

SELECTED TERM PROBLEMS
O NE PROBLEM ENTAILED THE prediction of
transient velocity profile development in
planar couette and pressure flows using the struc-
ture-dependent Maxwell model. Solutions obtained
via collocation techniques [6] revealed a wide
range of complicated behavior including oscilla-
tory approach to steady state. Uniaxial extensional
flow of polymer melts was reviewed by a member


CHEMICAL ENGINEERING EDUCATION








of the class, who was able to propose a new
constitutive equation. Preliminary evaluation of
this proposal shows promise and suggests further
work. Another project involved the application
of polymers as photoresist or e-beam resist ma-
terials in microelectronics industry. Resist
spinning on semiconductor wafers was modeled.
The relevant continuity and dynamic equations
were established in this effort. Analytical solution
was obtained only through the incorporation of
rather drastic assumptions. More accurate results
rely on incorporation of improved viscoelastic
equations and concentration-dependent solvent
diffusion rate expressions.
Other problems included the effect of pres-
sure-dependent viscosity on injection molding,
dynamic behavior of a single-screw extruder,
bubble rise in a viscous medium, and attempts at
modeling high-conversion polymerization reactors.
As a result of these class efforts, some potential
long-term research projects were nucleated. 0


I^ stirred pots

HEAT EXCHANGERS
The Agony and the Ecstasy
Premeditated motions
Control the beckoning valves.
Water begins its hereditary migration
Towards the shell side
While steam penetrates other water
Destined by ulterior motives to ramble
In a twisting gyrating frenzy
To the tube side.

Swept up in the confusion
Of bombarding torrents
A decision must be reached
By the bold few who dare
Comprehend heat exchangers,
IS there a heat balance ?

Time vacates as great minds
Ponder through flow rate commandments
And theories of original heat.
Minds seeking to know
Whys and wherefores,
Pros and cons,
Ins and outs,
And clues only heat exchangers can provides
The elusive stigma attached to heat transfer.


ACKNOWLEDGMENT

The author appreciates the support and en-
couragement of his colleagues in the development
of this course. Most of all, he thanks his students
for making the offering of this course an enjoyable
and rewarding experience.

REFERENCES
1. S. Middleman, "Fundamentals of Polymer Processing,"
McGraw-Hill, New York, 1977.
2. R. B. Bird, R. C. Armstrong, and 0. Hassager, "Dy-
namics of Polymeric Liquids, Vol. 1: Fluid Me-
chanics," Wiley, New York, 1977.
3. R. B. Bird, O. Hassager, R. C. Armstrong, and C. F.
Curtiss, "Dynamics of Polymeric Liquids, Vol. 2:
Kinetic Theory," Wiley, New York, 1977.
4. D. S. Soong and M. Shen, J. Rheol., 25, 259 (1981).
5. T. Y. Liu, D. S. Soong and M. C. Williams, Polym.
Eng. Sci., 21, 675 (1981).
6. J. Villadsen and M. L. Michelsen, "Solution of
Differential Equation Models by Polynomial Ap-
proximation," Prentice-Hall, N.J., 1978.


Peering through the cheap answers
The truth shyly steps forward;
Heat has indeed been abducted
By common two-bit fouling resistance schemes
Use primarily by alien heat exchangers
Affiliated with corporations of ill repute
And shady character profiles.
This then becomes ... the agony.

Despite seemingly corrupt odds,
Heat transfer does occur;
The hot gets colder
The cold gets hotter
And data gets its wish, a plot.

How can one put into words
The ecstasy of a well correlated Wilson plot?
How can one man conceived in liberty
And dedicated to the proposition
That all men are created equal
Stand up and boldly proclaim
"I have found it... heat exchangers!"

Let this man step forward and be heard,
For he has indeed found
The elusive truth;

And this is . . . the ecstasy.

Ellen Barrar, ChE '79
Oregon State University


FALL 1981










SSEPAlecuRATe cUeP i



SEPARATION PROCESSES


PHILLIP C. WANKAT
Purdue University
West Lafayette, IN 47907

SEPARATION PROCESSES AND MASS transfer have
long been an integral part of chemical engi-
neering education. At Purdue University two
graduate electives in separation processes and
one elective in mass transfer are offered. The
graduate students also all take a course in trans-
port processes, which covers the basics of mass
transfer.
One of the separation electives (ChE 558,
Equilibrium Stage Separation Processes) is a
dual level senior/graduate elective. This course
covers multicomponent distillation, absorption and
extraction and an optional section on chroma-
tography. C. Judson King's text Separation Pro-
cesses is used, and the course has been taught for
the last nine years (see Ref [1] for details).
The mass transfer elective (ChE 624, Mass
Transfer) has been taught as a special topics
course. Recently, this course has emphasized the
fundamentals of multicomponent systems, mass


Phil Wankat received his BSChE from Purdue and his PhD from
Princeton. He is currently a professor of chemical engineering at
Purdue. He is interested in teaching and counseling, has won several
teaching awards at Purdue, and is a part-time graduate student in
Education. Phil's research interests are in the area of separation
process with particular emphasis on cyclic separations, two-dimensional
separations, preparative chromatography, and high gradient magnetic
separation.


transport through membranes, convective mass
transfer, and the macroscopic mass balance. Ap-
plications emphasized have been in turbulent
diffusion, mass transfer at phase boundaries, mass
transfer with simultaneous chemical reaction,
fixed bed sorption, transport through polymers,
and biomedical devices.
The third elective in this area (ChE 623,
Separation Processes) is a much newer course and
has only been taught twice in its current form.
This course was designed to cover subjects not
covered in the other two electives, and to do it in
different ways. The result is a unique elective in
separation processes which is the subject of this
article.

COURSE PHILOSOPHY
IN DESIGNING CHE 623, a course philosophy had
to be developed and followed. The first tenet
was that as a special topics elective it is difficult
to say something must be part of the student's
education. Thus, I was willing to initially consider
almost any subject as long as it was in the general
area of separation processes. However, the second
tenet limited the first since I decided not to allow
substantial overlap with either ChE 558 or ChE
624. Thus, distillation, absorption, extraction and
fundamental mass transport theory would not be
covered.
My third decision was to spend close to half
the semester on operating techniques for adsorp-
tion, chromatography and ion exchange. The
major reason for this choice was selfish: this is
my research area (and I want to tell the world
about my research) and it is an important class
of separation techniques which I believe will be-
come increasingly more common in the future.
Because of my enthusiasm the students also be-
come interested and, in addition, it helps train
my graduate students for their research.
The fourth decision was to allow the students
to be selfish and to pick areas that interest them

� Copyright ChE Division, ASEE, 1981


CHEMICAL ENGINEERING EDUCATION











PERIODS)


TABLE 1
Preliminary Course Outline
SUBJECTS


1 Introduction
2 Overview and classification schemes [2, 3]
3-6 Fixed beds: Phenomena [4], column balances
[5, 6], local equilibrium theory [5, 6]
7 (R) Discussion of separations literature and of
topics for second half of course
8 Sorbex process [7] and two-dimensional
analogy [8]
9 (R) Discussion of experimental papers
10 Moving feed point chromatography [9]
11 Parametric pumping [4, 10]
12 (R) Discussion of theoretical papers
13 (R) Library search methods
14 Pressure swing adsorption [11, 12]
15 Cycling zone adsorption [4, 13, 14]
16 Application local equilibrium model to ion
exchange [5, 15]
17-18 Solution for local equilibrium with dispersion
and linear system analysis [16, 17]
19 Constant Pattern Solutions [6]
20-22 Thomas Solution Method [6, 16, 18]
23 Test
24 (R) No class, Individual meetings on course
project
25-26 Topics selected by class
27 (R) No class, Individual meetings
28-29 Topics selected by class
30 (R) No class, Individual project reports
31-34 Topics selected by class
35 (R) No class, Individual meetings
36-42 Topics selected by class
43-45 (R) Student presentations of course projects
Finals 2nd test (not a final)
(R) Periods spent on separations research and class research project.

for the second half of the semester. Thus I let the
class pick the topics, subject only to the first two
constraints.
The last three decisions were concerned with
the way the course was taught. Since the lecture
is an efficient method for presenting new informa-
tion, I decided that most of the content would be
transmitted by lecture. An assigned text was not
used, partially since there is no text covering the
diverse topics of this course, but also because I
wanted the students to get a feel for the separa-
tions literature. So a combination of textbooks,
journal articles, and handouts was used. Finally,
I wanted the students to get an idea of what re-
search in separations is like. This goal was
achieved with a course project which consisted of
a small, theoretical research project on an un-
solved problem.
The ways in which these decisions were imple-
mented is discussed in detail below.


We first started with ordinary
adsorption and then considered simulated
counter-current operation and the related moving
feed point chromatography.


COURSE SCHEDULE

TO MEET THE OBJECTIVES discussed above, the
preliminary schedule shown in Table 1 was
handed out the first day of class. Note that during
the first half of the course a variety of operating
methods for adsorption, chromatography and ion
exchange were covered, and that this portion of
the schedule is listed in detail. The schedule for
the second half of the semester was left open and
was filled in only after considerable discussion with
the students.
Throughout the semester, time was allotted
for discussion of the research literature in separa-
tions, and for the research project. Individual
meetings with the students were scheduled and
time was set aside for student presentations at the
end of the semester.

ADSORPTION, CHROMATOGRAPHY AND ION
EXCHANGE COVERAGE

T HE COURSE OUTLINE FOR coverage of adsorp-
tion, chromatography and ion exchange is
shown in Table 1. First we looked at the basic
equations of change for a packed bed in detail
[4, 5, 6]. Then the logical order to make assump-
tions was discussed [5, 6] and the solution by the
method of characteristics for the local equilibrium
model was developed [5, 6]. Once this basic model
had been developed, the local equilibrium model
was used to explain and contrast a variety of
operating methods. We first started with ordinary
adsorption [5, 6] and then considered simulated
counter-current operation [7] and the related
moving feed point chromatography [9]. The
students further explored these methods with the
local equilibrium model by solving homework
problems which are not in the literature. As an
aside we discussed how analogous two-dimensional
separators could be constructed and analyzed [8].
We then discussed a variety of cyclic operating
methods. Both direct and recuperative mode para-
metric pumping [4, 10] were discussed. The com-
mercially important pressure swing adsorption
system [4, 11] was studied and the limits of ap-
plicability of the local equilibrium model were
demonstrated [12]. Single and multicomponent


FALL 1981









cycling zone adsorption [4, 13, 14] were then ex-
plored. Finally, the local equilibrium model was
used to study binary ion exchange [5, 15], and
differences and similarities with Langmuir ad-
sorption were highlighted. Homework assignments
developed from my research were used to further
investigate these subjects.
Having looked at a variety of operating
methods we then studied several other mathe-
matical models. First the linear local equilibrium
model with dispersion [16, 17] was introduced, and
the use of superposition in the solution of linear
problems was studied. Then constant pattern
methods [6] were explained, and the section was
completed with the Thomas solution method
[6, 16, 18]. Again homework assignments provided
practice.


We discussed nucleation and
crystal growth, crystal size distributions,
and crystallization equipment.

Four homework assignments with a total of
twenty problems were passed out and a one hour
closed book test was given. Students were given
an equation sheet in advance so they did not have
to memorize equations.
In the past we covered interacting multicom-
ponent analysis by the local equilibrium method,
and very briefly discussed numerical methods. Be-
cause of time constraints these areas were not
covered this semester. In the future I would like
to include two or three classes on numerical
methods. Obviously, other topics could be included.
The selection used here satisfied my purposes. The
material was covered at a rapid but digestable
pace.

TOPICS SELECTED BY CLASS
Roughly half of the lecture periods were left
open for topics to be selected by the class. Since
students are not accustomed to selecting their
own topics, I lead them through the selection pro-
cess. The need to select topics was discussed
during the first class period and in the second
class period a variety of separation methods were
briefly discussed. During period seven the students
were to browse through a variety of journals and
look at articles on separation methods. Then they
developed and turned in a first list of topics of
interest.
I took these first lists and made a master list


which was returned to the students. They then
gave me enlarged second lists of their interests
and I again made a master list and distributed it.
The third time I asked for a list with items rank
ordered. I collated these lists and decided what
to cover during the remainder of the semester.
The two topics of interest to the majority of the
students were membrane separations and crystal-
lization. In addition, I decided to cover molecular
sieves, activated carbon and affinity chromatogra-
phy, which were all requested by one or two
students. These latter topics were connected with
the first half of the semester and could be covered
quickly. Although we were not able to include all
of the student requests, at least one topic from
each student's list was discussed.
After considerable reading, an outline and
reading list for the second half of the course was
developed (Table 2). We started by discussing
the characteristics of molecular sieve adsorbents
[19, 20] and of activated carbon [21] and solvent
recovery by activated carbon [22]. Activated
carbon was the one topic where students did not
like the assigned reading [21]. Affinity chroma-
tography was covered with an emphasis on princi-
ples and not the specific reactions [23].
Seven class periods were devoted to membrane
separations. We started by reviewing all types of
membrane separators [24], and studied reverse
osmosis and ultrafiltration in detail. Osmotic pres-
sure [25] was briefly discussed since everyone had


TABLE 2
Outline of Topics Selected by Class


PERIODS)


25
26
28
29
31

32

33

34 and 36
37
38-39

40-41
42


SUBJECT


Molecular Sieve Adsorbents [19, 20]
Activated Carbon Adsorption [21, 22]
Affinity Chromatography [23]
Introduction to Membrane Separations [24]
Osmotic Pressure [25] and start concentra-
tion polarization [26]
Concentration polarization without gelling
[26, 27]
Concentration polarization with gelling
[26, 28]
Transfer inside the membrane [29]
Equipment and cascades [28, 30, 31]
Crystallization from solution: Nucleation
and crystal growth [32, 33, 34]
Crystal Size Distributions [32-35]
Crystallization equipment and operation
[32, 34, 36]


Note: Missing class periods were used for research project purposes
and are listed in Table 1.


CHEMICAL ENGINEERING EDUCATION









The two topics of interest to
the majority of the students were
membrane separations and crystallization.

forgotten this portion of their physical chemistry.
Then the mathematical analysis of concentration
polarization both without [25, 27] and with gelling
[26, 28] was covered. We switched to irreversible
thermodynamics to study transfer inside the mem-
brane [29]. Finally we discussed membrane equip-
ment and cascades [28] with additional examples
of cascades presented in class [30, 31].
The student-selected topics were finished with
five periods on crystallization from solution. We
discussed nucleation and crystal growth, crystal
size distributions, and crystallization equipment.
The two basic references [32, 33] were supple-
mented by other sources [34-36].
The student-selected topics section included
three homework assignments with a total of a
dozen problems and a second closed book test was
given. I again gave the students equation sheets
before the test since this approach seemed to work
well.
One difficulty inherent in letting students select
the topics is that the professor may not know any-
thing about the topic. This was certainly the case
for crystallization, and I am not an expert in
membrane separations. I was aware of this po-
tential problem ahead of time, and warned the
students of its possibility. Throughout the se-
mester I spent considerable time reading up on
the various topics, and put crystallization last so
that I would have more time to prepare. Since
the course is in my research area, I was willing
to devote extra time to reading and learning. My
lack of expertness was only apparent a few times,
and the students were quite understanding. Over-
all, this portion of the course went very well.

SEPARATIONS RESEARCH AND RESEARCH PROJECT
SINCE ONE OF THE MAJOR course goals was to
introduce the students to separation research,
a considerable amount of effort was devoted to
the course project. To combat the nemesis of
student research projects, procrastination, I de-
veloped a pattern of exercises, small projects, and
check points which culminated in the final written
paper. The eleven classes labeled (R) in Table 1
are part of this pattern.
The pattern started with browsing through
journals and then listing (without reading) a


total of 15 articles on subjects of interest. The
students then read a recent experimental article
of their choice. This article was then analyzed in
detail starting with the bibliographic citation and
the purpose of the study. The methods, results
and authors' conclusions were described and finally
the student presented his evaluation of the study.
In class the students were divided into small
groups and informally discussed the papers they
had read. The same procedure was repeated for
theoretical papers. This activity was very popular
with the students. They felt they learned a lot in
the presentations, but weren't anxious because the
presentations were informal and ungraded. The
written papers were collected and graded.
The class heard a librarian lecture on library
search methods. As an assignment they were
asked to find certain articles from vague citations
and to list articles citing given papers or authors.
This was a useful activity, but the presentation
was at a somewhat too low level.
Next the students selected a general topic of
interest for their research project. They could
either select a topic of their own or pick from a
list I passed out and when they had selected a
topic, they were asked to meet individually with
me to discuss it. A citation search and literature
review were required.
Halfway through the semester a very specific
problem within their general topic area had to be
picked. I discussed these problems with each
student and requested that they develop a clear
and limited problem statement. The specific pro-
jects chosen are listed in Table 3. The projects
were to involve a theoretical analysis of a problem
which had not been solved or use of a new mathe-
matical method on a problem which had previously
been solved. Four of the seven students worked on
problems which I suggested. Two progress reports
were required during the second half of the se-
mester in order to stimulate continual progress.

