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CATALYTIC KINETICS
CATALYTIC KINETICS
Chemistry and Engineering
Second Edition
DMITRY YU. MURZIN AND TAPIO SALMI
AMSTERDAM • BOSTON • HEIDELBERG • LONDON • NEW YORK • OXFORD

PARIS • SAN DIEGO • SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO
Elsevier
Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands
The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, UK
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© 2016, 2005 Elsevier B.V. All rights reserved.
No part of this publication may be reproduced or transmitted in any form or by any means, electronic
or mechanical, including photocopying, recording, or any information storage and retrieval system,
without permission in writing from the publisher. Details on how to seek permission, further
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as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our
website: www.elsevier.com/permissions.
This book and the individual contributions contained in it are protected under copyright by the
Publisher (other than as may be noted herein).
Notices
Knowledge and best practice in this field are constantly changing. As new research and experience
broaden our understanding, changes in research methods, professional practices, or medical treatment
may become necessary.
Practitioners and researchers must always rely on their own experience and knowledge in evaluating
and using any information, methods, compounds, or experiments described herein. In using such
information or methods they should be mindful of their own safety and the safety of others, including
parties for whom they have a professional responsibility.
To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume
any liability for any injury and/or damage to persons or property as a matter of products liability,
negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas
contained in the material herein.
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ISBN: 978-0-444-63753-6
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ABOUT THE AUTHORS
Tapio Salmi and Dmitry Yu. Murzin
DMITRY YU. MURZIN

Education: 1986: MSc (Chemical Engineering) with honors, Mendeleev University of
Chemical Technology, Moscow; 1989: PhD, Karpov Physico-Chemical Institute,
Moscow; 1999: Doctor of Chemical Sciences, Karpov Physico-Chemical Institute.
Career: 1986–1992: Karpov Physico-Chemical Institute; 1992–1994: postdoctoral
experience (Université Louis Pasteur, Strasbourg, France; Åbo Akademi University,
Turku, Finland); 1995–2000: with BASF; since 2000: Professor in Chemical Technol-
ogy, Åbo Akademi University, Turku, Finland.
Editorial board member of several journals in catalysis and chemical engineering field.
Vice-president of the European Federation of Catalysis Societies (2009–2013).
An author of textbooks (Engineering Catalysis, DeGruyter, 2013; and Chemical Reaction
Technology, DeGruyter, 2015) and author and co-author of over 650 journal articles
on kinetics and catalysis.
TAPIO SALMI
Education: 1980: MSc (Chemical Engineering), Åbo Akademi University, Turku,
Finland; 1986: Doctor of Technology, Åbo Akademi University.
Career: 1985 Researcher at Technical University of Denmark; 1990–1998: Associate
Professor; since 1998: Professor in Chemical Reaction Engineering, Åbo Akademi
University, Turku, Finland; Academy Professor, Academy of Finland.
A co-author of Chemical Reaction Engineering and Reactor Technology (CRC Press, 2011)
and author and co-author of over 500 journal articles on various aspects of chemical
reaction engineering. Member of the European Federation of Chemical Engineering
Working Party on Chemical Engineering.
ix
PREFACE
Diversity of catalysts, for example, catalysis by mineral acids, complexes of transition

metals, organic molecules, enzymes, and alumosilicates, resulted in fragmentation of
the discipline. Separate courses are given based on textbooks covering separately, despite
all similarities, homogeneous, heterogeneous, and enzymatic catalysis. More general
books on physical chemistry, while discussing some aspects of catalytic kinetics, cannot
go into details to the extent that is often needed.
Although in the chemical industry, the main focus is currently on heterogeneous
catalysis, other fields (homogeneous, enzymatic, photochemical, electrochemical
catalysis) should not be overlooked, as very often the industrial aim is to produce a certain
chemical in the most optimal way, but not with a particular type of catalyst. The industrial
importance of catalysis also dictates a necessity to have a book devoted to the fundamental
aspects of catalytic kinetics, as well as catalytic engineering and, more specifically,
transport phenomena.
Such an integrated approach to kinetics and transport phenomena in catalysis, while
still recognizing the fundamental differences among different types of catalysis, was
applied in the first edition of this book, published in 2005.
The authors have received a number of encouraging comments as well as critique about
what was missing and suggestions for how the book could be improved. We were also very
happy to learn that due to a positive response, Elsevier decided to proceed with the second
edition of this book on catalytic kinetics. The authors carefully discussed the material to be
included in the revised version. Material for chapters 10.1–10.2, 10.4, and 11.3–11.6 was
prepared by Tapio Salmi, while the remaining text was written by Dmitry Yu. Murzin,
who also oversaw the second edition and implementation of all changes.
In this edition, the content was expanded to cover in more depth several areas, such as
organocatalysis; enzymatic kinetics; nonlinear dynamics; solvent effects; nanokinetics
(structure sensitivity); kinetic isotope effects; and polynomial kinetics, to name a few.
In addition, a separate chapter on cascade catalysis has been written.
Each and every chapter in the second edition also contains examples and exercises,
which facilitates understanding and mastering of the underlying concepts.
In order to stay more focused on the core of catalytic kinetics, a section on gas-liquid
mass transfer, which was present in the first edition, was not included.
In addition to these changes, unfortunate misprints were corrected and general edit-
ing of the text, introducing new figures and examples, was performed.
xi
xii Preface
Similar to the previous edition, the authors limited themselves to the main mono-
graphs, review articles, and key references without extensive coverage of original
literature.
It is the pleasure of the authors to acknowledge many colleagues from academia and
industry who, through the years, shared their knowledge and expertise in fundamental
and applied aspects of catalytic kinetics. The late Professor M.I. Temkin deserves a special
mention as a role model of an exemplary person and scientist for the author of these words.
The authors hope that the second edition will be useful for students and researchers
working in the field of catalytic kinetics.
Dmitry Yu. Murzin

