1

Introduction

Catalysis is the phenomenon in which a relatively small amount of a foreign

material, called a catalyst, increases the rate of a chemical reaction without
itself being consumed. Although widely utilized now in many industrial
processes, catalysis was not even recognized until the 19th century when
Berzelius introduced the term in 1836. Other early pioneers in this field
during this century include Davy, Faraday, Bertholet, Ostwald, and Sabatier
[1–3]. Tremendous advances in catalytic processing were made at the begin-
ning of the 20th century as hydrogenation of oils, fats, and waxes to food
stuffs, ammonia synthesis from N2 and H2 , ammonia oxidation to nitric
acid, and the synthesis of hydrocarbons and organics from H2 and CO were
developed. However, the modeling of quantitative kinetics of reactions
occurring on catalytic surfaces essentially did not begin until the contribu-
tions of Langmuir between 1915 and 1920, which provided a relationship
between adsorbed species and measurable experimental parameters [2,4].
This approach was subsequently broadened and utilized by Hinshelwood,
Taylor, Rideal, Eley, Hougen, Watson and others who were among the first
to determine and model the kinetics of reactions on heterogeneous catalysts.
This book reviews, analyzes and builds on these earlier models.
Catalysis is an interdisciplinary field, and a thorough study of catalytic
reactions requires knowledge from chemistry, physics, mathematics, chem-
ical engineering and materials science, for example. Few, if any, investigators
can claim to be an ‘‘expert’’ in all these fields, but such a requirement is not
necessary; however, one must have sufficient understanding of each disci-
pline to: a) properly design kinetic experiments, b) satisfactorily characterize
catalysts, c) acquire valid rate data and correctly express it, d) test for
artifacts in these kinetic data, e) propose reasonable reaction models,
f) derive proper rate expressions based on these models and, finally, g)
evaluate the physical and thermodynamic consistency of the fitting param-
eters contained in these rate equations. The background information re-
quired for all these capabilities is very diverse and it is infrequently
contained in detail in a single book. The goal here is to provide between
these covers sufficient information about the techniques required, the theory

1
2 1. Introduction

behind them, and their appropriate utilization, not only to allow a practi-
tioner in heterogeneous catalysis to properly conduct kinetic studies of
catalyzed reactions, but also to provide an overview of the kinetics of
catalyzed reactions for a graduate course, presumably in chemical engineer-
ing or chemistry.
The chapters in this book are based on notes used in a graduate course in
heterogeneous catalysis that the author taught at Penn State, with continu-
ous updating, for over 25 years [5]. They contain numerous examples and
illustrations of catalyst characterization, reaction modeling, and rate law
evaluation largely derived from the research undertaken in his laboratory
during this period of time. One advantage of such an approach is that the
chemisorption techniques described for the characterization of catalysts,
dispersed metal catalysts in particular, include some of the most recent
methods reported in the open literature. Another reason for the inclusion
of a relatively large number of examples for kinetic modeling of real systems,
both as illustrations and as homework problems, is the scarcity of such
problems in most textbooks on kinetics and/or reactor design. If nothing
else, this book will provide examples of consistent kinetic models and rate
expressions that have successfully fit experimental rate data acquired from a
variety of catalyzed reactions.
The approach taken in this book is largely a continuation of the ‘‘Boudart
school of kinetics’’. The academic geneology of this school is quite interest-
ing and worthy of mention. Michel Boudart’s advising professor at Prince-
ton University was Sir Hugh Taylor. Taylor, in turn, worked with Basset in
Liverpool, Arrhenius in Stockholm, and Bodenstein in Hannover to obtain
his Ph.D. Arrhenius worked with Ostwald, Kohlrausch, Boltzmann and
van’t Hoff after receiving his doctorate, while Bodenstein also conducted
postdoctoral research with Ostwald [2]. Clearly, a solid foundation in
thermodynamics, kinetics and catalysis was established by this research
lineage.
If I were to take the liberty to summarize Boudart’s philosophy about
kinetics and catalysis, I would do so as follows:
A) First, obtain reproducible experimental rate data.
B) These data must then be tested and checked to verify the absence of
artifacts, such as mass and heat transfer limitations.
C) A catalytic cycle, preferably comprised of a series of elementary steps, is
proposed.
D) Assumptions are made regarding dominant surface species and relative
rates of the elementary steps to allow the derivation of a rate expression
consistent with the data. This process also includes the choice of an ideal
or nonideal catalytic surface.
E) The kinetic and adsorption equilibrium constants contained in the rate
expression are evaluated using a set of guidelines to verify they are
physically reasonable and thermodynamically consistent.
 1. Introduction 3