TABLE 3
Student Research Projects
Analysis of multicomponent, equilibrium, pressure swing
adsorption.
Numerical analysis for supercritical fluid adsorption.
Numerical solution for affinity chromatography.
Determination of adsorption isotherms by a continuous
flow method.
Dynamic behavior of discrete cycling zone extraction.
Cylindrical rotating continuous flow electrophoresis.
Mathematical modeling of rotary thermal diffusion
columns.


FALL 1981











To combat the nemesis of student
research projects, procrastination, I developed
a pattern of exercises, small projects, and
check points which culminated in the
final written paper



To encourage a carefully written paper, an out-
line was required a week prior to the oral report.
These outlines were commented on and returned
to the students. A rough draft of the entire paper
was then required when the student presented his
oral report on his project and these were graded
and returned before the students wrote their final
draft.
Despite this structure there was some pro-
crastination. However, it was significantly less
than I have observed in any other class. Two
students ran out of time, but five of the seven
projects listed in Table 3 were completed. The
projects were all quite ambitious and several had
significant results. In my opinion, four of the
projects would be totally acceptable as research
papers in the open literature if the results were
significantly fleshed out. I have encouraged the
students to do this. Compared to the previous
time I taught ChE 623 when no structure was em-
ployed in developing research projects, these re-
search projects and oral reports were much more
professional and results were much more sig-
nificant.

SUMMARY AND CONCLUSIONS
ChE 623, Separation Processes, was designed
to include three major threads. The first of these
was the study of operating methods for adsorption,
chromatography, and ion exchange in a pattern
set by the instructor. The second thread was the
study of topics selected by the students with the
assignments and lectures being developed by the
instructor. The third thread was the course project
done by each student. A structure was used to dis-
courage procrastination on the research project.
The first half of the course was enthusi-
astically accepted by the students. They became
quite interested in the material, and five of the
later research projects were related to that ma-
terial. The second half of the course also went
well, although the students were somewhat less
enthusiastic, perhaps because they were working
on their research projects.


The research project which was structured to
encourage work throughout the semester de-
creased, but did not prevent, procrastination. The
resulting research projects were much better than
those turned in after the previous course was
offered. I recommend that other professors con-
sider a similar paced structure when a course
project is a major part of a course. E

REFERENCES
1. Wankat, P. C., "A Modified Personalized Instruction-
Lecture Course," in J. M. Biedenback and L. P.
Grayson (eds.), Proceedings of the Third Annual
Frontiers in Education Conference, IEEE, NY, 1973,
144-148.
2. Karger, B. L., L. R. Snyder and C. Horvath, jAn
Introduction to Separation Science, Wiley, NY, 1973,
Chapter 4.
3. Lee, H., E. N. Lightfoot, J. F. G. Reis and M. D.
Waissbluth, "The Systematic Description and Develop-
ment of Separations Processes," in N. N. Li (ed.)
Recent Developments in Separation Science, Vol. III,
Part A, CRC Press, Cleveland, 1977, 1-69.
4. Wankat, P. C., "Cyclic Separations: Parametric
Pumping, Pressure Swing Adsorption and Cycling
Zone Adsorption," CHEMI module to be published
by AIChE.
5. Course handout. Mass and Energy Balances and
Local Equilibrium Solution. (Copies are available
from the author).
6. Sherwood, T. K., R. L. Pigford and C. R. Wilke,
Mass Transfer, McGraw-Hill, NY, 1975, Chapter 10.
7. Broughton, D. B., R. W. Neuzil, J. M. Pharis and
C. S. Breasley, "The Parex Process for Recovering
Paraxylene," Chem. Eng. Prog., 66 (9), 70, (1970).
8. Wankat, P. C., "The Relationship Between One-
Dimensional and Two-Dimensional Separation Pro-
cesses," AIChE Journal, 23, 859 (1977).
9. Wankat, P. C., "Improved Efficiency in Preparative
Chromatographic Columns Using a Moving Feed,"
Ind. Eng. Chem. Fundam., 16, 468 (1977).
10. Pigford, R. L., B. Baker and D. E. Blum, "Equi-
librium Theory of Parametric Pump," Ind. Eng.
Chem. Fundam., 8, 144 (1969).
11. Skarstrom, C. W., "Heatless Fractionation of Gases
Over Solid Adsorbents," in N. N. Li (ed.), Recent
Developments in Separation Science, Vol. II, p. 95,
CRC Press, Cleveland, 1972.
12. Wong, Y. W., F. B. Hill, and Y. N. I. Chan, "Studies
of the Separation of Hydrogen Isotopes by a Pressure
Swing Adsorption Process," Separat. Sci. Technol.,
15 (3), 423 (1980).
13. Baker, B. and R. L. Pigford, "Cycling Zone Adsorp-
tion: Quantitative Theory and Experimental Results,"
Ind. Eng. Chem. Fundam., 10, 283 (1971).
14. Foo, S. C., K. H. Bergsman and P. C. Wankat,
"Multicomponent Fractionation by Direct Thermal
Mode Cycling Zone Adsorption," Ind. Eng. Chem.
Fundam., 19, 86 (1980).
15. Anderson, R. E., "Ion-Exchange Separations," in
P. A. Schweitzer (ed.), Handbook of Separation


CHEMICAL ENGINEERING EDUCATION


212









Techniques for Chemical Engineers, Sect. 1.12,
McGraw-Hill, NY, 1979.
16. Lightfoot, E. N., R. J. Sanchez-Palma and D. C.
Edwards, "Chromatography and Allied Fixed Bed
Separations Processes" in H. M. Schoen (ed.), New
Chemical Engineering Separation Techniques, Inter-
science, NY, p. 125 (1962).
17. Lapidus, L. and N. R. Amundson, "Mathematics of
Adsorption in Beds. VI. The Effect of Longitudinal
Diffusion in Ion Exchange and Chromatic Columns,"
J. Phys. Chem., 56, 984 (1952).
18. Thomas, H. C., "Chromatography: A Problem in
Kinetics," Annals New York Academy of Science,
49, 161 (1948).
19. Lee, M. N. Y., "Novel Separations with Molecular
Sieves Adsorption," in N. N. Li, Recent Developments
in Separation Science, Vol. II, (1972), p. 75.
20. Breck, D. W., Zeolite Molecular Sieves, Wiley, NY,
1978.
21. Mantell, C. L., Carbon and Graphite Handbook, Inter-
science, (1968), Chapter 13.
22. Wankat, P. C., and L. R. Partin, "Process for Re-
covery of Solvent Vapors with Activated Carbon,"
Ind. Eng. Chem. Process Des. Dev., 19, 446 (1980).
23. May, S. W., and L. M. Landgraff, "Separation
Techniques Based on Biological Specificity," in N. N.
Li (ed.), Recent Developments in Separation Science,
Vol. V., 227-255 (1979).
24. Lacey, R. E., "Membrane Separation Processes,"
Chem. Eng., Sept. 4, 1972, p. 56-74.
25. Reid, C. E., "Principles of Reverse Osmosis," in U.
Merten (ed.), Desalination by Reverse Osmosis, 1966,
p. 1-14.
26. Blatt, W. F., A. Dravid, A. S. Michaels, and L. Nelsen,
in "Solute Polarization and Cake Formation in
Membrane Ultrafiltration" in J. E. Flinn (ed.), Mem-
brane Science and Technology, p. 47-74, 1970.
27. Sherwood, T. K., P. L. T. Brian, R. E. Fisher and L.
Dresner, "Salt Concentration at Phase Boundaries in
Desalination by Reverse Osmosis," IEC Fundamentals,
4, 113, (1965).
28. Porter, M.C., "Membrane Filtration," in P. Schweitzer
(ed.), Handbook of Separation Techniques for Chemi-
cal Engineers, McGraw-Hill, NY, 1979, Sect. 2.1.
29. Merten, U., "Transport Properties of Osmotic Mem-
branes" in U. Merten, Desalination by Reverse Os-
mosis, MIT Press (1966), Pages 15 to 54.
30. Sourirajan, S. (ed.), Reverse Osmosis and Synthetic
Membrane, National Research Council, Canada,
(1977).
31. Hwang, S. T. and J. M. Thorman, "The Continuous
Membrane Column," AIChE Journal, 26, 558 (1980).
32. McCabe, W. L. and J. C. Smith, Unit Operations of
Chemical Engineering, 3rd ed. McGraw-Hill, NY, 1976,
Chapter 28.
33. Larson, M. A. and A. D. Randolph, "Size Distribution
Analysis in Continuous Crystallization," CEP Symp.
Ser., Vol. 65, #95, p. 1 (1969).
34. Randolph, A. D. and M. A. Larson, "Theory of Par-
ticulate Process," Academic, NY, 1971, Chapters 4
to 9.
35. Garside, J. and M. B. Shah, "Crystallization Kinetics
from MSMPR Crystallizers," Ind. Eng. Chem. Process


Des. Develop., 19, 509 (1980).
36. Singh, G., "Crystallization from Solutions," in P.
Schweitzer (ed.) Handbook of Separation Techniques
for Chemical Engineers, McGraw Hill, NY, 1979, Sect.
2.4.



COAL LIQUEFACTION
Continued from page 182.
Present and Developing Methods, in press, Marcel
Dekker, Inc., New York (1981).
Bl. Liu, Y. A. and G. E. Crow, "Studies in Magneto-
chemical Engineering: I. A. Pilot-Scale Study of
High-Gradient Magnetic Desulfurization of Solvent-
Refined Coal," Fuel, 58, 345 (1979).
B12. Liu, Y. A. and M. J. Oak, "Studies in Magneto-
chemical Engineering: II. Theoretical Development
of a Practical Model for High Gradient Magnetic
Separation, and III. Experimental Applications of a
Practical Model of High Gradient Magnetic Separa-
tion to Pilot-Scale Coal Beneficiation," AIChE J.,
in press (1981).
B13. Eissenberg, D. M. and Y. A. Liu, "High Gradient
Magnetic Beneficiation of Dry Pulverized Coal via
Upwardly-Directed Recirculating Fluidization,"
U.S. Patent number 4,212,651, issued on July 15,
1980.
B14. Liu, Y. A., "Novel High Gradient Magnetic Separa-
tion Processes for Desulfurization of Dry Pulverized
Coal," Chap. 9 in Recent Development in Separation
Science: Volume VI, Norman N. Li, Editor, CRC
Press, Boca Raton, FL (1981).

C. SELECTED RECENT THESES FROM THE AUBURN
COAL RESEARCH PROGRAM

C1. McCord, T. H., "A Feasibility Study of Novel High
Gradient Magnetic Separation Processes for De-
sulfurization of Dry Pulverized Coal" (1979).
C2. Jeng, J. F., "Determination of a Solvent Quality
Index for Coal Liquefaction," (1979).
C3. Fan, C. W., "Heteroatom Removal from Model Com-
pounds by Coal Mineral Catalysts," (1979).
C4. Henson, B. J., "Solubilities of H2 and CO2 in Coal
Liquids," (1980).
C5.. Majlessi, S.H.R., "Synergistic and Phase Behavior
Effects Among Aliphatic and Aromatic Compounds
in Coal Liquefaction," (1980).
C6. Wagner, R. G., "A Feasibility Study of Novel Con-
tinuous Superconducting High Gradient Magnetic
Separation Process for Desulfurization of Dry Pul-
verized Coal," (1980).
C7. Brook, D., "Effect of Pyrite on Liquefaction
Catalysis," (1981).
C8. Crawford, J., "Kinetics of Pyrite-to-Pyrrhotite
Transformation," (1981).
C9. Pehler, F. A., "Development and Demonstration of
the Auburn Fluidized-Bed Superconducting High
Gradient Magnetic Separation Process for Desulfur-
ization of Dry Pulverized Coal," (1981).
C10. Smith, N., "NMR Investigation of Recycle Solvent
Quality," (1981).


FALL 1981










4 Couiaie in


HETEROGENEOUS CATALYSIS

Principles, Practice and Modern Experimental Techniques


EDUARDO E. WOLF
University of Notre Dame
Notre Dame, IN 46556

H ETEROGENEOUS CATALYSIS PLAYS a key role in
the chemical process industry as well as in
energy conversion and pollution control processes.
The development of new processes is often pre-
ceded by the discovery of a new catalyst. A case
in point is, among many others, catalytic cracking
in petroleum refining. The first cracking processes
were non-catalytic, thermal processes designed to
increase the fraction of petroleum that could be
utilized as gasoline. The first catalytic cracking
process used a treated clay as a catalyst which de-
activated rapidly. Reactors were then developed
to regenerate the coked catalyst by using cycling
feeds, moving beds and fluidized beds. Synthetic
silica alumina catalysts replaced the natural
treated clays and these were superseded by
catalysts containing zeolites dispersed on an
amorphous silica alumina matrix. Optimum opera-
tion of the new zeolite cracking catalyst required
short contact times and higher temperatures. This














Eduardo E. Wolf is an Associate Professor of Chemical Engineering
at Notre Dame where he has been a faculty member since 1975. He
received his BS from the University of Chile in Santiago, MS from the
University of California at Davis and Ph.D. from the University of
California at Berkeley. His research interests are in the area. of
applied and fundamental catalysis, catalytic reaction engineering and
catalytic coal conversion.


Catalysis is a multidisciplinary
subject wherein collaboration among
chemists, physicists, material scientists and
engineers render the best results.

led to the replacement of the fluid bed reactor by
the riser cracker or transport line reactor in
which the vaporized feed is contacted and trans-
ported upward with regenerated catalyst in a
vertical pipe. The strategic and economic implica-
tions of new catalysts development are evident
when considering the history and present status
of coal conversion processes. Such processes, first
used in Germany during WW II, were briefly con-
sidered in the U. S. in the fifties, but finds its
present full scale development and application in
South Africa. Present efforts in synfuels develop-
ment are a challenge open to future generations of
scientists and engineers. The answers lie, in part,
in our ability to develop new, more active and re-
sistant catalysts which can withstand operation in
the demanding environment of coal conversion pro-
cesses. The task requires that we possess a better
understanding of catalytic reactions and surfaces,
as well as a command of the modern tools used
for surface analysis and catalyst characteriza-
tion.
The advent of new spectroscopic tools for
direct probing of surfaces requires an intro-
duction to the methods of other disciplines not
currently included in the traditional chemical
engineering curriculum. Catalysis is a multidis-
ciplinary subject wherein collaboration among
chemists, physicists, material scientists and engi-
neers render the best results. For this to occur,
researchers in this area need to be equipped
with the basic understanding of the comple-
mentary disciplines and tools, otherwise the dialog
does not bear fruit. The course outline which
follows has been organized in this multidisciplin-
ary context comprising fundamental, practical,

� CopyVght ChE Division, ASEE, 1981


CHEMICAL ENGINEERING EDUCATION


214








and experimental aspects of heterogeneous
catalysis.

COURSE STRUCTURE AND DESCRIPTION

THE COURSE IS STRUCTURED so that lecture ma-
terials are combined with demonstration ex-
periments dealing with the use of spectroscopic
techniques for surface analysis. Table 1 presents
an outline of the course in the form of a table of
contents divided into three parts and subsections
or chapters. Parts I and II comprise the lecture
material whereas Part III consists of a brief de-
scription of the demonstration experiments. The
experiments are also indicated in parenthesis in
Part I to indicate the appropriate combination of
lectures and experiments.
The list of experiments presented in Part III
is incomplete since there are many other tech-
niques for surface analysis and catalyst charac-
terization. However, in practice, availability of
equipment places a restriction on the types of ex-
periments which can be conducted during the
course. When I teach the course at Notre Dame,
nine experiments are run for which I borrow the
facilities of Chemistry (XPS), Materials Science
(X-ray diffraction, SEM, TEM), our college
(AES) and our own catalysis laboratories (FTIR,
adsorption, kinetics). Fig. 1 shows some of the
equipment used.
The demonstration experiments are presented
to groups of three or four students. One lecture is
conducted prior to the experiment to explain the
basic characteristics and operation of the equip-
ment and the type of data obtained. Emphasis is
given to sample preparation and interpretation of
results rather than to details concerning the ap-
paratus hardware. The results obtained during the
session are distributed among the students for
their analyses, which are submitted later in the
form of a short written report.
Part I is devoted to the principles and funda-
mentals of heterogeneous catalysis and related
topics. Due to the diversity of the subjects treated
(some of which could constitute a separate course)
the scope of the treatment is limited to those
aspects which are of import to catalysis.
The lecture material starts with an introduc-
tion to the solid state. It focuses on the nature of
bonding in solids, structure of crystals and
electronic structure of solids. The x-ray diffrac-
tion laboratory and transmission electron micro-
scopy (TEM) laboratories are discussed and
carried out concurrently with these lectures.