Turku/Åbo, November 2015
CHAPTER 1
Setting the Scene
1.1. HISTORY
All processes occur over a time ranging from femtosecond to billions of years. The same
holds for chemical and biochemical transformations. Kinetics (derived from the Greek
word κινητιχοζ meaning dissolution) is a science which investigates rates of processes.
Chemical kinetics is the study of reaction rates.
However complex a process is, it can be, in principle, divided into a number of
elementary processes which can be studied separately.
Chemical kinetics emerged as a branch of physical chemistry in the 1880s, with sem-
inal works of Harcourt and Esson demonstrating the dependence of reaction rates on the
concentrations of reactants. It was German scientist K. Wenzel who stated that the affin-
ity of solid materials towards a solvent is inversely proportional to dissolution time.
100 years after that Guldberg and Waage (Norway) formulated a law, which was later
coined the “law of mass action,” meaning that the reaction “forces” are proportional
to the product of the concentrations of the reactants.
When the rate of a certain process is measured, especially if it is of practical impor-
tance, a curious mind is always eager to know if it is possible to accelerate its velocity.
Moreover, one could even imagine a situation that for a system demonstrating complete
inertness, the introduction of a foreign substance could enhance the rate dramatically.
Conversion of starch to sugars in the presence of acids, combustion of hydrogen over
platinum, decomposition of hydrogen peroxide in alkaline and water solutions in the
presence of metals, etc., were critically summarized by Swedish scientist J.J. Berzelius
in 1836, who proposed the existence of a certain body, which “effecting the (chemical)
changes does not take part in the reaction and remains unaltered through the reaction.”
He called this unknown force catalytic force and defined catalysis as decomposition of
bodies by this force.
This new concept was immediately criticized by Liebig, as this notion was putting
catalysis somewhat outside other chemical disciplines. A catalyst was later defined by
Ostwald as a compound, which increases the rate of a chemical reaction, but which
Catalytic Kinetics © 2016 Elsevier B.V.

http://dx.doi.org/10.1016/B978-0-444-63753-6.00001-4 All rights reserved. 1
2 Catalytic Kinetics
Jöns Jakob Berzelius Wilhelm Ostwald and Svante Arrhenius
is not consumed by the reaction. This definition allows for the possibility that small
amounts of the catalyst are lost in the reaction or that the catalytic activity is slowly lost.
1.2. CATALYSIS
Already from these definitions, it is clear that there is a direct link between chemical
kinetics and catalysis; according to the very definition of catalysis, it is a kinetic process.
There are different views, however, on the interrelation between kinetics and catalysis.
While some authors state that catalysis is a part of kinetics, others treat kinetics as a part of
a broader phenomenon of catalysis.
Despite the fact that catalysis is a kinetic phenomenon, there are many issues in catal-
ysis which are not related to kinetics. Mechanisms of catalytic reactions, elementary
reactions, surface reactivity, adsorption of reactants on the solid surfaces, synthesis
and structure of solid materials, enzymes or organometallic complexes, not to
mention engineering aspects of catalysis, are obviously outside the scope of chemical
kinetics.
Some discrepancy exists whether chemical kinetics include also the mechanisms of
reactions. In fact, if reaction mechanisms are included in the definition of catalytic kinet-
ics, it will be an unnecessary generalization, as catalysis should cover mechanisms.
Catalysis is of crucial importance for the chemical industry. The number of catalysts
applied in industry is very large, and catalysts come in many different forms, from het-
erogeneous catalysts in the form of porous solids to homogeneous catalysts dissolved in
the liquid reaction mixture to biological catalysts in the form of enzymes. Catalysis is a
multidisciplinary field requiring efforts of specialists in different fields of chemistry,
Setting the Scene 3
physics and biology to work together to achieve the goals set by mankind. Knowledge of
inorganic, organometallic, organic chemistry, materials and surface science, solid state
physics, spectroscopy, reaction engineering and enzymology is required for the advance-
ments of the discipline of catalysis.
Despite the fundamental differences between elementary steps in catalytic process on
surfaces, there are striking similarities also in terms of chemical kinetics with enzymes or
homogeneous organometallic complexes. Although superficially it is difficult to find
something in common between the reaction of nitrogen and hydrogen forming ammo-
nia on a surface of iron, D-fructose 6-phosphate reaction with ATP involving an enzyme
phosphofructokinase or ozone decomposition in the atmosphere in the presence of NOx,
all these transformations require that the catalyst forms bonds with the reacting molecules.
Such a complex then reacts to products, leaving the catalyst unaltered and ready for taking
part in a next catalytic cycle.
Fig. 1.1 is an example of a catalytic reaction between two molecules A and B with the
involvement of a catalyst.
In order to understand how a catalyst can accelerate a reaction, a potential energy
diagram should be considered.
Fig. 1.2 represents a concept for a non-catalytic reaction. Arrhenius suggested that
reactions should overcome a certain barrier before a reaction can proceed.
The change in the Gibbs free energy between the reactants and the products ΔG does
not change in case of a catalytic reaction; however, the catalyst provides an alternative
path for the reaction (Fig. 1.3).
START A
t
uc
od
Pr
Catalyst Reagent A
on to catalyst
Product
leaves
Catalyst
Catalyst
A
Product
Reaction B
occurs on catalyst Catalyst Reagent B
on to catalyst
B A
Fig. 1.1 Catalytic cycle.