F) Based on this reaction model, additional tests of its validity can be

proposed and conducted, if possible.
G) The catalyst is characterized to determine the active surface area and, if
possible, to count the number of active sites. Additional information
about the chemical state of the working catalyst is also very desirable, if
it can be obtained.
Having a rate expression that is consistent with data taken in the kinetic
control regime and which contains physically and thermodynamically con-
sistent parameters still does not guarantee that the reaction model upon
which it is based is the correct one. However, it does show that the model
could be the correct one, and it provides much more information than a
simple power rate law because the model gives insight into the state of the
working catalyst. This provides some knowledge about the catalytic pro-
cesses on the surface and allows reasonable extrapolation of the model to
conditions outside of the experimental region examined.
Use of the information in these chapters will allow a researcher conduct-
ing experiments with catalysts in either an industrial or an academic labora-
tory to assess their results and determine the presence or absence of heat and
mass transfer effects. Proper catalyst characterization provides the capabil-
ity to report kinetic results properly in the form of specific or normalized
activity, preferably in the form of a turnover frequency. The utilization and
justification of reaction models based on uniform or ideal surfaces is dis-
cussed in detail, and numerous examples are provided. However, kinetic rate
expressions based on the premise of nonuniform surfaces are also examined
in depth to provide an alternate route to obtain a rate law, should the
investigator wish to do so. In most studies of catalyzed reactions, the kinetics
of these reactions lie at the heart of the investigation, not only because
accurate comparisons of performance among different catalysts must be
obtained, but also because accurate rate expressions can provide insight
about the surface chemistry involved and they must be available for proper
reactor design.
It is worthwhile to mention here several topics that are NOT going to be
discussed in any detail. This book is oriented toward the typical investigator
in catalysis, who has access to readily available experimental tools and
techniques; thus, catalyst characterization based on ultra high vacuum
(UHV) techniques, Mössbauer spectroscopy, electron paramagnetic reso-
nance (EPR) spectroscopy, nuclear magnetic resonance (NMR) spectros-
copy and magnetic susceptibility is discussed little or not at all, and extended
x-ray absorption fine structure (EXAFS) is mentioned but not discussed in
detail. This is because only a small fraction of researchers have ready access
to these methods. Also, the microkinetic approach to rate expressions [6] is
not discussed, even though the resulting rate laws are admittedly preferred
when they can be accurately obtained. This choice was made not only
because this approach depends so heavily on rate constants obtained using
4 1. Introduction

UHV systems, which are seldom available for such measurements and are
time and cost intensive, but also because these more detailed microkinetic
rate laws typically simplify to more conventional rate expressions over a
chosen range of reaction conditions [6].
One final comment should be made to facilitate reading this book. Chem-
ical reactions are identified by numbers on the left margin whereas equations
are identified by numbers on the right margin. Also, these numbers in
illustrations and problems are distinguished by being italicized and do not
include the chapter number.

References
1. R. L. Burwell, Jr., Chemtech, 17 (1987) 586.
2. K. J. Laidler, ‘‘Chemical Kinetics’’, 3rd ed., Harper & Row, NY, 1987.
3. J. M. Thomas and W. J. Thomas, ‘‘Principles and Practice of Heterogeneous
Catalysis’’, VCH, Weinheim, 1997.
4. I. Langmuir, J. Am. Chem. Soc., 40 (1918) 1361.
5. M. A. Vannice, Chem. Eng. Education, Fall, 1979.
6. J. A. Dumesic, D. F. Rudd, L. M. Aparicio, J. E. Rekoske and A. A. Trevino,
‘‘The Microkinetics of Heterogeneous Catalysis’’, Am. Chem. Soc., Washington,
D.C., 1993.