Following the introduction to the solid state
there is an introduction to surface chemistry
paralleling many of the concepts presented pre-
viously on geometrical and electronic structure of
solids. Emphasis is given to electron emission and
relaxation processes which are the basis of electron
spectroscopy. The lecture material is demonstrated
in the SEM x-ray dispersive analysis laboratory, x-
ray photoelectron spectroscopy laboratory (XPS)
and Auger electron spectroscopy laboratory
(Scanning Auger, SAM).
Once the fundamentals of the solid-state and
surfaces and the corresponding probing tech-
niques are introduced, the more classical concepts
of gas-surface interactions, such as physisorption,
chemisorption and surface reactions are treated.
Experimental demonstrations of BET adsorp-
tion infrared spectroscopy and selective chemi-
sorption of gases are presented concurrently with
this material. A discussion of selected examples of



. .


FIGURE 1. Fourier Transform Infrared Spectrometer
(FTIR) in the author's laboratory, showing
the data acquisition system, spectrometer
and GC/IR interface.
catalyst preparation for laboratory testing closes
Part I.
Part II deals with the more empirical but no
less significant subject of applied and industrial
catalysis. Beginning with an introduction on the
development and preparation of industrial cata-
lysts, there follows a discussion of reaction engi-
neering aspects of catalysts and catalytic reactors.
Mass and heat transport limitations in catalysts
pellets are analyzed in terms of observables. A
short discussion of catalyst deactivation analyzes
its different causes and remedies. The balance of
the lecture material is devoted to a description of
some of the major industrial catalytic processes
grouped according to the chemical elements in-


FALL 1981









TABLE 1


Principles, Practice and Modern Experimental Techniques in Heterogeneous Catalysts


PART I: INTRODUCTION TO THE PRINCIPLES OF
HETEROGENEOUS CATALYSIS
1. Introduction
1.1 Catalyst, Types and Physical Characteristics
1.2 Catalysis, Catalytic Sequence, Energetics
2. Introduction to the Solid State
2.1 Nature of Bonding in Solids
2.3 Structure of Crystals
(X-ray Diffraction Laboratory, Experiment No.
1, Section 13)
2.4 Electronic Structure of Solids
2.5 Imperfections in Solids
(Transmission Electron Microscopy
Laboratory, Experiment No. 2, Section 14)
2.6 Structural Transformations in Solids
2.7 Summary
3. Introduction to Surface Chemistry
3.1 Structure and Description of Solid Surfaces
(Low Energy Electron Diffraction (LEED)
Laboratory, Section 16)
3.2 Thermodynamics of Surfaces
(Scanning Electron Microscopy-Energy
Dispersive X-ray Analysis Laboratory, Experi-
ment No. 3, Section 15)
3.3 Emission and Relaxation Processes Involving
Valence Electrons and Inner Electron Shells
3.3 Principles of Electron Spectroscopy
Auger Electron Spectroscopy
X-ray Photoelectron Spectroscopy
(Scanning Auger Microprobe Laboratory, Ex-
periment No. 4, Section 15)
Other Spectroscopic Techniques
(XPS Laboratory, Experiment No. 5, Section 15)
3.4 Summary
4. Interaction of Gases with Surfaces
4.1 Gas-Surface Interactions-Adsorption
4.2 Physical Adsorption; Isotherms, Energetics
(BET Laboratory, Experiment No. 7, Section 17)
4.3 Chemisorption, Molecular Aspects, Isotherms,
Heats of Chemisorption, Rates of Adsorption-
Desorption
4.4 The Surface Chemical Bond
(Infrared Spectroscopy Laboratory, Experi-
ment No. 6, Section 16)
4.5 Kinetic of Catalytic Reactions, Site Balances
4.6 Empirical Activity Patterns and Activity Cor-
relations; Acidity, Geometric Correlations,
Electronic Correlations (H2 Chemisorption
Laboratory, Experiment No. 8, Section 17)
4.7 Preparation and Characterization of Catalysts
for Laboratory Testing
4.8 Summary
(Catalytic Kinetic Laboratory, Experiment No.
9, Section 20)

PART II: INDUSTRIAL AND APPLIED CATALYSIS
5. Industrial Catalysts
5.1 The Development of Industrial Catalysts and
Catalytic Processes


5.2 Preparation of Industrial Catalysts
5.3 Mass and Heat-Transport Effects in Catalyst
Design
5.4 Reaction Engineering Considerations
5.5 Catalyst Deactivation
5.6 Summary
INDUSTRIAL CATALYTIC PROCESSES
6. Reactions of C-H
6.1 Petroleum Refining-Overview
6.2 Catalytic Cracking
6.3 Catalytic Naphtha Reforming
6.4 Hydrocracking
6.5 Catalytic Alkylation
7. Reactions of C-O-H
7.1 Steam Reforming
7.2 Methanol Synthesis
7.3 Fischer-Tropsch Synthesis
7.4 Water Shift Reaction
7.5 Methanation
7.6 Partial Oxidation of Hydrocarbons
8. Reactions of N-H-O
8.1 Ammonia Synthesis
8.2 Ammonia Oxidation, Urea
8.3 Acrilonitrile Production
9. Reactions of S-O, S-H
9.1 S-Oxidation, Sulfuric Acid Manufacture
9.2 S-Production, Claus Process
10. Complex Systems
10.1 Automobile Pollution Control
10.2 Coal Gasification-Liquefaction
10.3 Hydroprocessing of Heavy Oils and Coal Liquids
10.4 Demetallization of Heavy Oils
11. Other Catalytic Processes
PART III: MODERN EXPERIMENTAL TECHNIQUES
FOR CATALYST CHARACTERIZATION
12. X-ray Diffraction
Experiment No. 1
13. Electron Microscopy
Experiment No. 2, Transmission Electron
Microscopy
Experiment No. 3, SEiM, X-ray Dispersive
Analysis
14. Electron Spectroscopy
Experiment No. 4, Auger Electron Spectroscopy
Experiment No. 5, X-ray Photoelectron
Spectroscopy
Other Spectroscopic Techniques
15. Low Energy Electron Diffraction
Introduction
16. Infrared Spectroscopy
Experiment No. 6, Fourier Transform IR, GC/IR
17. Gas Adsorption Techniques
Experiment No. 7, BET Adsorption
Experiment No. 8, H2 Chemisorption
18. Catalytic Kinetic
Experiment No. 9, Fixed Bed, Differential and
CSTCR Reactors
19. Other Experimental Techniques


CHEMICAL ENGINEERING EDUCATION


216









volved in the main reactions (i.e., C-H, C-O, etc.).
Each process is described in terms of the chemis-
try involved, thermodynamics, and kinetics
aspects. Emphasis is given to the catalyst ac-
tivity, selectivity and deactivation in relation to
process operation and reaction engineering
aspects. Cross reference is made to the funda-
mental aspects discussed in Part I whenever
possible.
The typical enrollment in the course is ten to
fifteen graduate students from chemical engineer-
ing and science. The material is presented in two,
75 minute lectures, and about one laboratory
session per week. Grades are assigned on the basis
of a written exam and a term paper. The latter
consists of a written report and an oral presenta-
tion which provides stimulating discussion as well
as fresh references and new ideas on specialized
topics. The research papers focused on energy re-
lated catalytic processes with emphasis in fossil
fuel and coal processing.
No text is available which covers all the ma-
terial included in Table 1. Hence I prepared a set
of notes based on more specialized books and
papers dealing with specific subjects and tech-
niques as well as information and experience ac-
cumulated in our own laboratory.
The combination of theory and experiments
has a strong impact on the students, even though
in some cases they do not directly operate the
equipment due to its complexity and specializa-
tion. The majority of the engineering students
have not been exposed to surface analysis and
electron microscopy techniques, and thus feel that
they acquired new knowledge in the course. The
combination of principles, industrial application
and experiments equips the students with a new
perspective of catalysis and catalytic reaction
engineering which enables them to face a larger
variety of problems with a larger diversity of
tools.
I enjoyed teaching the course because it pro-
vides an opportunity for interaction with col-
leagues from other disciplines, which enriched my
own knowledge and perspective of the subject. Ol

REFERENCES
(A list of references, including journal articles, is too
extensive, thus only books are cited.)
C. Kittel, "Introduction to Solid State Physics," John
Wiley, 1976.
G. Somorjai, "Principles of Surface Chemistry," Prentice-
Hall, 1972.
N. B. Hannay, "Solid State Chemistry," Prentice Hall,


1965.
W. N. Eelgass, G. L. Haller, R. Kellerman, J. H. Lundsford,
"Spectroscopy in Heterogeneous Catalysis," Academic
Press, 1979.
A. W. Adamson, "Physical Chemistry of Surfaces," John
Wiley, 1976.
T. A. Carlson, "Photoelectron and Auger Spectroscopy,"
Plenum Press, New York, 1975.
B. C. Gates, J. R. Katzer, G. C. Schuit, "Chemistry of
Catalytic Processes," McGraw-Hill, 1979.
D. L. Trim, "Design of Industrial Catalysts," Elsevier,
1980.
C. N. Satterfield, "Heterogeneous Catalysis," McGraw-
Hill, 1980.
J. J. Carberry, "Chemical and Catalytic Reaction Engi-
neering," McGraw-Hill, 1976.
J. M. Thomas, R. M. Lambert, "Characterization of
Catalysts," John Wiley, 1980.
R. B. Anderson, "Experimental Methods for Catalysts
Characterization," Academic Press, Vol I, 1968; Vol
III, 1976.
J. Butt, "Reaction Kinetics and Reactor Design," Prentice
Hall International, 1980.
J. M. Thomas and W. J. Thomas, "Introduction to the
Principles of Heterogeneous Catalysis," Academic
Press, 1967.
A. Clark, "The Theory of Adsorption and Catalysis,"
Academic Press, 1970.
P. A. Delmon, P. A. Jacobs and G. Poncelet, "Preparation
of Catalysts," Elsevier, Vol I, 1975 and Vol II, 1978.
B. Imelik, C. Naccache, Y. B. Taarit, J. C. Vedrine, G.
Coudurier and H. Prahand, Eds., "Catalysis by
Zeolites," Elsevier, 1980.


CLASSICAL THERMODYNAMICS
Continued from page 158.
17, 531 (1962).
3. Gibbs, R. E., and H. C. Van Ness, Ind. Eng. Chem.
Fundam., 11, 410 (1972).
4. Van Ness, H. C., and M. M. Abbott, Ind. Eng. Chem.
Fundam., 17, 66 (1978).
5. Van Ness, H. C., AIChE J., 16, 18 (1970).
6. Barker, J. A., Austral. J. Chem., 6, 207 (1953).
7. Abbott, M. M., and H. C. Van Ness, AIChE J., �1,
62 (1975).
8. Mrazek, R. V., and H. C. Van Ness, AIChE J., 7,
190 (1961).
9. Savini, C. G., et al., J. Chem. Eng. Data, 11, 40 (1966).
10. Winterhalter, D. H., and H. C. Van Ness, J. Chem.
Eng. Data, 11, 189 (1966).
11. Losito, N. A., Jr., Ph.D. Thesis, Rensselaer Poly-
technic Institute, (in preparation).
12. Wilson, G. M., J. Am. Chem. Soc., 86, 127 (1964).
13. Renon, H., and J. M. Prausnitz, AIChE J., 14, 135
(1968).
14. Abrams, D. S., and J. M. Prausnitz, AIChE J., 1,
116 (1975).
15. Fredenslund, Aa., et al., "Vapor-Liquid Equilibria
using UNIFAC," Elsevier, Amsterdam (1977).
16. Kojima, K., and T. Tochigi, "Prediction of Vapor-
Liquid Equilibria by the ASOG Method," Elsevier,
Amsterdam (1979).


FALL 1981






"Just over two years with DuPont, and

'm a process engineer on a

multimillion dollar plant expansion."
Maria Williams, BS, Chemical Engineering

"In just over two years, I've
gone from college to designing
and specifying equipment for the
expansion of one of Du Pont's
Textile Fibers plants.
'"As a process engineer, I'm
not only involved with all kinds of
equipment, but I'm also getting
the chance to work with design
engineers, construction engi-
neers, architects, even outside
suppliers. It's a big responsibility,
and I really enjoy it.
"I had a lot of job offers
during my last semester at
Cornell, but I chose Du Pont
because they offered me an
assignment with real respon-
sibility, right from the beginning.
They put me in charge of finding
the cause of product defects
and determining the process
changes necessary to
correct them.
"Now I'm a process engineer
on a multimillion-dollar project.
Du Pont gave me a chance to go
a long way in a short time.'
If you're a graduating engi-
neer who wants responsibility
and the opportunity to start a
challenging career, set up an
interview next time a Du Pont
representative is on campus. Or
write: Du Pont Company, Room
38244, Wilmington, DE 19898.
At Du Pont...there's a
P "world of things you can
do something about.




9L :.- K Anjual Oppcoruru Employei M F








COAL PROCESSING
Continued from page 186.
The lectures or chapters cover a wide range of
topics starting with the origin and formation of
coal and continuing through the physical and
chemical structure and properties of coal, and
methods for processing and utilizing various kinds
of coal. Although established technology is re-
viewed, there is an important emphasis on newer
techniques such as fluidized bed combustion, super-
critical gas extraction, and the production of
carbon fibers. New processes under development
for manufacturing gaseous and liquid fuels from
coal are also discussed. There is an additional
chapter not covered by the original lectures which
deals with the application of high resolution
electron microscopy to study the microstructure
of graphitized and partially graphitized carbons
derived from coal.
The volume is highly readable and provides a
basic but rather brief (210 pages) introduction to
the science and technology of coal utilization. It
does not probe any topic in great depth nor pro-
vide many details and the list of references at the
end of each chapter is short. On the other hand, it
does provide a good overview of a number of
topical areas and should appeal to a great many
readers who desire a brief introduction to the
subject. Furthermore, even though the book tends
to emphasize technology which is of particular
interest to the British, it includes enough material
about new developments in the United States and
other countries to insure world-wide interest. The
volume could well serve as a text for an intro-
ductory course on coal science and technology for
college students with some background in chemis-
try and chemical engineering. O


THE CHEMICAL REACTOR OMNIBOOK

By Octave Levenspiel; published by the author and
distributed by Oregon State University Book
Stores, Corvallis, OR 97330

Reviewed by Rutherford Aris
University of Minnesota
As one who has often been puzzled by the ways
of publishers it is refreshing to find them at once
so right and so wrong. So wrong those conven-
tional publishers who declined a book of Octave
Levenspiel's; so right, the author and the Oregon


State University Book Stores who published the
book in the form which it takes. In it the problems
are beautifully typed and are linked by chapters in
Levenspiel's own hand. This is a round cursive of
admirable clarity and consistency and in itself
conveys the vitality and interest of the spoken
word. When linked with his figures and sketches in
the organic way which he achieves, we have the
effect of being in the classroom with a teacher of
known and valued vitality and his pages have all
the immediacy and effectiveness of the author's
presence.
One of the first things the teacher of chemical
engineering will spot is that here is a positive
gold mine of problems. There are no less than
1394, though it must be admitted that many are
one-line modifications of their neighbors. The book
is divided into seven main divisions (numbered to
leave a small remainder when 10 n is subtracted,
n = 0, 2, 3, 4, 5, 6, 8) with an interlude between
the first two and a coda on "Dimensions units, con-
versions and the orders of magnitude of this and
that." Single phase reactors are the burden of
the first division which is divided into seven
sections and has more than a third of the problems.
The interlude (sec. 11) is on the background of
multiphase reactors and leads to a division on
secss. 21-25) reactors with solid catalysts that
ranges from the particle to the fluidized bed. Then
there is a discussion secss. 31-34) of catalytic re-
actors with changing phases, of gas/liquid and
liquid/liquid reactions secss. 41, 42) and the re-
actions of solids secss. 51-55). Levenspiel next
groups together some discussions of the flow of
materials through reactors secss. 61-64, 66, 68)
and concludes with a section on biochemical re-
actors using enzymes and microbes secss. 81-85).
It is interesting to speculate whether a future doc-
torate (a D.Ed. perhaps) will be awarded for dis-
cussion of what forms of life might once have
played in these "Lacunae of Levenspiel" secss. 65,
67, and the 70's).
The style of the text sections is, by design,
sketchy. More often than not, it jumps from the
statement of a problem and its background to a
conclusion and adds certain comments afterwards.
This makes it an interesting book to think of using
in a course since, although one would be to some
extent committed to its notation (and who among
us is not fiercely jealous of their own) it would
provide a most useful framework with the least
restriction. Indeed Levenspiel suggests that its use
might be as a supplementary text in a course and


FALL 1981








very helpfully explains how he himself has used it.
It can also be used for a self-paced/self-study
course on the subject and is certainly a useful
book to have for reference. The reader using the
Omnibook for self-study would no doubt wish
for more references, for these are not given in
any complete and systematic way. I would have
liked to have seen Levenspiel's presentation of
the dynamics of reactors, for his virtuosity in the
integration of text and figure would have been
extended by a description of the recent work on


possible behaviors of the stirred tank. But I must
not get carried away on my hobby horses.
The last chapter (sec. 100) is an admirable
collection of units and conversions between them.
I trust I shall never need to use a number with a
dimension, but if such disaster should come upon
me, I shall flee for refuge to this "Miscellany". As
in so many places throughout the book, Levenspiel
has here an original touch; he gives "spectra" of
the orders of magnitude of various diffusivities,
conductivities and rates of reaction. O


[I )1 class and home problems


The object of this column is to enhance our readers' collection of interesting and novel problems in
Chemical Engineering. Problems of the type that can be used to motivate the student by presenting a
particular principle in class or in a new light or that can be assigned as a novel home problem are re-
quested as well as those that are more traditional in nature that elucidate difficult concepts. Please sub-
mit them to Professor H. Scott Fogler, ChE Department, University of Michigan, Ann Arbor, MI 48109.
Our undergraduate student readers are encouraged to submit their solution to the following problem to Prof. Ray
Fahien, Editor, CEE, ChE Department, University of Florida, Gainesville, FL 32611, before January 1, 1982. A compli-
mentary subscription to CEE will be awarded, to begin immediately or, if preferred, after graduation, for the best solu-
tion submitted (Oregon State students are not eligible). We will publish Prof. Levenspiel's solution in a subsequent issue.