X‡
ΔG‡
G
A+B
Δ Greaction
P+Q
Reaction coordinate
Fig. 1.2 Potential energy diagram.
X‡
Uncatalyzed ‡
ΔΔGcat
(the reduction
in ΔG‡ by the
catalyst)
G
Catalyzed
A+B
P+Q
A + B GP + Q
Reaction coordinate
Fig. 1.3 Potential energy diagram for catalytic reactions.
In general, reaction rates increase with increasing temperature. Kooij and van’t Hoff
(1893) proposed an equation for the temperature dependence of reaction rates:
Ea
k ¼ AT m e =RT (1.1)
where A is pre-exponential factor and activation energy, Ea, is related to the potential
energy barrier. This equation, which could be derived on the basis of transition sate the-
ory, in a slightly simplified form
Ea
k ¼ ko e =RT (1.2)
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Setting the Scene 5
Concentration
A
Time
Fig. 1.4 Concentration versus time dependences for a reversible reaction.
was applied by Arrhenius and is referred to as the Arrhenius law. It is immediately clear
from Eq. (1.2) that a decrease in activation energy will lead to an increase of the rate con-
stant, thus the reaction rate (a discussion on the relationship between the rate and rate
constant will be given below).
At the same time, the catalyst (heterogeneous, homogeneous, or enzymatic) affects
only the rate of the reaction; it changes neither the thermodynamics of the reaction
(Gibbs energy) nor the equilibrium composition. An important conclusion is that a cat-
alyst can change kinetics but not thermodynamics of a reaction. If a process is thermo-
dynamically unfavorable, there is no need to apply any modern and fancy methods (high
throughput screening and the like) to find such catalyst.
The dashed line in Fig. 1.4 demonstrates the equilibrium that cannot be overcome for
a given set of parameters.
Furthermore, the ratio of rate constants in the forward and reverse direction for cat-
alytic and non-catalytic reactions is the same:
k kcat ½P eq
¼ ¼ ¼K (1.3)
k0 kcat 0 ½Aeq
It also implies that if a catalyst is active in enhancing a rate of the forward reaction, it will
do the same with a reverse reaction.
Fig. 1.3 is somewhat simplified, as it does not take into account possible bonding of
the catalyst and reactant. In order for a catalyst to be effective, the energy barrier between
the catalyst-substrate and activated complex must be less than that between substrate and
activated complex in the un-catalyzed reaction. The binding of substrate to an enzyme
lowers the free energy of the catalyst substrate complex relative to the substrate (Fig. 1.5).
This is a general feature of catalysis and is relevant for heterogeneous, homogeneous, and
enzymatic catalysis. If the energy is lowered too much without a greater lowering of the
activation energy, then catalysis would not take place, meaning that bonding between a
Transition
state
Energy +
ES+
Substrates
ES
Products
Binding Catalysis EP
Reaction coordinate
Fig. 1.5 Potential energy diagram of an enzymatic reaction. (From https://upload.wikimedia.org/
wikipedia/commons/thumb/c/c0/Enzyme_catalysis_energy_levels_2.svg/1280px-Enzyme_catalysis_
energy_levels_2.svg.png?1450038342767).
catalyst and a reactant should not be too strong. Alternatively, if it is too weak, then the
catalytic cycle could not proceed.
Chemical kinetics as a discipline addresses how the reaction rates depend on reactant
concentration, temperature, nature of catalysts, pH, and solvent, to name a few reaction
parameters.
Chemical kinetics, together with other means of studying catalytic reactions like spec-
troscopy of catalysts and catalyst models, quantum-chemical calculations for reactants,
intermediates and products, calculation of the thermodynamics of reactants, intermedi-
ates and products from measured spectra and quantum-chemical calculations, form the
modern basis for understanding catalysis.
Kinetic investigations are one of the ways to reveal reaction mechanisms. The follow-
ing problems can be solved using the kinetic model:
• choosing the catalyst and comparing the selectivity and activity of catalysts and their
performance under optimum conditions for each catalyst;
• the determination of the optimum sizes and structure of catalyst grains and the neces-
sary amount of the catalyst to achieve the specified values of the selectivity of the pro-
cess and conversion of the starting products;
• the determination of the composition of all byproducts formed during the process;
• the determination of the stability of steady states and parametric sensitivity; that is, the
influence of deviations of all parameters on the steady-state regime and the behavior of
the reactor under unsteady state conditions;
• the study of the dynamics of the process and deciding if the process should be carried
out under unsteady-state conditions;
• the study of the influence of mass and heat transfer processes on the chemical reaction
rate and the determination of the kinetic region of the process;
• selection of the reactor type and structure of the contact unit providing the best
approximations to the optimum conditions.
Setting the Scene 7
Very often, the rates of chemical transformations are affected by the rates of other pro-
cesses, such as heat and mass transfer. The process should be treated as a part of kinetics.
The gas/liquid mass transfer in multiphase heterogeneous and homogeneous catalytic
reactions could be treated in a similar way. The mathematical framework for modeling
diffusion inside solid catalyst particles of supported metal catalysts or immobilized
enzymes does not differ that much, but proper care should be taken of the reaction
kinetics.
The immense importance of catalysis in chemical industry is manifested by the fact
that roughly 85–90% of all chemical products have seen a catalyst during the course
of production.
Fig. 1.6 demonstrates applications of catalysis in industry. In the last few years, there is
an increase of catalytic applications also for non-chemical industries, including treatment
of exhaust gases from cars and other mobile sources, as well as power plants (Fig. 1.7).
Worldwide merchant catalyst markets
Chemical Chemical
1997 2003
2.0 2.2 Polymer

Polymer
1.7 2.3
2.1 2.3
Refinery Refinery
2.1*
1.6*
Environmental Environmental
Billion US$ 7.4 9.0
* Toll manufacturing fees only

The catalyst group: The intelligence report: global shifts in the catalyst industry
Fig. 1.6 Worldwide catalyst market.
(A) (B)
Fig. 1.7 Catalytic treatment of NOx in (A) mobile and (B) stationary sources.
A comparison between homogeneous and heterogeneous catalysts from the view-