DOLPHIN PROBLEM


OCTAVE LEVENSPIEL
Oregon State University
Corvallis, OR 97331
Whales, dolphins and porpoises are able to
maintain surprisingly high body temperatures
even though they are immersed continuously in
cold, cold water. Since the extremities of these
animals (tails, fins, flukes) have a large surface
to volume ratio, a large portion of the heat loss
occurs there.
a) Now an ordinary engineering junior de-
signing a dolphin from first principles might view
the flipper as a flat single pass heat exchanger
with heat transfer occurring between a blood vessel
passing through the flipper and the flipper itself
which is assumed to be at the water ambient
temperature.
Let us suppose that blood'at 40�C enters the
flipper at 0.3 kg/s, feeds the flipper, is cooled
somewhat, and then returns to the main part of
the body. The dolphin swims in 4�C water, the
overall heat transfer coefficient is 100 cal/s'm2"K
and the heat transfer area is 3 m2. At what
temperature does the blood reenter the main part


of the body of the dolphin?
b) Frankly, the ordinary engineer above
(which you obviously are not) would design a
lousy dolphin. Let's try to do better; in fact let us
try to learn from nature. Let us see if we can
reduce some of the undesirable heat loss by insert-
ing an internal heat exchanger B ahead of the
flipper exchanger A above. This internal ex-
changer is a countercurrent one which transfers
heat from the outgoing warm arterial blood to
the cooled venous blood returning from the flipper.
Heat conservation of this sort, by having arteries
and veins closely paralleling each other, in
counterflow, is one of nature's clever tricks.
Assume for this internal exchanger B that
As = 2 m2
and
UB = 150 cal/s'm2"K

With this extra exchanger find T3, the tem-
perature of blood returning to the main part of
the body; and, in addition, the fraction of original
heat loss which is saved. Approximate the proper-
ties of blood by water. El


CHEMICAL ENGINEERING EDUCATION


220




Good engineers are in a

position to choose.

So why choose FMC?


"I was really impressed by
FMC's involvement in so
many types of products and
processes. Here, there is
always the chance to work on
optimizations and designs.
Learning day-to-day opera-
tions from FMC experts and
assuming major responsibil-
ity for projects have been
great challenges. I'm looking
forward to even greater ones
in the future."


"FMC offered me the best
opportunities for advance-
ment in a variety of situa-
tions. Working in four dif-
ferent departments has
increased my knowledge
enormously. At FMC, I've
been able to explore manu-
facturing and production
engineering. It gives me great
satisfaction to know that I am
a major contributor to our
overall plant operations."


Larry Ligawa earned his BS in
Industrial Technology at Indiana
State University in 1974 and went on
to complete his MS in Industrial
Professional Technology at ISU in
1976 before joining FMC. As an
Industrial Engineer with the Chain
Division in Indianapolis, Ind., Larry
studies and audits both labor- and
capital-intensive work processes and
recommends methods to increase
productivity.


Helen E. Bilson joined the Technical
Department of the FMC Agricultural
Chemical Group's plant in Baltimore,
Md., after earning her BS in Chemical
Engineering from Virginia
Polytechnic Institute and State
University in 1978. Beth's first
assignment was to implement a
wastewater treatment technique
developed in FMC's own labs. She's
presently working on a project team
to design and engineer a production
plant for one of our important
chemical intermediates.


In four years at FMC, Stan Butkivich
progressed from an associate to a
senior level Industrial Engineer. Now,
as the Assistant Supervisor in the
Cost Control Engineering Depart-
ment of FMC's San Jose Ordnance
Plant in California, he is directly
involved with a most important
aspect of production-its costs. Stan
received his.BS in Engineering Tech-
nology from California Polytechnic
State University in 1975.


Choosing FMC means...
...joining a major international producer of machinery and chemicals for
industry and agriculture with 1978 sales of $2.91 billion. FMC Corporation,
headquartered in Chicago, has more than 45,000 employees worldwide,
located at 136 manufacturing facilities in 33 states and 15 other nations. FMC
products include food and agricultural machinery and chemicals, industrial
chemicals, material and natural resource handling equipment, construction
and power transmission products, government and municipal equipment. We
offer a range of rewarding careers for engineers and other techrnica!, rady-
ates. See us on campus or contact your placement office.


A


FMC
FMC is an equal opportunity
employer, M/F.


"At the outset, I knew that
working for FMC would mean
becoming a valued member
of their team. FMC is recog-
nized as a large corporation,
and it is-in terms of size,
varied product lines and
growth opportunities. Yet, the
people are warm and friendly,
and creativity is encouraged.
At FMC, people count, and
that has made the difference
to me."









Ya Mem&oiam

HERBERT E. SCHWEYER
Herbert E. Schweyer was born in Easton, PA,
in 1910. He received his bachelor of science de-
gree in chemical engineering and a masters in
metallurgy from Lafayette College in the early
thirties. His interest in asphalt technology and
rheology was aroused during his college days and
employment with Barber Asphalt Company.
Eugene C. Bingham, Herb's physical chemistry
professor, was trying to demonstrate that rigid
materials such as marble, actually flowed. Other
noted rheologists, Marcus Reiner and H. Hencky
were working with Bingham at the time. Herb
worked with Ralph Traxler, a well known asphalt
technologist, up to 1937 when he left the Barber
Asphalt Company to pursue a Doctor of Philoso-
phy degree in chemical engineering at Columbia
University. During World War II he was em-
ployed as a research chemical engineer for Texaco
in Port Neches, Texas. In 1946 he started his
teaching career at the University of Florida. In
addition to teaching and supervision of candi-
dates for the Masters and Doctor of Philosophy
degrees, he was heavily involved in research with
the Florida Department of Transportation and
obtained several grants from the National
Science Foundation. As a member of eight pro-
fessional and technical societies, Herb was active
in committee work and was a frequent contributor
of technical papers. Over the years he authored
about 100 technical papers on asphalt rheology,
economics, and other subjects. He authored two
books on engineering economics and received
several patents.
He gave technical matters a high priority. At
professional meetings he was a frequent con-
tributor of new concepts. Discussions at meetings
were usually very lively, especially when Herb
considered somebody's technical view to be com-
pletely wrong. He always took time toi explain
concepts, testing methods, or other technical
aspects to individuals who were genuinely inter-
ested in the subject. In particular, he was con-
vinced that young engineers and scientists were
the key to technological advancements in the
future. Therefore, he felt it was important to
explain his concepts and instill in the younger
engineers an interest to carry on using his
knowledge as a foundation for new developments.


Students who worked on Herb's research pro-
jects often called him "Doc." He enjoyed his
students and they soon came to understand his
brisk and blunt manner of telling them, in no
uncertain terms, that they had messed up the test.
If a student needed assistance, Herb was there
willing to help them in any way possible. His
depth of experience and creative ideas were a
boon to students and colleagues alike.
Humor and an ability to laugh at himself was
not a shortcoming of Herb's personality. He en-
joyed hearing and conveying jokes or bits of dry
humor. As John Ferguson of Winnepeg, Canada,
put it: "His technical contributions have improved
our understanding of rheology. With his input, a
void would exist. However, our greatest loss will
be the absence of his humorous comments which
brought levity to the meetings.
He was a member of three honor societies and
the recipient of various awards and citations for
service. Probably the most significant award was
the Lafayette College Alumni Citation for teach-
ing chemical engineering. Herb was extremely
proud of his Alma Mater, which was most evident
when he wore his Lafayete cap or blazer with the
Lafayette College crest.
His tireless years of research for the Florida
Department of Transportation laid the ground-
work for improvements in testing procedures and
asphalt specifications. His involvement in the re-
cycling of asphalt pavements resulted in the de-
velopment of quality control requirements.
I believe that the culmination of his career
goals occurred within the last four years. His
forty some years of research had "paid off." Herb's
understanding of asphalt flow characteristics, re-
ferred to as rheology, was complete. The testing
device which he developed facilitated test measure-
ments of theological properties. The simplified
theological approach established by Herb has
gained in acceptance in the technical community.
Even some of his strongest opponents have
recognized the validity and need for his rheologi-
cal concepts.
A simple statement which I think summarizes
Herbert Schweyer's efforts and contributions was
made by Charles Potts: "He gave much more than
he received." We shall miss him very much.
Byron E. Ruth
University of Florida


CHEMICAL ENGINEERING EDUCATION











CHEMICAL ENGINEERING EDUCATION INDEX Volumes XI-XV

AUTHOR INDEX


A
Abbott, M. M. --_... XI, 154; XV, 156
Ahlert, R. C. -------- -----XIII, 78
Alonso, J. ----- __ XII, 136
Anderson, T. J. XIV, 120
Angus, J. C. -_- XI, 4; XV, 25
Aris, R. _ __XI, 68; XII, 71, 148;
XV, 12, 219
Arkis, J. . -__..--__-.-- ___ XI, 28
B
Baasel, W. D. ----_- XI, 34; XII, 78
Baiker, A. --- -- XII, 112
Balch, C. W. - . .--- XIII, 104
Barker, D. H. .--_ XI, 60, 104
Barrows, H. S. -.. .---- XIV, 91
Bartholomew, C. H. -_.....___ XV, 188
Basio, A. .--_______.--___ XIV, 47
Beckwith, W. F. .. .__ . XI, 46
Beckmann, R. B. _ ---- XV, 146
Beer, J. M. --_____-...-----__ XIII, 80
Bethea, R. M. _______.----__ XI, 181
Birchenall, C. E. .-____- XI, 167
Bird, R. B. -. ___- XIV, 152
Blanch, H. ____ _ XI, 170
Blanks, R. F. -_ ~_ XIII, 14
Brewer, C. -------- -- XIII, 40
Buehler, R. J. - _- - XIV, 206
Butt, J. B. XII, 152; XIV, 12; XV, 160
C
CACHE, Trustees of _ XIV, 84
Carberry, J. J. ------- XIV, 78
Carbonell, R. G. ----- XII, 182
Carleson, T. E. -_.______..... XI, 118
Cassano, A. E. --..___.--__ XIV, 14
Cayrol, B. XV, 26
Charrier, J. M. ---___ -__ XI, 122
Chartoff, R. P. __ -__ - XI, 174
Cheh, H. Y. ___ --- XI, 3
Chen, H. T. _---- _ XV, 166
Chorneyko, D. M. _ _ XIII, 132
Christmas, R. J. _- __- _ XIII, 132
Christy, R. S- ---_ ------- XI, 185
Churchill, S. W. __........--- XV, 74
Cise, M. D. ---__........- --- _ XI, 34
Cloutier, R. J. ..- ...- XII, 47
Cohen, K. C. --------- XII, 136
Cooney, D. O. __ XII, 129; XIV, 147
Corcoran, W. H. ... XI, 38; XII, 72
Cosic, S .. ------ -.... XIII, 132
Crowe, C. M. _______ XII, 98
Culberson, O. L. ..____ ----- XIII, 168
Cullinan, H. T. Jr. - --.____- XII, 56
Curtis, C. W. --...... XV, 178
Cussler, E. L. X-.___ _ XI, 176
Cutlip, M. B. . .. - XV, 78
Cyert, R. M. XIII, 145
D
Dadyburjor, D. B. _----XV, 54
Darby, R. L.... . XIV, 114
Daugherty, R. L. .______- - ..- XI, 41
Davidson, B. ------ ------. XI, 54
Davis, H. T. __. XIII, 198; XIV, 126
deNevers, N. XII, 199
Dennett, C. R. _. -_- .. XI, 32
Deshpande, P. B. _ XIII, 138; XIV, 26
Dibbs, S. E. - XIII, 132
DiBella, C. A. W. - .------ XI, 53
Dippold, B. -.... ____-. .__ XII, 50
Doig, I. D. ___ ..... XIV, 130


Drinkenburg, A. A. H. .-__ -.. XII, 38
Duckler, A. E. . ------ XI, 108
Dumesic, J. A. -_ ----- XI, 160
Dunn, R. W. -......- XII, 116; XIII, 64
E


Eagleton, L. C. ..- .
Echols, G. _--
Economides, M. J.
Edgar, T. F. -
]
Fahidy, T. Z. ------
Felder, R. M. .-...
Finlayson, B. A. -
Frank, C. W. .
Frankel, D. S. -
Freighter, J. W. ---
Fricke, A. L. -_
Fry, C. M. ----
Fuller, 0. M. ----


Gilot, B. _-- -
Gordon, R. J. --
Greenberg, D. B. ----
Greenlee, R. N. -
Griskey, R. G.--
Gubbins, K. E. XIII,
Guin, J. A. ~---
Guiraud, R. ---
Gully, A. J. -----


Hall, K. R. --.-
Hallman, J. R. -
Hamielec, C. M. -
Han, C. D. _ ------
Hanesian, D. _--
Hanks, R. W.
Hanley, T. R. -
Hanratty, T. J. -
Hansen, D. ----_---
Harriott, P.
Harrison, D. P.
Hartley, E. -_
Hassler, J. C. -
Haugrud, B. --
Heenan, W. A. -
Heichelheim, H. R.
Henley, E. J. -----
Henry, J. M. .-.. .-
Hill, J. C. --
Himmelblau, D. M.
Himmelstein, K. J.
Hittner, P. M.
Hollein, H. C. -----
Hottel, H. C.
Houze, R. N. _..--
Howard, G. M. ----
Howard, J. B. - ..---
Huang, C. R. -
Hudgins, R. R.


--...-------- XI, 130
--_ _- XI, 28
_... XII, 122, 151
_ XIV, 99, 156


SXIV, 94; XV, 92
XII, 2; XIII, 116
---- - XV, 20
..-----_ XIII, 190
--- XII, 18
-.-__. XIV, 91
---___ XV, 122
_--- _- XI, 24
XIV, 130


- - XII, 140
-- XIV, 46
.--- XIV, 138
-. __ - XI, 32
-- XII, 44, 65
69; XV, 97, 172
__ XV, 178
--. _ XII, 140
.-__-.___ XI, 181


_____ XIII, 110
-- __- -- XII, 92
-- XIII, 132
----..-. . XV, 59
_ XI, 134, 149
___XIII, 46
_ -- XIII, 84
- _ XIV, 162
- XI, 3; XII, 73
- XIII, 12
-- _ XIII, 54
- _ XIV, 114
--- XV, 192
. XV, 40
._. __- XI, 64
--.... .... XI, 181
_- XI, 64; XII, 136
---__-----__.. XIII, 84
.._..._ XIII, 34
. ..... XII, 26
..... ____ XIV, 99
----__XIV, 138
._.-_--.__ XV, 166
------- XIII, 80
__ XIV, 114
-_____-.____ XIV, 66
.....------I.. XIII, 80
---_----- XV, 166
-___-__- XV, 26


J
Jackson, S. C. --.- . -. XII, 30
Johnson, H. F. .-_-. XI, 98
Jolls, K. R. -- ...--- - XIII, 75
Jorne, J. ------------- XI, 164
K
Kabel, R. L .----..-. XII, 158; XIII, 39,


70, 155; XIV, 45, 70, 198, 199;
XV, 38
Kenney, C. N. ..---- __ XIV, 168
Kerobo, C. 0. -__ XV, 166
Kershenbaum, L. S....... --- XIV, 174
King, C. J. __ _ XII, 3, 70; XIV 130
King, F. G. -____- XIII, 120
Klvana, D. ---- __ XII, 140
Kniebes, D. V. - - __.- XII, 118
Koukios, E. G. - ___ - XV, 140
Krantz, W. B. -...--.- XIV, 54; XV, 137
Kreith, F. -_-_............___ _ XI, 2
Kung, H. ----_ -----__- XV, 160
L
Lacksonen, J. W. - - - XIII, 92
Lahti, L. E. ---- XIII, 104
Laukhuf, W. L. S. --- XIV, 26
LeBlanc, D. --------_--- XI, 32
Lees, F. P. _ ____--...__ XIV, 180
Leesley, M. E. ___ XII, 188; XIV, 208
Leonard, E. F. .--.... XI, 3; XII, 55
Levenspiel, O. --.._______ XV, 220
Licht, W. __..__ - XIV, 146
Liu, B. Y. H. ...------------- XII, 101
Liu, Y. A. __.--_- XIV, 184; XV, 178
Locke, M. __.-.. - ..--- _____. . XV, 36
Lockhart, F. J. ._-- XIV, 205
Longwell, J. P.---____--- XIII, 80
Luks, K. D.- --- __ XII, 163
Lynn, S. --___-----.____. XIV, 130


McCollister, R. D.
McGee, H. A., Jr.
McNeil, K. M. -


. - XI, 118
--_ --XI, 39
--._ XII, 130


MacLeod, L. K. _ _ XIII, 132
Macosko, C. ---------- XII, 144
Maloney, J. 0. ---- XII, 122
Marsland, D. B. ____ .. XIII, 116
Martin, J. J. ..__.-. XII, 73; XIII, 73
Martinez, E. N. - XI, 78
Mellichamp, D. A. XIV, 18
Melrose, J. C. _... .--____ XII, 143
Mensing, R. W. .___._ .....- XII, 37
Michelsen, D. L. -.. XI, 28
Middleman, S. - XII, 164
Miller, C. A. --___ - XV, 198
Miller, D. ---____- XI, 10
Minnesota Colleagues --___..- XIII, 8
Missen, R. W. - _- ..- XIII, 26
Moore, R. F. ---- __ XIII, 132
Moo-Young, M. _- XII, 88
Morari, M. ----..._. XIII, 160; XIV, 32
Murray, J. ----...-- ..---.. XV, 112
Myers, A. L. -..--_ ...___- XIV, 8
N
Neufeld, V. R. - XIV, 91
Neumann, P. D. -. ..___.--_-- XII, 92
Newton, J. J. --_-_______--. XII, 116
Noble, R. D. -.~~ - XIII, 142
Norman, G. R. -----------XIV, 91
Norman, S. L. _.- _ XIII, 132
Notre Dame Faculty --__-----_ XV, 2

0
O
O'Connell, J. P. __..... XIV, 120
Oliver, B. F. ....- ------ - XI, 103


223


FALL 1981









Ollis, D. F. --- __
Oscarson, J. L. _ __
P
Paspek, S. C. - ------_
Patke, N. G. ---
Patterson, G. K. _----_---
Peck, R. ___-----___
Penn, M. _- -----_-
Peppas, N. A. XIV, 188; X7
Perkins, J. D. __ -
Perlmutter, D. D. - XII, 1
Peters, M. S. .-------_
Petersen, E. E. __--
Plank, C. A. .---__-_-_-_.
Poehlein, G. W.
Prieve, D. C ....---- XII, 1
Prud'homme, R. K. --_
Purkapple, J. D. ___ _
Pyle, D. L. __-__ - --


Quentin, G. H.


XIII, 176 Schowalter, W. R.
XIII, 46 Schultz, J. S. _
Sears, J. T. -----
Seborg, D. E. .
XIV, 78 Senkan, S. M. _.
- XIV, 76 Shacham, M. _--
_ XIV, 26 Shah, D. 0. ----
-- XIII, 76 Shaheen, E. I. -
_XI, 68 Shinnar, R.
---, 1 X, 68 Silveston, P. L.
, 120, 135 Smith, W. R- .
XIV, 174 Snider, E. H.-
18; xv, 14 Sommerfeld, J. T.
XV, 144 Soong, D. S.
XII, 152 Sprague, C. H.
XIII, 138 Stadtherr, M. -
.02 XIV, 2 Stanford, T. G. _
02; XV, 54 Stankovich, R. J.
XV, 130 Sterling, A. M.
--XI, 185 Stevens, J. D. -
XIV, 174 Stevenson, J. F.
Stewart, W. E.
Street, W. B. --
XI, 24 Stroeve, P. _ ---
Sundberg, D. C.
Sussman, M. V.


Rajagopalan, R. __------ XII, 172
Ramkrishna, D. __ XII, 14; XIII, 172
Ranz, W. E. .. ..______.- XIV, 112
Rao, Y. K. -..-- -------XIII, 147
Ray, W. H. ....... XIII, 160; XIV, 32
Reid, R. C. ___ XII, 60, 108, 194
Retzloff, D. _-- __ .. ... XI, 168
Richarz, W. --- --_ XII, 112
Rodriguez, F. -__ ____....._ XIII, 96
Rosner, D. E. -_ . XIV, 192, 193
Rousseau, R. W. .--__. XIII, 72; XV, 8
Russel, W. B. ....-.__ .. ___ XIII, 176
Russell, T. W. F. _. XI, 41, 74, 170;
XII, 18; XIII, 194
Ryan, J. T. _....---------------.. XV, 40

S


Sacco, A., Jr. --
Sarofim, A. F.
Saville, D. A.
Schechter, R. S.


------ XV, 121
___XIII, 80
.--_- XIII, 176
XIV, 156


Tanner, R. D. .---.......
Tarbell, J. M. ____.
Tarrar, A. R .. ..._......
Tassios, D. ---~_- -
Taylor, W. K. __---
Thatcher, C. M.
Theodore, L. ---
Thomson, W. J. __ ---
Threadgill, D.
Timmerhaus, K. D. -..
Tock, R. W. .---
Turner, H. E. _
Tyne, S. C. - --_.....
U
Uhl, V. W. ---


VanNess, H. C.


......-.__ .. XIII, 176
. ----- XII, 4
--.--_. XII, 74
XIV, 42; XV, 106
___- XIV, 200
.----- XV, 78
-XI, 14
------- XII, 118
-- -_ --- XI, 150
----- XIV, 130
-.----- XIII, 26
XI, 44
.__ XIII, 126; XV, 86
- - XV, 204
- __- _ XI, 24
X~_ IV, 114
----- XI, 186
-- XIII, 132
-___- XIII, 54
.-.--- XIV, 136
-. ---- XII, 30
----- XII, 72
------ XV, 172
XV, 126
---_- XI, 118
-. --- XII, 34


..---.- XIII, 145
-- XII, 8
--------- XV, 178
- XV, 133
- - XIV, 88
XIV, 96
XII, 198
- XV, 184
XIV, 108
~_ XV, 68
-- - XIII, 40
- XI, 74
__ XIII, 132


Vannice, M. A. ----___ XIII, 164
Varma, A. _--- XIII, 131, 184; XIV, 78
Vermeulen, T. _--- - XIII, 156
Vernor, T. E. --- _ XI, 185
Veronda, W. -__ - _ XIV, 60
Vivian, J. E. ---- - XIV, 200

W
Wall, J. D. -.. _-..-. XI, 138
Waller, K. V. - __ _ -- XV, 30
Walter, C. -___ ---_-- XII, 23
Wankat, P. C. - --- 2 XV, 208
Ware, C. H., Jr. -__. XIV, 24
Ward, T. J. ____ XIV, 38
Wasan, D. ------ XI, 10
Watson, C. G. ---- XIV, 90
Webster, D. J. _ _ XII, 116
Weinstock, I. B. -__- XII, 206
Wengrow, H. R. --- XI, 32
Westerberg, A. W.- XIV, 72
Westwater, J. W. ----- XI, 53; XII, 73
Wheelock, T. D. __ XII, 178; XV, 186
Whitaker, S. ------- XII, 182
White, J. L. - . _-- ~ XIII, 87
White, R. E. _-- _ XIII, 110
Whitney, R. P. -------.- _ XII, 56
Wicks, C. E. ----- - XIV, 102
Wilcox, W. R. _____ _ XIII, 88
Williams, D. C. --__--- XV, 178
Williams, G. C. -- .... XIII, 80
Williams, M. L. -- -- XII, 188
Willis, M. S. __ ___ XIII, 170
Wills, G. B. ---- XIV, 142
Wisconsin Colleagues -------- XIII, 60
Wolf, E. E. -- _ - XV, 214
Wong, L. K. .__----_- XIII, 132
Woods, D. R.__.._ XI, 86, 140;
XII, 116, XIII, 64, 132; XIV, 88,
92, 130


Yen, T. F. _ ----- XIII, 180
XI, 149 Youngquist, G. R. ._ XII, 202; XIII, 20


-.-...---- XI, 154


Zipf, K. ------.------... .. ----- XII, 33


TITLE INDEX


A
Air Pollution, Engineering Control of* ----__ XIV, 146
Analysis, Chemical Engineering . ---~ XV, 192
Audio Visual Aids Subcommittee Activities __--- XI, 46
AWARD LECTURES:
Cryogenic Heat Transfer ____------ - XV, 68
Dynamics of Runaway Systems __-_....------ XIII, 156
Kinetics of Coal Processing _-._._....- .__------- XV, 14
Superheated Liquids --- __ _- XII, 60, 108, 194
B
Bachelors-Masters Program, A Combined --~_.. XIII, 138
Biochemical Engineering, A Course in -------- XI, 170
Biochemical Engineering Programs: A Survey of
U.S. and Canadian ChE Departments ... ------ . XII, 88
Biomedical Engineering Principles* -- ..__ .. XII, 55
Biophysical Chemistry* __. - ~_. _ - XIV, 147
C
CACHE, What is __ --- -- ---- XIV, 84
Catalysis and Catalytic Reaction Engineering,
Research on ._____.__.. ---- __.... XV, 160
Cellulose as a Chemical and Energy Resource* ----- XII, 23
Chemical Engineering and Modular Instruction _ XII, 136
Chemical Engineering Education Revisited ----___ XII, 198
Chemical Reaction Engineering, Influential
Papers in -.---- -------------- -- ..- -------XII, 158


Chemical Reaction Engineering Science -__ -- XI, 168
Chemical Reactor Design for Process Plants* ------ XIV, 24
Chemical Reactor Engineering _ ---_ XII, 152
Chemical Reactor Omnibook* ------- XV, 219
Chemical Reactor Theory, A Review of* .__ XIII, 131
Chemical Reactors, A Course in --. __ XIV, 168
Chemical Stoichiometry, What is e -----_ . XIII, 26
Chemists, A 15-Month MS ChE Degree
Program for --___ __ __---- XIII, 46
Classical Thermodynamics XV, 156
Close Encounters of a Sparse Kind -------XIV, 72
Coal and Modern Coal Processing* -_ - _ XV, 186
Coal Liquefaction and Desulfurization ------~~~. XV, 178
Coal Liquefaction Processes ------- XIII, 180
Coal Science and Technology _-........___--- _- XII, 178
Colloidal Phenomena, A Course on __--_-- XIII, 176
Combustion Science and Technology - - XIV, 193
Computer-Aided Curriculum Analysis ------_ XI, 64
Computer-Aided Process Design __ .. _ XIII. 126
Computer-Based Instruction ___ ---_ ___ XV, 78
Contact Catalysis* _--. XIV, 12
Continuum Thermodynamics, Foundations of* --- XII, 143
Co-Op Ph.D. Programme in ChE .- XIV, 94
Course Types by Descriptive and Prescriptive
Educational Factors, Comparison of ..---_ - _ XII, 74
Creation, The ---- - - - _ - XIII, 209

*Book Review


CHEMICAL ENGINEERING EDUCATION


-------------









D
DEPARTMENTS:
Brigham Young _.-_. __.- --_.--- -___--__--- XI, 104
Carnegie-Mellon _---------- - -__ - ...--- -- XII, 102
Case Western Reserve .-------------------------- XI, 4
Colorado ___------__ __________- __ .---- XIV, 54
Georgia Tech ______ -_____ XIV, 2
Institute of Paper Chemistry --- - -- XII, 56
LSU .---- - XIII, 54
N.C. State ....------------------.--- XIII, 2
Notre Dame .----------- ---------- --__--- XV, 2
Oregon State ---___------- -- --------- --- XIV, 102
Penn State - .. --_.- -.-....-----.. XII, 8
Rolla, U. Missouri -------------------------- - XV, 62
Rutgers -___--------__ ---- XI, 54
Santa Barbara, U. C. ----- - .------- XV, 106
Texas A & M - -- ~~___~_- - XIII, 110
Departments, Too Many _-------_-- -----__.....-- _ XI, 39
Design, Internship in ChE ___--- - XI, 74
Diffusion and Surface Reaction in Heterogeneous
Catalysis - __ -.________.___ --____ -_______ .. XII, 112
Division Activities --___-__ XII, 107; XIV, 113; XV, 96, 118
E
Economics, A Doctoral Level ChE Course _----- XIII, 168
EDUCATORS:
Bennett, Gary, of Toledo .-_..---------------- XIII, 104
Bird, R. Byron, of Wisconsin --- -- - XIII, 60
Brainard, Alan J., of Pittsburgh .- ---- XII, 50
Corcoran, William H., of Caltech - _ XIV, 60
Felder, Richard M., of N.C. State XV, 8
Fogler, Scott, A Teacher of Learning ------- XII, 4
Humphrey, Art, University of Pennsylvania -- XIV, 8
Peck, Ralph, of Illinois Tech ___ ---- XL, 10
RA of Minnesota .---....---------------------- XIII, 8
Ruckenstein, Eli., of SUNY Buffalo -.......----- XV, 54
Scriven, Skip, of Minnesota ___--- XI, 50
Sparks, Bob, of Washington University -- XV, 112
Tanner, Bob, of Vanderbilt ---- - XIV, 108
White, Jim, of Tennessee ...---------------..- -- XI, 98
Woods, Don, of McMaster ---- - XII, 98
Electrochemical Engineering, A Course in ------_ XI, 164
Enrollment by Professional Society Action, Can
We Limit _________------- __-_ XI, 41
Enrollments, Coping With Bulging ChE ---.. ..... XV, 146
Entrance Region Mass Transfer Experiment ----- XIII, 20
Equipment, A Course in ChE -_______- - XIII, 88
Examinations as a Method of Teaching _--------- XIII, 76
Examinations in ChE, Usage of Multiple Choice -- XV, 86
Experience at One University _ ~_- _ XI, 181
Experiments for Estimating Free Convection and
Radiation Heat Transfer Coefficients .----- XII, 122
Experiments in Undergraduate Reaction Engineering:
Startup and Transient Response of CSTR's
in Series _- __ --___ - - XI, 118
Experiments, Teaching of ChE Thermodynamics _ XII, 130
F
Faculty-Student Consultant Teams to Solve
Industrial Problems, Using Summer _----- XI, 28
Faculty Work Load Measurement - -------_ XI, 134
Faculty Workload Measurement at Penn State __ XI, 130
Filtration: Principles and Practices, Part 1* --... XIII, 170
Financial Decision Making in the Process
Industry* -------- ----------- ------- ---- XI, 149
Finite Element, Some Infinite Possibilities .------ XV, 20
Fluid Flow and Electric Circuitry, Analogy
Between -- - -----------.- XIII, 96
Fluid Mechanics Can Be Fun ----- -- XIII, 14
Fossil Fuels Program, M.I.T.'s -__--------------------.----- XIII, 80
Freeze Drying of Fruits and Vegetables: A
Laboratory Experiment ---_--- XIII, 142
Functional Analysis for ChE's, A Course on ----- XIII, 172
G
Gas Chromatography, Simple and Rapid Method of
Determining the Vapor Pressure of
Liquids by .---- ----- -- XII, 140