point of a homogeneous catalysis expert is presented below:
Homogeneous Heterogeneous
Activity High Variable
Selectivity High Variable
Conditions of reaction Mild Harsh
Lifetime of catalyst Variable Long
Sensitivity to deactivation Low High
Problems due to diffusion None Difficult to solve
Recycling of catalyst Usually difficult Can easily be done
Steric and electronic properties Easily changed No variation possible
Mechanism Realistic models exist Not obvious
The topics addressed above will be discussed in more detail in the subsequent chapters.
A great variety of homogeneous catalysts are known, including metal complexes and
ions, Brønsted and Lewis acids, and enzymes. Homogeneous transition metals are used in
several industrial processes, a few of them are given below:
World capacity
Process (million t/a) Catalyst Temperature (K) Pressure (bar)
Acetaldehyde 2.5 Pd/Cu 375–405 3–8
Acetic acid 4.0 Rh 425–475 30–60
Oxo-alcohols 7 Co or Rh 335–470 200/30
Dimethyl terephthalate 3.3 Co 415–445 4–8
Terephthalic acid 9.4 Co 450–505 15–30
Metal complexes can have a very sophisticated structure with a variety of ligands. An
example of such ligands for Rh catalyzed hydroformylation is given below (Fig. 1.8)
along with some images of heterogeneous catalysts (Fig. 1.9).
Enzymes represent a special type of homogeneous catalyst. They are large proteins
(Fig. 1.10) capable of increasing the reaction rates by a factor of 106 at mild reaction con-
ditions and displaying very high specificity and capability of regulation.
Specificity (Fig. 1.11) is controlled by the enzyme structure; more precisely, a unique
fit of substrate with the enzyme that controls the selectivity for the substrate and the prod-
uct yield.
Superficially, there is not that much in common between a large protein and a Pt/
Al2O3 heterogeneous catalyst. At the same time, the chemical reactions which occur with
both types of catalysts involve certain active sites; for example, regions where catalysis
occurs. Whatever the specific reaction, it can be schematically represented by
Fig. 1.8 A ligand for Rh catalyzed hydroformylation.
Fig. 1.9 Images of heterogeneous catalysts.
Fig. 1.10 A schematic view on an enzyme structure. (From https://upload.wikimedia.org/wikipedia/

commons/b/b4/Protein_ACE2_PDB_1r42.png).
Active center
of the enzyme
(His - 57)
(Asp - 102)
O (Ser - 195)
– H N N H O
O
O
R1 N C
H R2
Peptide bond acting

as the substrate
©CSLS/The University of Tokyo
Fig. 1.11 Specificity of enzyme catalysis. (From http://csls-text3.c.u-tokyo.ac.jp/large_fig/fig04_05.html.

Copyright © 2011 Division of Life Sciences, Komaba Organization for Educational Excellence, College of
Arts and Sciences, The University of Tokyo).
Fig. 1.5. This in turn means that the kinetics of either heterogeneous or homogeneous
catalytic reactions can be very similar, and in fact it is.
1.3. FORMAL KINETICS

Chemical kinetics as a discipline concerns the rates (the velocities) of chemical reactions
and deals with experimental measurements of the velocities in batch, semibatch or con-
tinuous reactors.
Interpretation of the experimental data is currently done using the laws of physical
chemistry.
One of the fathers of chemical kinetics, Louis Jacques Thénard, discovered hydrogen
peroxide and measured its decomposition rates. He demonstrated for the first time that
rates of chemical reactions varied with the concentrations of the reactants. In later study,
Ludwig Ferdinand Wilhelmy investigated the inversion of cane sugar in the presence of
acids and developed a rate equation, which was the first attempt to interpret the temper-
ature dependence of the rate constant. Unfortunately, this work remained in oblivion
until 1884. In 1865, the rate laws combined with mass balances for a batch reactor were
proposed by Augustus George Vernon Harcourt and William Esson, giving a mathemat-
ical expression for concentration versus t for first order, second order and consecutive
reactions, representing a major breakthrough for modern chemical kinetics.
Following the footsteps of the great scientists of the 19th century, let us try to consider
reaction rates for a chemical reaction described by the following equation:
aA + bB ¼ cC + dD (1.4)
Setting the Scene 11
where A and B are reactants, C and D products, and a, b, c, and d are stoichiometric coef-
ficients. An equation for a chemical reaction is written in such a way that all the molecules
participating in the reaction are balanced.
Very often in chemical reaction engineering, the stoichiometric coefficient νi is
defined as the amount of product produced after one run of the reaction. It implies that
the stoichiometric coefficient is positive for a product and negative for a reactant.
Thus, for the reaction:
A + B)C (1.5)
The following stoichiometric coefficients hold:
vA ¼ 1, vB ¼ 1, vC ¼ + 1 (1.6)
An extensive quantity describing the progress of a chemical reaction equal to the number
of chemical transformations (the total number of reaction runs) divided by Avogadro’s
number (it is essentially the amount of chemical transformations) is called the extent of
reaction. The change in the extent of reaction is given by dξ ¼ dni/νi, where νi is the
stoichiometric number of any reaction entity i (reactant or product) and ni is the correspond-
ing amount in moles.
Thus, dξ/dt is an extensive property, which is measured in moles and cannot be con-
sidered a reaction rate, as it is proportional to the size of the reactor.
In general, for a homogeneous reaction for which both the reaction rate changes with
time and is not uniform over a volume of a reactor, the reaction rate is:
@2ξ
r¼ (1.7)
@t@V
where V stands for the reactor volume. If the reactor volume is constant, then the reac-
tion rate is simply:
1 dCi
ri ¼ (1.8)
νi dt
where i is the reactant or product with corresponding stoichiometric coefficient νi, and Ci
is the concentration of component i. For a reaction:
A + B)C (1.9)
the rate of consumption of reactant A is then:
1 dnA dCA d ½A
rA ¼ ¼ ¼ (1.10)
νA Vdt dt dt
where nA is the number of moles of A in the reactor and [A] is the concentration of A.
Similarly, for the reaction:
2NOCl ðgÞ ) 2 NOðgÞ + 1 Cl2 ðgÞ (1.11)
2 mol of NOCl disappear for every 1 mol Cl2 formed; therefore, the rate is defined as:
1 d ½NOCl 1 d ½NO d½Cl2
rate ¼ ¼ + ¼ + (1.12)
2 dt 2 dt dt
For a heterogeneous reaction occurring on the surface S of a catalyst, the following
expression holds:
@2ξ
r¼ (1.13)
@t@S
which, if the rate is uniform across the surface, can be further simplified to:
1 @ξ
r¼ (1.14)
S @t
Rate laws express how the rate depends on concentration. If a reaction follows Eq. (1.4),
the law of mass action could be applied leading to a following equation:
r ¼ r + r ¼ k + ½Aa ½Bb k ½C c ½Dd (1.15)
where k+ and k are reaction rate constants and stoichiometric coefficients appear as the
powers (reaction orders towards particular components).
In reality, the chemical equation (1.4) does not tell us how reactants become products;
it is a summary of the overall process. In fact, it is molecularity; for example, the number
of species that must collide to produce the reaction which determines the form of a rate
equation. Reactions whose rate laws can be written from their molecularity are called
elementary. The kinetics of the elementary step depend only on the number of reactant
molecules in that step.
For the reaction:
2NO2 ðgÞ + Cl2 ðgÞ ) 2 NO2 Cl ðgÞ (1.16)
the rate expression based on the formal kinetics is:
r ¼ k ½NO2 2 ½Cl2 (1.17)
with the overall order defined as the sum of orders to each reactant being equal to 3.
However, the reaction mechanism is more complicated and consists of several elemen-
tary steps:
ðaÞ NO2 ðgÞ + Cl2 ðgÞ ) NO2 ClðgÞ + ClðgÞ
(1.18)
ðbÞ NO2 ðgÞ + ClðgÞ ) NO2 ClðgÞ
If the rate of the overall process is determined by the first step a, then the rate is defined as:
r ¼ k ½NO2 ½Cl2 (1.19)
and the overall order is just two.
Fig. 1.12 Representation of reaction kinetics of different orders.
For elementary reactions, the reaction orders have orders that are integers, which
are usually equal to one or two (Fig. 1.12), and occasionally three for trimolecular
reactions.
In practice, reaction orders can be fractional, indicating a complex reaction mecha-
nism. The majority of this book is devoted to catalytic reaction mechanisms, which are
typical examples of complex reactions.
Reaction orders for a reaction A ) P described by a following equation for
the rate:
dcA
¼ rA ¼ kcAn (1.20)
dt
are determined using logarithmic plots:

dcA
ln ¼ ln k + n lncA (1.21)
dt
with the reaction order corresponding to the slope (Fig. 1.13).

ln r
slope = n
0
0 ln c
Fig. 1.13 Determination of reaction orders.
1.4. ACQUISITION OF KINETIC DATA

Kinetic data for a chemical reaction are gathered in different type of reactors, and we will
briefly mention some requirements for chemical reactors from the viewpoint of kinetic
analysis. A high precision of the data is needed as large deviations in the values of the
experimentally measured rates will be a serious obstacle for quantitative considerations.
Reproducibility of rate measurements over a broad range of parameters is also of impor-
tance. Another necessary feature is the possibility to reach a goal of obtaining the max-
imum amount of kinetic information in minimum time. Analysis of products as well as
reactor layout should preferably be as easy as possible.
Essential features for catalytic reactions are the readiness in reduction/activation of
heterogeneous catalysts and a possibility to utilize them in the needed geometrical form.
Despite the strict definition of catalysis, which states that the catalyst does not change
during the catalytic reactions, some activity deterioration takes place; therefore, measure-
ments of catalytic kinetics should always monitor the catalyst activity.
Different types of reactors are applied in practice (Fig. 1.14). Stirred tank reactors
(STR), very often applied for homogeneous, enzymatic and multiphase heterogeneous
catalytic reactions, can be operated batch-wise (batch reactor, BR), semi-batch-wise
(semi-batch reactor, SBR) or continuously (continuous stirred tank reactor, CSTR).
Alternatively, tubular reactors with plug flow (piston flow) (PFR) are used and oper-
ate in continuous mode (Fig. 1.15).
Fig. 1.14 Different types of stirred tank reactors.
Fig. 1.15 Tubular reactors.

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Fig. 1.16 Approach to kinetic analysis in batch reactors.
1.4.1 Batch Reactors

The batch mode of operation (Fig. 1.16) brings several advantages, as it allows us to mon-
itor the progress of the reaction over time and thus acquires the whole kinetic curve in
one experiment.
The high precision and wide range of parameters afforded by this operation mode
made batch reactors very popular for kinetic studies, especially in the field of fine and
pharmaceutical chemicals. Another advantage is the possibility to utilize heterogeneous
catalysts of different geometrical shapes.
Such reactors can be made either of glass (Fig. 1.17A) or stainless steel to sustain high
pressures (Fig. 1.17B) and can be applied in a parallel mode (Fig. 1.17C).
At the same time, activity control presents a challenge for heterogeneous catalytic
reactions and will be discussed further in Chapter 9. Moreover, catalyst pretreatment
(reduction) and regeneration are not straightforward. Quantitative treatment is not easy
and will be briefly discussed below.
Fig. 1.17 Batch reactors: (A) glass, (B) high pressure, and (C) in parallel mode. (From http://
www.parrinst.com/wp-content/uploads/2011/03/MRS-5000_burettes.jpg. © Parr Instrument Company).
V
Flow
Flow
nA ṅA
ṅ0A
Fig. 1.18 A volume element.
For an infinitesimal volume element ΔV in Fig. 1.18, the mass balance could be writ-
ten in a form:
IN + GENERATION ¼ OUT + ACCUMULATION
leading to a following equation in terms of moles:
dnA
n_0A + ηA rA ΔV ¼ n_A + (1.22)
dt
where n_0A and n_A are the mole fluxes, ηA is the catalyst effectiveness factor (Chapter 10)
taking into account mass transfer.
For a batch reactor it holds that IN ¼ 0, OUT ¼ 0; therefore:
dnA
ηA rA V ¼ (1.23)
dt
If the volume is constant, one gets:
dnA dðcA V Þ dcA
¼ ¼V (1.24)
dt dt dt
From Eqs. (1.23) and (1.24):
dcA
¼ ηA rA (1.25)
dt
making use of the relationship between concentration and conversion α:
CA ¼ CAo ð1 αÞ (1.26)
Assuming that the catalyst effectiveness factor ηA is equal to 1 and taking into account
boundary conditions (t ¼ 0, α ¼ 0), we arrive at:
ðα
dα
t ¼ CAo (1.27)
rA
0
In fact, treatment of heterogeneous, homogeneous and enzymatic reactions is basically

the same with the only difference in the expressions of reaction rates, which reflect dif-
ferent reaction mechanisms. Some specific cases will be discussed in Chapters 5–7. Here
we present few examples:
Inserting the expression of reaction rate in Eq. (1.25) for a reaction A ) P, which
occurs over a catalyst:
dCA
¼ ηkCAn (1.28)
dt
and assuming that n ¼ 1 and ηA ¼ 1, we arrive at:
dCA
¼ kCA0 ð1 αÞ (1.29)
dt
which after integration gives an expression for reaction time:
ðα
1 dα 1
t¼ ¼ ln ð1 αÞ (1.30)
k 1α k
0
For the first order, reaction k has units of s1 (the rates are given in mol l1 s1).
For a second order, reaction with ηA ¼ 1 instead of Eq. (1.30) one arrives at:

1 1 1
t¼ (1.31)
k CA0 CA
with k in l/mol s, and for a zero order reaction, units of k are mol/l s and:
1 0
t¼ CA CA (1.32)
k
Eqs. (1.30)–(1.32) can be applied for batch reactors independent of the type of catalysis
that is operative, if reactions could be described by zero, first or second order. More com-
plicated cases for Langmuir kinetics or Michaelis-Menten kinetics will be considered
further.
1.4.2 CSTR
Examples of continuous stirred tank reactors are presented in Fig. 1.14 (right). Such a
system can be applied for both homogeneous and heterogeneous reactions. Fig. 1.19
illustrates the differences between batch and CSTR reactors.
For a perfectly mixed CSTR at steady state, it holds that there is no accumulation:
dnA
¼0 (1.33)
dt
therefore:
n_0A n_A + ηA rA V ¼ 0 (1.34)
Batch stirred Continuous stirred

tank reactor tank reactor
Substrate
Product
Immobilized Immobilized
catalyst
(A) (B) catalyst
Fig. 1.19 Stirred tank reactors in (A) batch and (B) continuous mode.
Substituting concentration and volumetric flows for molar flows:

c0A V_ 0 cA V_ + ηA rA V ¼ 0 (1.35)
and assuming that volumetric flows in and out are equal (eg, density is constant):
V_ 0 ¼ V_ (1.36)
and introducing residence time as the ratio of reactor volume to volumetric flow rate:
V =V_ 0 ¼ τ (1.37)
we arrive at:
c0A cA + ηA rA τ ¼ 0 (1.38)
which can be further transformed to:
cA c0A
τ¼ (1.39)
ηA rA
In the case of a first order reaction, the expression for the residence time becomes:
cA c0A
τ¼ (1.40)
ηA kCA
1.4.3 Plug Flow Reactors

An example of a tubular reactor is presented in Fig. 1.20.
For heterogeneous catalysis, the catalyst is packed in such reactors, which are easy to
design and control, as the gases or liquids pass through the reactor and are analyzed. Such
Fig. 1.20 A tubular reactor.
reactors are efficient for catalyst screening, especially when they are arranged in a parallel
mode (Fig. 1.21).
The apparent drawback is that one experiment leads to only one data point. On the
other hand, catalyst deactivation with time on stream could be easily seen (Fig. 1.22).
Quantitative treatment of plug flow reactors is somewhat cumbersome; therefore,
several assumptions are usually made. The fluid composition is considered to be uniform
along the reactor cross section (ie, there is no radial dispersion). This is valid only when:
dcat 1
< (1.41)
dreact 30
Fig. 1.21 Multitubular reactor.