Gas Engineering at the Algerian Petroleum
Institute, Training and _ --______ XII, 118
Graduate Education on a Statewide Closed-Circuit
Television Network _-...... ---.---- - -..... . XI, 186
Graduate Programs for Non-Chemical Engineers __ XI, 176
Graduate School Through Undergraduate
Research--- ---------- XV, 135
Growth in ChE, Practical Limits to __----.. ____ XI, 38
H
Heterogeneous Catalysis, A Course in __-.-.__ XV, 214
Heterogeneous Catalysis, A Course on __-..--- XIII, 164
Horses of Other Colors: Some Notes on
Seminars in a ChE Department _ -- XII, 148
Hydrocolloidal Systems, The Dynamics of -----__ XII, 172
I
Industrial Chemistry: Principles of* -- _ XV, 144
Industrial Crystallization* _____-- --- _ XIII, 72
Industrial Implications in a Polymer
Engineering Course, Stressing ___- _ XI, 122
In Situ Processing, Research on . -- _ XIV, 156
Interface Between Industry and the Academic
World ___- -------__ _- XI, 150
K


Kinetics and Catalysis


XV, 188


L
Large Classes, Handling ___------- -XIV, 114
Lessons in a Lab: Incorporating Laboratory
Exercises into Industrial Practices __- __ XII, 92
Letters To The Editor ----- XI, 3, 53, 149; XII, 47, 129, 151
XIII, 19, 63, 68, 91; XIV, 68; XV, 25, 116
Library, Organization of a Functional ChE ------------ XI, 44
Liquids and Solutions: Structure and Dynamics* __ XIII, 69
Liquids and Their Properties* ---___- XV, 97
M
Market Analysis, Teaching --__---_~_ --__.. _ XV, 40
Material Balance Calculations with Reaction:
Steady-State Flow Processes -__ -- XIII, 92
Materials Course, Experiences in a Senior
ChE - XIV, 120
Materials Education, What Does the Practicing
ChE Want in - ___- __________ XII, 44
Materials Science, Introduction to (SI Edition)* -- XI, 167
Materials, The Nature and Properties of
Engineering* -___- _ -___ XIII, 87
Mathematical Methods in ChE, A Course in __ XIII, 184
Mathematical Modeling, The Application of, to
Process Development and Design* -.__ - XI, 53
MEMORIAL:
Biery, John C. __- ------ - .._----- --... . XV, 60
Chen, Huang Tsung -----_...... . .. . ---XV, 171
Lapidus, Leon- __ ___ ..---. XI, 148
Parravano, Guiseppe --...-... ____--_____..... XII, 163
Peebles, Fred N. -- XIV, 145
Schweyer, Herbert E. - X--_____..--___ ___.-- XV, 122
Shen, Mitchel ------ - - __ ----- XIII, 204
Stevens, John D. -- __ __- XIV, 77
Treybal, Robert E. ----- XIII, 204
Mexico, ChE Education in Methodology and
Evaluation --_-..................._____--_______.__ .... XI, 78
MIT School of ChE Practice ----_-__ XIV, 200
Modified Carnot Cycle, A . .---. . . XIII, 147
Molecular Theory of Fluid Microstructures ..__ XIV, 126
Molecular Theory of Thermodynamics,
Introduction -------- ---- XIII, 198
Molecular Thermodynamics and Computer
Simulation ---_- XV, 172
Multiple Choice Examinations in ChE, Usage of __ XV, 86
N
News, ChE _______-- XI, 53; XII, 135, 144; XIII, 32, 52, 94,
108, 115, 203; XIV, 44, 98, 208
*Book Review


FALL 1981








O
Oil Shale Char Reactions ____------___ - XV, 184
Operational Amplifiers in
Chemical Instrumentation* ..____ ..- ____ - . XIII, 75
Optimization Theory, Introduction to* -.....-- . XIV, 99

P
Parametric Pumping, Research on _ -- - XV, 166
Petroleum and the Continental Shelf of
North West Europe* _~~~~- XI, 138
Piping Layout as a Laboratory Project ---------- XIII, 64
Plant Engineering at Loughborough -__- - XIV, 180
Pollution Control, Strategy of* ___--_ - ---- XII, 199
Polymer Fluid Dynamics, Research on --------_ XIV, 152
Polymerization Reaction Engineering _... ____ XIV, 188
Polymer Processing, A Course in ___ - _- XV, 204
Polymer Processing, A Graduate Course in -..-- XII, 164
Polymer Processing, Principles of* _...____ - XV, 59
Polymer Science and Engineering, Courses in .---. XI, 174
Polymer Science, Two Courses in ___ ..__ XIII, 190
Population Balances, The Prospects of .-- __ XII, 14
Practice School __--- -----___- XIII, 84
Primary Battery, The* __.. _ ---__..... .__ -. XII, 206
Problem Solving, On Teaching
Part 1: What is Being Done ..---___ XI, 86
Part 2: The Challenges ---- ---- _ XI, 140
Problem Solving, Patterns of* --.----------- XIII, 145
Problem Solving, What is ..----.-.. ------.----.... XIII, 132
PROBLEMS:
Dolphin Problem --___ ------_. XV, 220
Iceberg Problem, The .----- ___- XIII, 70
In the "Heat" of the Night .....- ___-. - --.... XIV, 46
In the Heat of the Night: Two Dimensional
Heat Transport ---____-----___--- XIV, 47
Mirror Fog Problem, The --. ____.. XIII, 155
Mirror Fog Problem: Solution _. _ XIV, 45
Prairie Dog Appendix, A _------__.----_.___ XIV, 199
Prairie Dog Appendix: Solution ----_- XV, 38
Prairie Dog Problem - ____-__~_---__ XIV, 70
Prairie Dog Problem: Solution ---- - XIV, 198
Process Control Education in the U.S. and
Canada, A Survey of ___-__ _____ __ XIV, 42
Process Control Engineering at UT Permian -....-- _ XI, 24
Process Control Experiments, Advanced --__ ... . XIV, 26
Process Control, A Flexible Self-Paced Course -_ XIII, 120
Process Control Education and Research in
the USA, Impressions of ________ ___-- _ XV, 30
Process Control Experiment: The Toilet Tank ... XIV, 38
Process Design, Applied Chemical* _-.........._ XIV, 205
Process Design, Teaching the Basic Elements
of, With a Business Game ___--......_____ .... XII, 18
Processes, Elementary Principles of Chemical* .- XIV, 136
Processing Industries, The Structure of Chemical XIII, 194
Process Simulation, We Can Do: UCAN-II - XIV, 138
Process Synthesis, A Course in _ XIV, 184
Process Systems, Chemical: A Second Course in __ XIII, 116
R
Radiative Heat Transfer, Engineering
Calculations in* __ -------------------- __ - --_ XI, 2
Ranking ChE Departments in Terms of
Productivity Indices .... _-_______ - _-.__ -. . ...- XII, 65
Ranking of Departments: Is Productivity the
Same as Quality: Editorial --__---__---__---- XII, 64
Rate Data, Interpretation and Use of -... _--. XIII, 39
Rate of Reactions: A Definition or the Result
of a Conservation Equation _____ XIV, 14
Rate Phenomena in Process Metallurgy* _...--_ --. XI, 103
Reactor Design From a Stability Viewpoint ----- XII, 168
Reactor Design, Kinetics in a*--- - _ ------- XIV, 99
Real-Time Computing, A Full-Year Course
Sequence in ___. ....- ---__ - XIV, 18
Real-Time Computing, Integration of, into
Process Control Teaching
Part I: The Graduate Course -------- XIII, 160
Part II: The Undergraduate Course . .. XIV, 32
Recycle Reactor, Utilization of the, In
Determining Kinetics of Gas-Solid Catalytic


Reactions -___-___-....- ..-..-----....---
Refinery II: Collograph -----_ ---
Research with Senior Level Students -
Reynolds' Number Song, The _
Road to Hell, The ...- -----


- XIV, 78
SXIV, 192
XV, 133
XIII, 12
XII, 33


Sciences and the Humanities, The .._____ - XI, 68
Scientists Must Write* ------- - XIV, 208
Seminars in a ChE Department, Some Notes on _ XII, 148
Separation Processes, An Elective Course in .- XV, 208
Separation Processes, Use and Abuse of
Efficiencies in ---- -- ---------- XII, 38
SI Units in ChE and Technology* ... ----- XII, 202
Smoke, Dust and Haze: Fundamentals of
Aerosol Behavior* -__ -- ___ - XII, 101
Sodales Princetonienses ------ _ - XV, 12
Special Functions and Applications - .---_ XV, 92
Statistical Methods for Engineers and
Scientists* -- ---- _____ XII, 37
Statistics for Experimenters: Introduction to
Design, Data Analysis and Model Building* _- XIV, 206
Student Point of View, A .-- ---..- XI, 185
Study-Travel Program, Virginia Tech's -------- XIV, 142
Summer School in Snowmass ---- _ _ XII, 3
Surface Science, The World of _-...--__- ~~_ XI, 14
Sycons, A Systems Control Simulator _ - - XI, 32
Symposium at Carnegie-Mellon, ChE _ --_- XV, 36
Systems Modelling and Control - __- XIV, 174
T
Take Two Pills Every Four Hours: A Hydrodynamic
Analog for Drug Dosage Regimens -- __ XII, 30
Teaching From an Assistant Professor's Point
of View, The Importance of _--- ._- XIV, 66
Technical Communication at Texas Tech,
Renewed Emphasis on ___- .....-- ... XIII, 40
Technical Prose: English or Techlish ---- XI, 154
Telephone Tutorial Service, A - _ --- XII, 26
Theoretical Rheology* ------_ XII, 144
Thermochemical Kinetics* ------- - XIII, 145
Thermodynamic Heresies ---- ______ XII, 34
Thermodynamics, Chemical and Engineering* __ XIV, 96
Thermodynamics: Fundamentals, Applications* -- XII, 163
Transport Phenomena in Multicomponent,
Multiphase Reacting Systems ..._____ .. XII, 182
Transport Phenomena in the Delaware -_____ XV, 74
Traveling Circus as a Means of Introducing
Practical Hardware, The - ... - -------XII, 116
Trouble Shooting at Canadian Industries
Limited -____._--_--- --___- XIV, 88
Trouble Shooting at McMaster __---- - XIV, 92
Trouble Shooting at the University of Wisconsin _ XIV, 90
Trouble Shooting Cases at McMaster
Health Sciences - -~__ - _ XIV, 91
Trouble Shooting Problems, Using -. XIV, 88; XIV, 130
Tubular Reactor Experiment, A Simple - - XV, 26
Turbulent Mixing in Non-Reactive and
Reactive Flows* _~___----- __ - XIV, 112
Turbulent Transport Processes, Models for _------ XIII, 34
Two Phase Flow, The Role of Waves in -- - XI, 108

U


Undergraduate Curricula 1976
Undergraduate Research -
Underground Processing -


---- XI, 60
.XV, 120-144
-_- XV, 198


Wall Turbulence, Research on - --------. XIV, 162
Waste-Water Treatment Processes,
Introduction to* ----- ----- XIII, 78
When is a Man Half a Horse __. -- - -_ XIII, 73
Where is the Roller Coaster Headed _--- - XI, 34
Why PSI? How to Stop Demotivating Students __ XII, 78
Write, All a Chemical Engineer Does is . -..---- XII, 188


*Book Review


CHEMICAL ENGINEERING EDUCATION







STHE UNIVERSITY OF ARIZONA

TUCSON, AZ




The Chemical Engineering Department at the University of Arizona is young and dynamic with a fully accredited
undergraduate degree program and M.S. and Ph.D. graduate programs. Financial support is available through gov-
ernment grants and contracts, teaching, and research assistantships, traineeships and industrial grants. The faculty
assures full opportunity to study in all major areas of chemical engineering.

THE FACULTY AND THEIR RESEARCH INTERESTS ARE:


JOSEPH F. GROSS, Professor
Ph.D., Purdue University, 1956
Boundary Layer Theory, Pharmacokinetics, Fluid Me-
chanics and Mass Transfer in The Microcirculation,
Biorheology

ALAN D. RANDOLPH, Professor
Ph.D., Iowa State University, 1962
Simulation and Design of Crystallization Processes,
Nucleation Phenomena, Particulate Processes, Explo-
sives Initiation Mechanisms

THOMAS R. REHM, Professor and Acting Head
Ph.D., University of Washington, 1960
Mass Transfer, Process Instrumentation, Packed Column
Distillation, Applied Design

JOST O.L. WENDT, Professor
Ph.D., Johns Hopkins University, 1968
Combustion Generated Air Pollution, Nitrogen and Sul-
fur Oxide Abatement, Chemical Kinetics, Thermody-
namics Interfacial Phenomena







Tucson has an excellent climate and
many recreational opportunities. It
is a growing, modern city of
450,000 that retains much of the
old Southwestern atmosphere.




For further information.
write to:
Dr'. J. 0. L. II'endt
Graduate Study Committee
Department of
Chemical Engineering
University of .4rizona
Tucson, Arizona 85721


The University of Arizona is an
equal opporlunily educational
instilution/equal opportun;ly employer


DON H. WHITE, Professor
Ph.D., Iowa State University, 1949
Polymers Fundamentals and Processes, Solar Energy,
Microbial and Enzymatic Processes


WILLIAM P. COSART, Assoc. Professor
Ph.D. Oregon State University, 1973
Transpiration Cooling, Heat Transfer in
teams, Blood Processing


Biological Sys-


THOMAS W. PETERSON, Asst. Professor
Ph.D., California Institute of Technology, 1977
Atmospheric Modeling of Aerosol Pollutants,
Long-Range Pollutant Transport, Particulate
Growth Kinetics.

FARHANG SHADMAN, Asst. Professor
Ph.D., University of California-Berkeley, 1972
Reaction Engineering, Kinetics, Catalysis







I:


SI


: *4-


0I -


1 :I1 ' F


i


I,


4~h~


Ei�


rl - =1 :








Chemical Engineering at



UNIVERSITY OF ALBERTA


EDMONTON, CANADA


Faculty and Research Interests
I. G. Dalla Lana, Ph.D. (Minnesota):
Kinetics, Heterogeneous Catalysis.
D. G. Fisher, Ph.D. (Michigan): Process
Dynamics and Control, Real-Time
Computer Applications, Process
Design.
C. Kiparissides, Ph.D. (McMaster):
Polymer Reactor Engineering, Op-
timization, Modelling, Stochastic
Control.
D. Lynch, Ph.D. (Alberta): Kinetic
Modelling, Numerical Methods,
Computer Aided Design.
J. H. Masliyah, Ph.D. (British Colum-
bia): Transport Phenomena,
Numerical Analysis, In-Situ Recovery
of Oil Sands.
A. E. Mather, Ph.D. (Michigan): Phase
Equilibria, Fluid Properties at High
Pressures, Thermodynamics.
W. Nader, Dr. Phil, (Vienna): Heat
Transfer, Air Pollution, Transport
Phenomena in Porous Media, Applied
Mathematics.
F. D. Otto (Chairman), Ph.D. (Michi-
gan): Mass Transfer, Gas-Liquid Re-
actions, Separation Processes, En-
vironmental Engineering.
D. Quon, Sc.D. (MIT), Professor Emeri-
tus: Energy Modelling and Economics,
Linear Programming, Network
Theory.
D. B. Robinson, Ph.D. (Michigan):
Thermal and Volumetric Properties of
Fluids. Phase Equilibria, Thermody-
namics.
J. T. Ryan, Ph.D. (Missouri): Process
Economics, Energy Economics and
Supply.
S. L. Shah, Ph.D. (Alberta): Linear
Systems Theory, Adaptive Control,
Stability Theory, Stochastic Control.
S. E. Wanke, Ph.D. (California-Davis):
Catalysis, Kinetics.
R. K. Wood, Ph.D. (Northwestern):
Process Dynamics and Identification,
Control of Distillation Columns,
Modelling of Crushing and Grinding
Circuits.


I

Graduate Study
U of A's Chemical Engineering gradu-
ate program offers exciting research
opportunities to graduate students moti-
vated towards advanced training and
research. Graduate programs leading to
the degrees of Master of Science, Master
of Engineering and Doctor of Philosophy
are offered. There are currently 13 full-
time faculty members, a few visiting
faculty, several post-doctoral research
associates and 35 graduate students.



Financial Aid
Financial support is available to full-
time graduate students in the form of
fellowships, teaching assistantships and
research assistantships.



The University of Alberta
U of A is one of Canada's largest
Universities and engineering schools
with total enrollment of over 25,000
students. The campus is located in the
city of Edmonton and overlooks the
scenic North Saskatchewan River Valley.
Edmonton is a cosmopolitan modern
city of over 600,000 people. It enjoys a
renowned resident professional theatre,
symphony orchestra and professional
football, hockey and soccer leagues.
The famous Banff and Jasper National
Parks in the Canadian Rocky Mountains
are within easy driving distance.









Applications for additional information
write to:

CHAIRMAN,
Department of Chemical Engineering
University of Alberta
Edmonton, Canada T6G 206


FALL 1981










I"' THE UNIVERSITY OF flKRON
fWkron,OH 44325


DEPARTMENT OF

CHEMICAL ENGINEERING



GRADUATE PROGRAM


FACULTY


RESEARCH INTERESTS


G. A. ATWOOD -____ ..----. Digital Control, Polymeric Diffusivities, Multicomponent Adsorption.
J. M. BERTY Reactor Design.
L. G. FOCHT ___ Fixed Bed Adsorption, Design and Process Analysis.
H. L. GREENE Biorheology, Kinetic Modeling, Contaminant Removal from Coal Gasification.
S. LEE -- ---___________- _ -- ..Coal Gasification, Kinetic Modeling, Digital Simulation.
J. P. LENCZYK High Pressure Kinetics, Activity and Diffusion Coefficients via Ultracentrifuge.
R. W. ROBERTS .__ __ Atomization Processes, Fusion and Adhesion Characteristics of Polymer Powders.
R. F. SAVINELL ___Electrochemical Phenomena.
M. S. WILLIS Multiphase Theory, Filtration and Diffusion in Foamed Plastics.




Graduate assistant stipends for teaching and research start at $4,200. Industrially
sponsored fellowships available up to $9,000. These awards include waiver of
tuition and fees. Cooperative Graduate Education Program is also available. The
deadline for assistantship application is March 1.





ADDITIONAL INFORMATION WRITE:
Dr. Howard L. Greene, Head
Department of Chemical Engineering
University of Akron
Akron, Ohio 44325


CHEMICAL ENGINEERING EDUCATION










ARIZONA STATE

UNIVERSITY

Graduate Programs
for M.S. and Ph.D. Degrees
in Chemical and Bio Engineering



Research Specializations Include:
ENERGY CONVERSION ADSORPTION/SEPARATION *
BIOMEDICAL ENGINEERING *TRANSPORT PHENOMENA*
SURFACE PHENOMENA REACTION ENGINEERING.
ENVIRONMENTAL CONTROL* ENGINEERING DESIGN*

Our excellent facilities for research and teaching are complemented
by a highly-respected faculty:
James R. Beckman, University of Arizona, 1976
Lynn Bellamy, Tulane University, 1966
Nell S. Berman, University of Texas, 1962
William J. Crowe, University of Florida, 1969 (Adjunct)
William J. Dorson, Jr., University of Cincinnati, 1967
Eric J. Guilbeau, Louisiana Tech University, 1971
James T. Kuester, Texas A&M University, 1970
Kim L. Nelson, University of Delaware, 1981
Castle 0. Reiser, University of Wisconsin, 1945 (Emeritus)
Vernon E. Sater, Illinois Institute of Technology, 1963
Robert S. Torrest, University of Minnesota, 1967
Bruce C. Towe, Pennsylvania State University, 1978
Imre Zwiebel, Yale University, 1961
Fellowships and teaching and research assistantships are available to
qualified applicants.
ASU is in Tempe, a city of 120,000, part of the greater Phoenix
metropolitan area. More than 38,000 students are enrolled in ASU's
ten colleges; 10,000 of whom are in graduate study. Arizona's year-
round climate and scenic attractions add to ASU's own cultural and
recreational facilities.
FOR INFORMATION, CONTACT:
Imre Zwiebel, Chairman,
Department of Chemical and Bio Engineering
Arizona State University, Tempe, AZ 85287



!Simi









AUBURN UNIVERSITY

CHEMICAL ENGINEERING GRADUATE STUDIES


Graduate Degrees
The Department of Chemical Engineering
at Auburn University offers graduate work
leading to the M.S. and Ph.D. degrees in
chemical engineering. The research empha-
sizes experimental and theoretical work in
areas of current national interest. Modern
research equipment is available for ana-
lytical, process and computational studies.
Auburn University is an equal opportunity
Institution.

Area Description
Auburn University, which has 18,000
students, is located in Alabama between
Atlanta and Montgomery, Ala., with Co-
lumbus, the second largest city in Georgia,
only 35 miles away. The local population
is about 75,000. University-sponsored activi-
ties include a lecture series with nationally
known speakers, a series of plays and
artistic and cultural presentations of all
kinds. Recreational opportunities include
equipment at the University for participation
in almost every sport.


,


Research Areas
COAL: Coal liquefaction, magnetic de-
sulfurization and beneficiation, solvent re-
fining.
BIOMASS: Chemical and enzymatic con-
version of forest and agricultural waste to
fuels, petrochemicals and animal feed.
FUNDAMENTALS: Kinetics, catalysis, en-
zymatic and fermentation reactors, high
gradient magnetic separation, transport
phenomena, solid-liquid separation, bio-
medical engineering.
ENVIRONMENTAL: Air and water pollu-
tion control processes.
NEW TECHNOLOGY: Advanced coal con-
version, novel enzymatic reactors, applica-
tions of high gradient magnetic separation,
photography by immobilized enzymes,
novel thickener design, polymeric replace-
ment of textile size, enzymatic artificial
liver.
PROCESS SYNTHESIS AND CONTROL:
Design of optimal energy-integrated pro-
cesses and control of interactive, multivari-
able, nonlinear processes.






For financial aid and admission
application forms write:

Dr. R. P. Chambers, Head
Chemical Engineering
Auburn University, AL 36849


CHEMICAL ENGINEERING EDUCATION


r I










BRIGHAM YOUNG UNIVERSITY

PROVO,UTAH


* Ph.D., M.S., & M.E.
* ChE. Masters for Chemists Program
* Research


Biomedical Engineering
Catalysis
Coal Gasification


Combustion
Electrochemical Engineering
Fluid Mechanics


Fossil Fuels Recovery
High Pressure Chemistry
Thermochemistry &
Calorimetry


* Faculty
D. H. Barker, (Ph.D., Utah, 1951)
C. H. Bartholomew, (Ph.D., Stanford, 1972)
M W. Beckstead, (Ph.D., Utah, 1965)
D. N. Bennion, (Ph.D., Berkeley, 1964)
B. S. Brewster, (Ph.D., Utah, 1979)
J J. Christensen, (Ph.D., Carnegie Inst. Tech, 1958)
J. M. Glassett, (M.S., MIT, 1948)


R. W. Hanks, (Ph.D., Utah, 1961)
W. C. Hecker, (Ph.D., U.C. Berkeley,
1981)
P O. Hedman, (Ph.D., BYU, 1973)
J. L. Oscarson, (Ph.D., Michigan, 1979)
P. J. Smith, (Ph.D., BYU, 1979)
L. D. Smoot, (Ph.D., Washington, 1960)
K. A. Solen, (Ph.D., Wisconsin, 1974)


Beautiful campus located in the rugged Rocky Mountains
Financial aid available (We have lots of money.)
Address Inquiries to: Brigham Young University, Dr. Richard W. Hanks, Chairman
Chemical Engineering Dept. 350 CB Provo, Utah 84602


FALL 1981


233












The University of Calgary

Program of Study

The Department of Chemical Engineering provides unusual opportunities for research and study leading to the M.Eng., M.Sc. or Ph.D. degrees.
This dynamic department offers a wide variety of course work and research in the following areas: Petroleum Reservoir Engineering, Environ-
mental Engineering, Fluid Mechanics, Heat Transfer, Mass Transfer, Process Engineering, Rheology and Thermodynamics. The University operates
on an eight-month academic year, thus allowing four full months per year for research.
The requirements for the M.Eng. and M.Sc. degrees are 4 to 8 courses with a B standing or better and the submission of a thesis on a
research project.
The requirements for the Ph.D. degree are 6 to 10 courses and the submission of a thesis on an original research topic for those with a B.Sc.
degree.
The M.Eng. program is a part-time program designed for those who are working in industry and would like to enhance their technical educa-
tion. The M.Eng. thesis is usually of the design type and related to the industrial activity in which the student is engaged. Further details of this
program are available from the Department Head, or the Chairman of the Graduate Studies Committee.
Research Facilities

The Department of Chemical Engineering occupies one wing of the Engineering Complex. The building was designed to accommodate the
installation and operation of research equipment with a minimum of inconvenience to the researchers. The Department has at its disposal an
EAl 690 hybrid computer and a TR48 analog computer an Interdata 7132 mini computer for data acquisition and control and numerous direct
access terminals to the University's Honeywell level 68 DPS computing system. In addition, a well equipped Machine Shop and Chemical
Analysis Laboratory are operated by the Department. Other major research facilities include a highly instrumented and versatile multiphase pipeline
flow loop, an automated pilot plant unit based on the Girbotol Process for natural gas processing, an X-ray scanning unit for studying flow in
porous media, a fully instrumented adiabatic combustion tube for research on the in-situ recovery of hydrocarbons from oil sands, a laser ane-
mometer unit, and environmental research laboratories for air pollution, water pollution and oil spill studies.
Financial Aid

Fellowships and assistantships are available with remuneration of up to $15,000 per annum, with possible remission of fees. In addition, new
students may be eligible for a travel allowance of up to a maximum of $300. If required, loans are available from the Federal and Provincial
Governments to Canadian citizens and Landed Immigrants. There are also a number of bursaries, fellowships, and scholarships available on a
competition basis to full-time graduate students. Faculty members may also provide financial support from their research grants to students
electing to do research with them.
Cost of Study

The tuition fees for a full-time graduate student are $756 per year plus small incidental fees. Most full-time graduate students to date have had
their tuition fees remitted.
Cost of Living

Housing for single students in University dormitories range from $259/mo. for a double room, to $320/mo. for a single room, including board.
There are a number of new townhouses for married students available, ranging from $240/mo. for a 1-bedroom, to $300/mo. for a 2-bedroom
and to $278/mo. for a 3-bedroom unit, including utilities, major appliances and parking. Numerous apartments and private housing are within
easy access of the University. Food and clothing costs are comparable with those found in other major North American urban centres.
Student Body

The University is a cosmopolitan community attracting students from all parts of the globe. The current enrollment is about 11,000 with ap-
proximately 1,280 graduate students. Most full-time graduate students are currently receiving financial assistance either from internal or external
sources.
The Community

The University is a cosmopolitan community attracting students from all parts of the globe. The current enrollment is about 13,000 with ap-
the Old West with the sophistication of a modern, dynamic urban centre. Beautiful Banff National Park is 60 miles from the city and
the ski resorts of the Banff and Lake Louise areas are readily accessible. Jasper National Park is only five hours away by car via one of
the most scenic highways in the Canadian Rockies. A wide variety of cultural and recreational facilities are available both on campus and in
the community at large. Calgary is the business centre of the petroleum industry in Canada and as such has one of the highest concentrations
of engineering activity in the country.
The University

The University operated from 1945 until 1966 as an integral part of the University of Alberta. The present campus situated in the rolling hills
of northwest Calgary, was established in 1960, and in 1966 The University of Calgary was chartered as an autonomous institution by the
Province of Alberta. At present the University consists of 14 faculties. Off-campus institutions associated with The University of Calgary include
the Banff School of Fine Arts and Centre of Continuing Education located in Banff, Alberta, and the Kananaskis Environmental Research Station
located in the beautiful Bow Forest Reserve.
Applying

The Chairman, Graduate Studies Committee
Department of Chemical and Petroleum Engineering
The University of Calgary
Calgary, Alberta T2N 1N4
Canada


CHEMICAL ENGINEERING EDUCATION


234








UNIVERSITY OF CALIFORNIA

BERKELEY, CALIFORNIA


u^^^pw~" rA


RESEARCH FACULTY


ENERGY UTILIZATION

ENVIRONMENTAL PROTECTION
KINETICS AND CATALYSIS

THERMODYNAMICS

POLYMER TECHNOLOGY

ELECTROCHEMICAL ENGINEERING

PROCESS DESIGN AND DEVELOPMENT

SURFACE AND COLLOID SCIENCE

BIOCHEMICAL ENGINEERING

MATERIALS ENGINEERING

FLUID MECHANICS AND RHEOLOGY




FOR APPUCATIONS AND FURTHER INFORMATION, WRITE:


Alexis T. Bell (Chairman)
Harvey W. Blanch
Elton J. Cairns
Morton M. Denn
Alan S. Foss
Simon L. Goren
Edward A. Grens
Donald N. Hanson
Dennis W. Hess
C. Judson King
Scott Lynn
David N. Lyon
John S. Newman
Eugene E. Petersen
John M. Prausnitz
Clayton J. Radke
Edward K. Reiff, Jr
David S. Soong
Charles W. Tobias
Theodore Vermuelen
Charles R. Wilke
Michael C. Williams

Department of Chemical Engineering
UNIVERSITY OF CALIFORNIA
Berkeley, California 94720


VQI�









UNIVERSITY OF CALIFORNIA


DAVIS


Course Areas
Applied Kinetics and Reactor Design
Applied Mathematics
Biomedical, Biochemical Engineering
Catalysis
Fluid Mechanics
Heat Transfer
Mass Transfer
Process Dynamics
Separation Processes
Thermodynamics
Transport Processes in Porous Media
Faculty
RICHARD L. BELL, University of Washington
Mass Transfer, Biomedical Applications
RUBEN G. CARBONELL, Princeton University
Enzyme Kinetics, Applied Kinetics, Quantum
Statistical Mechanics, Transport Processes in
Porous Media
ALAN P. JACKMAN, University of Minnesota
Environmental Engineering, Transport Phenomena
BEN J. McCOY, University of Minnesota
Separation, and Transport Processes
DAVID F. OLLIS, Stanford University
Catalysis, Biochemical Engineering
JOE M. SMITH, Massachusetts Institute of Technology
Applied Kinetics and Reactor Design
PIETER STROEVE, Massachusetts Institute of Technology
Mass Transfer, Colloids
STEPHEN WHITAKER, University of Delaware
Fluid Mechanics, Interfacial Phenomena, Transport
Processes in Porous Media


Degrees Offered
Master of Science
Doctor of Philosophy


Program
UC Davis, with 17,500 students, is one of the major
campuses of the University of California system and
has developed great strength in many areas of the
biological and physical sciences. The Department of
Chemical Engineering emphasizes research and a pro-
gram of fundamental graduate courses in a wide variety
of fields of interest to chemical engineers. In addition,
the department can draw upon the expertise of faculty
in other areas in order to design individual programs
to meet the specific interests and needs of a student,
even at the M.S. level. This is done routinely in the areas
of environmental engineering, food engineering, bio-
chemical engineering and biomedical engineering.
Excellent laboratories, computation center and
electronic and mechanical shop facilities are available.
Fellowships, Teaching Assistantships and Research
Assistantships (all providing additional summer support
if desired) are available to qualified applicants.


Davis and Vicinity
The campus is a 20-minute drive from Sacramento
and just over an hour away from the San Francisco
Bay area. Outdoor sports enthusiasts can enjoy water
sports at nearby Lake Berryessa, skiing and other alpine
activities in the Sierra (2 hours from Davis). These rec-
reational opportunities combine with the friendly in-
formal spirit of the Davis campus to make it a pleasant
place in which to live and study.
Married student housing, at reasonable cost, is
located on campus. Both furnished and unfurnished
one- and two-bedroom apartments are available. The
town of Davis (population 36,000) is adjacent to the
campus, and within easy walking or cycling distance.






For further details on graduate study at Davis, please
write to:
Chemical Engineering Department
University of California
Davis, California 95616
or call (916) 752-0400


CHEMICAL ENGINEERING EDUCATION


236









CHEMICAL ENGINEERING


UNIVERSITY






ALIFORNIA






OS


PROGRAMS
UCLA's Chemical Engineering Depart-
ment maintains academic excellence in its
graduate programs by offering diversity in
both curriculum and research opportunities.
The department's continual growth is demon-
strated by the newly established Institute for
Medical Engineering and the National Center
for Intermedia Transport Research, adding to
the already wide spectrum of research
activities.

Fellowships are available for outstand-
ing applicants. A fellowship includes a waiver
of tuition and fees plus a stipend.

Located five miles from the Pacific
Coast, UCLA's expansive 417 acre campus
extends from Bel Air to Westwood Village.
Students have access to the highly-regarded
sciences programs and to a variety of expe-
riences in theatre, music, art and sports on
campus.