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that which has been before noticed as rather foolishly displayed on
the pages of certain writers of the preceding centuries. Thus,
Sigebert of Gemblours, and Marbœuf of Angers, are both spoken of
as Greek and Hebrew scholars. Sigebert is said by his biographer to
have been learned in the Hebrew Scriptures, which he used in his
controversies with the Jews. He was also a good Latin classic, and
much addicted to the composition of verses in imitation of his
favourite author Horace. He gave lectures on poetry and logic in
Paris, but his vanity was not proof against temptation, and led him
to take part with Henry IV. against the Holy See. He is the author of
a chronicle and other historical works, which he made the vehicle for
conveying grave calumnies against the Roman pontiffs. Dante to
whom his character as a Ghibelline partisan was itself a
recommendation, has placed him in Paradise and notices him as
lecturing on logic in the streets of Paris, to students seated, after the
custom of the time, on bundles of straw.[156]
It is difficult to determine how much the scholars of this period
were really in advance of their predecessors. Hallam, who is
generally so sparing of his praise when speaking of any period
earlier than that of the Cinque Cento, admits that at the close of the
eleventh century a good, and even elegant school of Latin writers
was springing up; and notices the Latin vocabulary of Papias as
evincing an amount of profane learning far superior to anything that
had hitherto been known. Du Cange, however, shows that Papias
drew his materials from a dictionary which had been compiled in the
Dark Ages, namely, that published in the tenth century, by Solomon,
abbot of St. Gall’s. Still, it may be concluded that classical studies
were more universally followed than they had hitherto been, and at
the same time extraordinary activity was displayed in the
multiplication of books and the collection of libraries. Useful results
sometimes flow from human infirmities, and there is said to have
mingled with the honest love of learning which encouraged this
activity, a certain spirit of rivalry and emulation among the different
monasteries and religious orders. The Black Monks did not like to be
cut out by the new Cistercians; and Bec, as a matter of course, was
not going to yield to Cluny. Mabillon says that it was the peculiar
pride of the Benedictine abbots of this time, to collect large libraries,
and to have their manuscripts handsomely written and adorned.
Never, therefore, was there a busier time in the scriptorium; a finer
character of writing, and a more convenient system of abbreviation
was introduced, and many abbots are mentioned as remarkable for
their skill as miniaturists. It is said, however, I know not with what
truth, that the copyists, if they got through a greater amount of
work, were often less accurate than their brethren of the eighth and
ninth centuries, and that in this, as in other things, the proverb held
good of “more haste and worse speed.” Hallam, whilst complaining
of the multiplication of blunders, does full justice to the prodigious
industry exhibited by the monastic copyists of this particular period.
As an illustration of the subject, we may quote the account which
Othlonus, the scholasticus of St. Emmeran’s, gives of his labours. He
seems to have been a Bavarian by birth, and his first school was that
of Tegernsee, in Bavaria, a monastery which had been founded in
994, and was famous for its teachers in utrâque linguâ, and even for
its Hebrew scholars. Here, in the twelfth century, lived the good
monk Metellus, whose eclogues, written in imitation of those of
Virgil, describe the monastic pastures and cattle, and the labours of
the monks in the fields. The library of Tegernsee was rich in classic
works, and possessed a fair illuminated copy of Pliny’s “Natural
History,” adorned with pictures of the different animals, from the
cunning hand of brother Ellinger. Medicine was likewise studied here,
to facilitate which, the monks had a good botanical garden. In such
a school Othlonus had every opportunity of cultivating his natural
taste for study, which grew by degrees to be a perfect passion. As a
child he had intended to embrace the monastic state, but the
persuasions of his father, and his own desire to give himself up
exclusively to learned pursuits, induced him to abandon this design,
and after leaving school he devoted himself for several years to
classical studies, with an ardour which his biographer finds no words
strong enough to express.
His only earthly desire at this time, as he himself tells us in one of
his later spiritual treatises, was to have time to study, and
abundance of books. It would seem, however, that this excessive
devotion to human learning had its usual results in the decay of
devotion. It is thus he describes himself at this period of his life, in
his versified treatise De doctrina Spirituali. “Desiring to search into
certain subtle matters, in the knowledge of which I saw that many
delighted, to the end that I might be held in greater esteem by the
world, I made all my profit to consist in keeping company with the
Gentiles. In those days what were not to me Socrates, Plato and
Aristotle, and Tully the rhetorician?... that threefold work of Maro,
and Lucan, whom then I loved best of all, and on whom I was so
intent, that I hardly did anything else but read him.... Yet what profit
did they give me, when I could not even sign my forehead with the
cross?”
However, two severe illnesses wrought a great change in his way
of looking at life, and in 1032, remembering his early dedication of
himself to God, he resolved to forsake the world and take the habit
of religion in the monastery of St. Emmeran’s, at Ratisbon, where he
gave up all thoughts of secular ambition, in order to devote himself
heart and soul to the duties of his state. St. Emmeran’s was, like
Tegernsee, possessed of an excellent school and library. In the
former many good scholars were reared, such as abbot William of
Hirschau, who became as learned in the liberal arts as in the study
of the Scriptures, and who afterwards made his own school at
Hirschau one of the most celebrated in Germany. Othlonus tells us
that in this monastery he found “several men in different classes,
some reading pagan authors, others the Holy Scriptures,” and that
he began to imitate the latter, and soon learnt to relish the Sacred
Books, which he had hitherto neglected, far above the writings of
Aristotle, Plato, or even Boëthius.[157]
It will be seen from this little sketch that Othlonus was not a mere
transcriber, and indeed he afterwards produced several treatises on
mystic theology, besides his “Life of St. Wolfgang,” and was regarded
by his brother monks as “a pious and austere man, possessed of an
immense love of books.” This love he showed not only by reading
them, but by multiplying them; and his achievements in this kind are
related by himself with a certain prolix eloquence which, in mercy to
the reader, I will somewhat abridge.
“I think it right,” he says, “to add some account of the great
capacity of writing which was given me by the Lord from my
childhood. When as yet a little child I was sent to school, and quickly
learnt my letters; and began long before the usual time of learning,
and without any order from the master, to learn the art of writing;
but in a furtive and unusual way, and without any teacher, so that I
got a bad habit of holding my pen in a wrong manner, nor were any
of my teachers afterwards able to correct me in that point. Many
who saw this, decided that I should never write well, but by the
grace of God it turned out otherwise. For, even in my childhood,
when, together with the other boys, the tablet was put into my
hands, it appeared that I had some notion of writing. Then, after a
time, I began to write so well and was so fond of it, that in the
monastery of Tegernsee, where I learned, I wrote many books, and
being sent into Franconia, I worked so hard as nearly to lose my
sight.... Then, after I became a monk of St. Emmeran’s, I was
induced again to occupy myself so much in writing, that I seldom
got an interval of rest except on festivals. Meantime there came
more work on me, for as they saw I was generally reading, writing,
or composing, they made me schoolmaster; by all which things I
was, through God’s grace, so fully occupied that I frequently could
not allow my body the necessary rest. When I had a mind to
compose anything, I could not find time for it, except on holidays or
at night, being tied down to the business of teaching the boys, and
transcribing what I had undertaken. Besides the books which I
composed myself I wrote nineteen missals, three books of the
Gospels, and two lectionaries; besides which I wrote four service
books for matins. Afterwards, old age and infirmity hindered me, and
the grief caused by the destruction of our monastery; but to Him
who is author of all good, and who has vouchsafed to give many
things to me unworthy, be praise eternal!” He then adds an account
of a vast number of other books written out by him and sent as