CONTACT
Admissions Officer
Chemical Engineering
NGELES 5405 Boelter Hall
Los Angeles, CA 90024
Los Angeles, CA 90024


FACULTY
D. N. Bennion
Yoram Cohen
S. M. Dinh
S. Fathi-Afshar
T. H. K. Frederking
S. K. Friedlander
E. L. Knuth
J. W. McCutchan


Ken Nobe
L. B. Robinson
0. I. Smith
W. D. Van Vorst
V. L. Vilker
F. E. Yates
M. M. Baizer


RESEARCH AREAS
Thermodynamics and Cryogenics
Reverse Osmosis and Membrane Transport
Process Design and Systems Analysis
Polymer Processing and Rheology
Mass Transfer and Fluid Mechanics
Kinetics, Combustion and Catalysis
Electrochemistry and Corrosion
Biochemical and Biomedical Engineering
Aerosol and Environmental Engineering












UNIVERSITY OF CALIFORNIA


SANTA BARBARA
..... __. __ _ - ,-"


FACULTY AND RESEARCH INTERESTS PROGRAMS AND FINANCIAL SUPPORT


SANJOY BANERJEE
Ph.D. (Waterloo)
Two Phase Flow, Reactor Safety,
Nuclear Fuel Cycle Analysis
and Wastes
H. CHIA CHANG Ph.D. (Princeton)
Chemical Reactor Modeling,
Applied Mathematics
HENRI FENECH Ph.D. (M.I.T.)
Nuclear Systems Design and Safety,
Nuclear Fuel Cycles, Two-Phase Flow,
Heat Transfer.
HUSAM GUROL Ph.D. (Michigan)
Statistical Mechanics, Polymers,
Radiation Damage to Materials,
Nuclear Reactor Theory.
OWEN T. HANNA Ph.D. (Purdue)
(Chairman)
Theoretical Methods, Chemical
Reactor Analysis, Transport
Phenomena.
GLENN E. LUCAS Ph.D. (M.I.T.)
Radiation Damage, Mechanics of
Materials.
DUNCAN A. MELLICHAMP
Ph.D. (Purdue)
Computer Control, Process
Dynamics, Real-Time Computing.


JOHN E. MYERS
Ph.D. (Michigan)
(Dean of Engineering)
Boiling Heat Transfer.

G. ROBERT ODETTE
Ph.D. (M.I.T.)
(Vice Chairman, Nuclear Engineering)
Radiation Effects in Solids, Energy
Related Materials Development.

A. EDWARD PROFIO
Ph.D. (M.I.T.)
Bionuclear Engineering, Fusion
Reactors, Radiation Transport
Analyses.

ROBERT G. RINKER
Ph.D. (Caltech)
Chemical Reactor Design, Catalysis,
Energy Conversion, Air Pollution.

ORVILLE C. SANDALL
Ph.D. (Berkeley)
Transport Phenomena, Separation
Processes.

DALE E. SEBORG
Ph.D. (Princeton)
Process Control, Computer Control,
Process Identification.


238


The Department offers M.S. and Ph.D. de-
gree programs. Financial aid, including
fellowships, teaching assistantships, and re-
search assistantships, is available. Some
awards provide limited moving expenses.


THE UNIVERSITY
One of the world's few seashore campuses,
UCSB is located on the Pacific Coast 100
miles northwest of Los Angeles and 330
miles south of San Francisco. The student
enrollment is over 14,000. The metropoli-
tan Santa Barbara area has over 150,000
residents and is famous for its mild, even
climate.


For additional information and applications,
write to:

Professor Owen T. Hanna, Chairman
Department of Chemical & Nuclear
Engineering
University of California,
Santa Barbara, CA 93106

CHEMICAL ENGINEERING EDUCATION



































PROGRAM OF STUDY Distinctive features of study in
chemical engineering at the California Institute of Tech-
nology are the creative research atmosphere and the strong
emphasis on basic chemical, physical, and mathematical
disciplines in the program of study. In this way a student
can properly prepare for a productive career of research,
development, or teaching in a rapidly changing and ex-
panding technological society.
A course of study is selected in consultation with one
or more of the faculty listed below. Required courses are
minimal. The Master of Science degree is normally com-
pleted in one academic year and a thesis is not required.
A special M.S. option, involving either research or an inte-
grated design project, is a feature to the overall program
of graduate study. The Ph.D. degree requires a minimum
of three years subsequent to the B.S. degree, consisting of
thesis research and further advanced study.


FINANCIAL ASSISTANCE Graduate students are sup.
ported by fellowship, research assistantship, or teaching
assistantship appointments during both the academic
year and the summer months. A student may carry a
full load of graduate study and research in addition to
any assigned assistantship duties. The Institute gives
consideration for admission and financial assistance to
all qualified applicants regardless of race, religion, or sex.
APPLICATIONS Further information and an application
form may be obtained by writing
Professor L. G. Leal
Chemical Engineering
California Institute of Technology
Pasadena, California 91125
It is advisable to submit applications before February
15, 1982.


FACULTY IN CHEMICAL ENGINEERING


JAMES E. BAILEY, Professor
Ph.D. (1969), Rice University
Biochemical engineering; chemical reaction
engineering.
WILLIAM H. CORCORAN, Institute Professor
Ph.D. (1948), California Institute of Technology
Kinetics and catalysis; biomedical engineering;
air and water quality.

GEORGE R. GAVALAS, Professor
Ph.D. (1964), University of Minnesota
Applied kinetics and catalysis; process control
andoptimization; coal gasification.
ERIC HERBOLZHEIMER, Assistant Professor
Ph.D. (1979), Stanford University
Fluid mechanics and transport phenomena
L. GARY LEAL, Professor
Ph.D. (1969), Stanford University
Theoretical and experimental fluid mechanics;
heat and mass transfer; suspension rheology;
mechanics of non-Newtonian fluids.


JOHN H. SEINFELD, Louis E. Nohl Professor,
Executive Officer
Ph.D. (1967), Princeton University
Air pollution; control and estimation theory.
FRED H. SHAIR, Professor
Ph.D. (1963), University of California, Berkeley
Plasma chemistry and physics; tracer studies
of various environmental problems.
GREGORY N. STEPHANOPOULOS, Assistant Pro-
fessor Ph.D. (1978), University of Minnesota
Biochemical engineering; chemical reaction
engineering.
NICHOLAS W. TSCHOEGL, Professor
Ph.D. (1958), University of New South Wales
Mechanical properties of polymeric materials;
theory of viscoelastic behavior; structure-
property relations in polymers.

W. HENRY WEINBERG, Chevron Professor
Ph.D. (1970), University of California, Berkeley
Surface chemistry and catalysis.








Have you considered Graduate
Studies in Biomedical Engineering/
Chemical Engineering
at
CARNEGIE-MELLON UNIVERSITY?


Break Through
Write: Chairman CarnegieMellon University Biomedical Engineering Program
Science1325 Pgh.Pa15213


CHEMICAL ENGINEERING EDUCATION





THE FINEST CHOICE


write
Graduate Chemical Engineering
Carnegie-MellonUniversity
Pittsburgh,Pennsylvania 15213


I ~I-~�L�~-1YPWr YYWLI�I.-~._i






























IS THERE LIFE
AFTER GRADUATE STUDY?
Want to find out? Heaven can't wait!
Write to:
Graduate Coordinator
Chemical Engineering Department
Case Western Reserve University
Cleveland, Ohio 44106
242 CHEMICAL ENGINEERING EDUCATION





The

UNIVERSITY

OF

CINCINNATI


"'�


iv;'


Research iacuity


Air Pollution Control
Biochemical Engineering
Biomedical Engineering
Electrochemical Engineering
Energy Utilization
Environmental Engineering
Heat Transfer
Kinetics & Catalysis
Polymers & Rheology
Process Dynamics & Control


James N. Anno
John M. Christenson
Stanley L. Cosgrove
Robert M. Delcamp
Leroy E. Eckart
Kenneth M. Emmerich
Joel R. Fried
Rakish Govind


David B. Greenberg
Daniel Hershey
Yuen-Koh Kao
Soon-Jai Khang
Robert Lemlich
William Licht
Alvin Shapiro
Joel Weisman


For Admission Information
Chairman
Graduate Studies Committee
Chemical and Nuclear Engineering (171)
University of Cincinnati
Cincinnati, Ohio 45221


GRADUATE STUDY in

Chemical Engineering

M.S. and Ph.D. Degrees







2 _____


Clarkson

1: * M.S. and Ph.D. Programs
0 0 * Friendly Atmosphere
* Vigorous Research Programs Supported by Government
and Industry
* Faculty with International Reputation
* * Skiing, Canoeing, Mountain Climbing and Other
Recreation in the Adirondacks
* Variety of Cultural Activities with Two Liberal Arts
Colleges Nearby
Faculty
S. V. Babu D. H. Rasmussen
Der-Tau Chin Herman L. Shulman
Robert Cole R. Shankar Subramanian
Sandra Harris Peter C. Sukanek
Angelo Lucia Ross Taylor
Richard J. McCluskey Thomas J. Ward
John B. McLaughlin Ralph H. Weiland
Richard J. Nunge William R. Wilcox
Nsima Tom Obot Gordon R. Youngquist
Research Projects are available in:
* Energy
* Materials Processing in Space
* Turbulent Flows
* Heat Transfer
* Electrochemical Engineering and Corrosion
* Polymer Processing
* Particle Separations
* Phase Transformations and Equilibria
* Reaction Engineering
* Optimization and Control
: Crystallization
SAnd More...
Financial aid in the form of fellowships, research
-. assistantships and teaching assistantships is
". 7 available. For more details, please write to:
Dean of the Graduate School
Clarkson College of Technology
Potsdam, New York 13676











COLORADO /


SCHOOL /


OF
1874

MINES LRo


THE FACULTY AND THEIR RESEARCH
P. F. Dickson, Professor and Head; Ph.D., University of
Minnesota. Oil-shale, shale oil processing, petro-
- chemical production from shale oil, heat transfer,
heat exchanger design.

J. H. Gary, Professor; Ph.D., University of Florida. Up-
grading of shale oil and coal liquids, petroleum re-
finery processing operations, heavy oil processing.
S A. J. Kidnay, Professor; D.Sc., Colorado School of Mines.
Thermodynamic properties of coal-derived liquids,
vapor-liquid equilibria in natural gas systems, cryo-
genic engineering.
R . M. Baldwin, Associate Professor, Ph.D., Colorado
School of Mines. Coal liquefaction by direct hydro-
genation, mechanisms of coal liquefaction, kinetics
of coal hydrogenation, relation of coal geochemistry
S to liquefaction kinetics, upgrading of coal-derived
asphaltenes.
M. S. Graboski, Associate Professor; Ph.D., Pennsylvania
State University. Coal and biomass gasification pro-
cesses, gasification kinetics, thermal conductivity of
coal liquids, kinetics of SNG upgrading.
M. C. Jones, Associate Professor; Ph.D., University of
California at Berkeley. Heat transfer and fluid me-
chanics in oil shale retorting, radiative heat transfer
in porous media, free convection in porous media.

E. D. Sloan, Jr., Associate Professor; Ph.D., Clemson Uni-
versity. Phase equilibrium thermodynamics measure-
ments of natural gas fluids and natural gas hydrates,
thermal conductivity measurements for coal derived
A -fluids, adsorption equilibria measurements, stage-
_wise processes, education methods research.
.,' YV. F. Yesavage, Associate Professor; Ph.D., University of
- . Michigan. Kinetic studies of shale oil, phase be-
S _ . - . , havior and enthalpy of synthetic fuels.

P I . A. L. Bunge, Assistant Professor; Ph.D., University of
SCalifornia at Berkeley. Enhanced oil recovery.

J.- For Applications and Further Information
On M.S., and Ph.D. Programs, Write
Chemical and Petroleum Refining Engineering
A _ Colorado School of Mines
S'", Golden, CO 80401


FALL 1981






Chemical Engineering at


CORNELL

UNIVERSITY


A place to grow...


with active research in

biochemical engineering
applied mathematics/computer simulation
energy technology
environmental engineering
kinetics and catalysis
surface science
heat and mass transfer
polymer science
fluid dynamics
rheology and biorheology
microscopy
reactor design
thermodynamics

with a diverse intellectual climate-graduate students arrange
individual programs with a core of chemical engineering
courses supplemented by work in other outstanding Cornell
departments including

chemistry
biological sciences
physics
computer science
food science
materials science
mechanical engineering
business administration
and others

with excellent recreational and cultural opportunities in one
of the most scenic regions of the United States.

Graduate programs lead to the degrees of Doctor of
Philosophy, Master of Science, and Master of Engineering
(the M.Eng. is a professional, design-oriented program).
Financial aid, including attractive fellowships, is available.

The faculty members are:
Joseph F. Cocchetto, Claude Cohen, Robert K. Finn, Keith E.
Gubbins, Peter Harriott, Robert P. Merrill, William L. Olbricht,
Ferdinand Rodriguez, George F. Scheele, Michael L. Shuler,
Julian C. Smith, William B. Street, Raymond G. Thorpe,
Robert L. Von Berg, Herbert F. Wiegandt.

FOR FURTHER INFORMATION: Write to
Professor Keith E. Gubbins
Cornell University
Olin Hall of Chemical Engineering
Ithaca, New York 14853































The

University

of %elaware

awards three

grzdua te

degrees for

studies and
practice in

theartand

science of

chemical

engineering.


An M.Ch.E. degree based upon course work and a thesis problem.
An M.Ch.E. degree based upon course work and a period of in-
dustrial internship with an experienced senior engineer in the
Delaware Valley chemical process industries.
A Ph.D. degree for original work presented in a dissertation.
THE REGULAR FACULTY ARE: CURRENT AREAS OF RESEARCH INCLUDE:
Gianni Astarita (1/2 time) Thermodynamics and Separ-
M. A. Barteau ation Process
C. E. Birchenall Rheology, Polymer Science
K. B. Bischoff (Chairman) and Engineering
C. D. Denson Materials Science and
B. C. Gates Metallurgy
M. T. Klein Fluid Mechanics, Heat and
R. L. McCullough Mass Transfer
A. B. Metzner Economics and Management
J. H. Olson in the Chemical Process Industries
M. E. Paulaitis Chemical Reaction Engi-
R. L. Pigford neering, Kinetics and
T. W. F. Russell Simulation
S. I. Sander Catalytic Science and
G. C. A. Schuit (/2 time) Technology
J. M. Schultz Biomedical Engineering-
L. A. Spielman Pharmacokinetics and
A. B. Stiles (1/2 time) Toxicology
R. S. Weber
FOR MORE INFORMATION AND ADMISSIONS MATERIALS, WRITE:
Graduate Advisor
Department of Chemical Engineering
University of Delaware
Newark, Delaware 19711


























Only the

University

of Florida's

Departmer

of Chemicc

Engineerin

gives you both
outstanding
academic
challenge
and all the
advantages of
the Florida clime


Current Research Areas
Fluid Mechanics
Rheology
Catalysis
Reaction Engineering
Biomedical Engineering
Electrochemical Engineering
Interfacial Phenomena
Semiconductor Processing
Thermodynamics
Energy Systems
Process Control
Mass Transfer
and more....


The Faculty
T.J. Anderson
S.S. Block
R.W. Fahien
R.J. Gordon
G.B. Hoflund
L.E. Johns
D.W. Kirmse
H.H. Lee
F.P. May
J.P. O'Connell
D.O. Shah
M. Tyner
R.D. Walker
G.B. Westermann-Clark


Gainesville is a city of 90,000 (plus 40,000 students)
located in the center of the Florida Peninsula, about
120 miles north of Tampa, and 70 and 50 miles from
the Atlantic and Gulf, respectively. The average yearly
temperature is 70 degrees. Need we say more?
For more information on admission and
financial aid, write:
Graduate Coordinator
Chemical Engineering Department
University of Florida
Gainesville, FL 32611
(904)392-0881 / .


An equal opportunity/affirmative action employer


______I











Graduate Programs in Chemical Engineering

University of Houston



The Department of Chemical Engineering at the University of
Houston has developed five areas of special research strength:
* Chemical reaction engineering
* Applied fluid mechanics and transfer processes
* Energy engineering
* Environmental engineering
* Process simulation and computer-aided design

The department occupies more than 52,000 square feet and is
equipped with more than $2.0 million worth of experimental
apparatus.

Financial support is available to full-time graduate students
with stipends ranging from $7,200 to $10,000 for twelve
months.
The faculty:
N. R. Amundson
E. L. Claridge
J. R. Crump
A. E. Dukler
R. W. Flumerfelt
E. ). Henley
C. J. Huang
R. Jackson
o nD. Luss
A. C. Payatakes
R. Pollard
H. W. Prengle, Jr.
J. T. Richardson
For more information or application forms write: F. M. Tiller
Director, Graduate Admissions J. Villadsen
Department of Chemical Engineering
University of Houston F. L. Worley, Jr.
4800 Calhoun
Houston, Texas 77004
(Phone 713/749-4407)


CHEMICAL ENGINEERING EDUCATION


250