presents to the monasteries of Fulda, Hirschfeld, Lorsch, Tegernsee,
and others, amounting in all to thirty volumes. His labours, so
cheerfully undertaken for the improvement of his convent, were
perhaps surpassed by those of the monk Jerome, who wrote out so
great a number of volumes, that it is said a wagon with six horses
would not have sufficed to draw them. But neither one nor the other
are to be compared to Diemudis, a devout nun of the monastery of
Wessobrun, who, besides writing out in clear and beautiful
characters five missals, with graduals and sequences attached, and
four other office books, for the use of the church, adorned the
library of her convent with two entire Bibles, eight volumes of St.
Gregory, seven of St. Augustine, the ecclesiastical histories of
Eusebius and Cassiodorus, and a vast number of sermons, homilies,
and other treatises, a list of which she left, as having all been
written by her own hand, to the praise of God and of the holy
apostles SS. Peter and Paul. This Diemudis was a contemporary of
Othlonus, and found time in the midst of her gigantic labours to
carry on a correspondence with Herluca, a nun of Eppach, to whom
she is said to have indited “many very sweet letters,” which were
long preserved.
I have mentioned as one of the scholars of St. Emmeran’s the holy
William of Hirschau, who was chosen abbot of his monastery in
1070, and applied himself to make his monks as learned and as
indefatigable in all useful labours as he was himself. He had about
250 monks at Hirschau, and founded no fewer than fifteen other
religious houses, for the government of which he drew up a body of
excellent statutes. These new foundations he carefully supplied with
books, which necessitated constant work in the scriptorium. And a
most stately and noble place was the scriptorium of Hirschau,
wherein each one was employed according to his talent, binding,
painting, gilding, writing, or correcting. The twelve best writers were
reserved for transcribing the Scriptures and the Holy Fathers, and
one of the twelve, most learned in the sciences, presided over the
tasks of the others, chose the books to be copied, and corrected the
faults of the younger scribes. The art of painting was studied in a
separate school, and here, among others, was trained the good
monk Thiemon, who, after decorating half the monasteries of
Germany with the productions of his pencil, became archbishop of
Saltzburg, and died in odour of sanctity. The statutes with which
abbot William provided his monasteries, were chiefly drawn up from
those in use at St. Emmeran’s, but he was desirous of yet further
improving them, and in particular of assimilating them to those of
Cluny, which was then at the height of its renown. It was at his
request that St. Ulric of Cluny wrote out his “Customary,” in which,
among other things, he gives a description of the manner in which
the Holy Scriptures were read through in the refectory in the course
of the year. This “Customary” is one of the most valuable
monuments of monastic times which remains to us; it shows us the
interior of the monastery, painted by the hand of one of its inmates,
taking us through each office, the library, the infirmary, the sacristy,
the bakehouse, the kitchen, and the school. How beautiful is the
order which it displays, as observed in choir, where, on solemn days,
all the singers stood vested in copes, the very seats being covered
with embroidered tapestry! Three days in the week the right side of
the choir communicated, and the other three the left; during Holy
Week they washed the feet of as many poor as there were brethren
in the house, and the abbot added others also to represent absent
friends. When the Passion was sung, they had a custom of tearing a
piece of stuff at the words “they parted my garments;” and the new
fire of Holy Saturday was struck, not from a flint, but a precious
beryl. There were numberless beautiful rites of benediction
observed, as that of the ripe grapes, which were blessed on the altar
during mass, on the 6th of August, and afterwards distributed in the
refectory, of new beans, and of the freshly-pressed juice of the
grape. The ceremonies observed in making the altar breads were
also most worthy of note. The grains of wheat were chosen one by
one, were carefully washed and put aside in a sack, which was
carried by one known to be pure in life and conversation to the mill.
There they were ground and sifted, he who performed this duty
being clothed in alb and amice. Two priests and two deacons clothed
in like manner prepared the breads, and a lay brother, having gloves
on his hands, held the irons in which they were baked. The very
wood of the fire was chosen of the best and driest. And whilst these
processes were being gone through, the brethren engaged ceased
not to sing psalms, or sometimes recited Our Lady’s office. A
separate chapter in the “Customary” is devoted to the children and
their master, and the discipline under which they were trained is
minutely described. We seem to see them seated in their cloister
with the vigilant eye of the master presiding over their work. An
open space is left between the two rows of scholars, but there is no
one in the monastery who dare pass through their ranks. They go to
confession twice a week, and always to the abbot or the prior. And
such is the scrupulous care bestowed on their education, and the
vigilance to which they are subjected, both by day and night, that,
says Ulric, “I think it would be difficult for a king’s son to be brought
up in a palace with greater care than the humblest boy enjoys at
Cluny.”
This “Customary” was drawn up during the government of St.
Hugh of Cluny, whose letter to William the Conqueror displays
something of the independence of mind with which abbots of those
days treated the great ones of the earth. William had written to him
requesting him to send some of his monks to England, and offering
him a hundred pounds for every monk he would send. This method
of buying up his monks at so much a head offended the good abbot,
who wrote back to the king declining to part with any of his
community at such a price, and adding that he would himself give an
equal sum for every good monk whom he could draw to Cluny.
During the sixty-two years that he governed his abbey, he is said to
have professed more than 10,000 subjects. Enough has been said to
show that the monastic institute was still strong and vigorous in the
eleventh century. Cluny, indeed, represented monasticism rather in
its magnificence than in the more evangelic aspect of poverty and
abasement, yet in the midst of all her lordly splendour, she
continued fruitful in saints. Even the austere St. Peter Damian, whilst
he disapproved of the wealth of the monks, was edified at their
sanctity, and left them, marvelling how men so rich could live so
holily. Their revenues were not spent on luxury; they went to feed
17,000 poor people, and to collect a library of Greek, Latin, and
Hebrew authors, such as had not its equal in Europe. It contained
among other treasures a certain Bible, called in the chronicle, “great,
wonderful, and precious for its writing, correctness, and rich binding,
adorned with beryl stones,” which had been written by the single
hand of the monk Albert. The following inscription inserted in the
volume attests the piety as well as the industry of the writer. “This
book was written by a certain monk of Cluny, named Albert, formerly
of Treves. It was done by the order and at the expense of the
venerable abbot Pontius, Peter being at that time the librarian, and
providing all things necessary with joy and diligence. And the
aforesaid monk, in company with a certain brother named Opizo,
diligently read through the whole book, that he might be able to
improve it according to the authority of other books; and he twice
corrected it. Therefore Brother Albert a sinner, prostrating himself at
the feet of the brethren of Cluny, humbly begs of them to pray to
God for himself and for his father, that they may obtain the
forgiveness of their sins.”[158]
Elsewhere also the monastic schools continued to produce a
number of excellent masters who thoroughly entered into the revival
of classical studies, which we have noticed as having at this time
sprung up. At Fleury the monk Raoul taught the art of versification
to a crowded audience, and in his own poems advocated the study
of the ancient models, especially of Horace. Quotations from the
same poet, as well as from Virgil and Statius, not unfrequently
appear in the lives of the saints, and even the sermons of this
period, a fact not adduced as an instance of the good taste, but
simply of the erudition, of the authors. In the school of Stavelot,
even Greek poetry was studied. Here was trained the celebrated
Wibald, successively abbot of Stavelot, Monte Cassino, and Corby.
The letters and other remains of this remarkable man have been
inserted by Martene in his collection, and throw much light on the
history of the times. He filled several important offices under the
Emperor Conrad, who confided to him the education of his son and
successor Henry; but whilst constantly immersed in public business
he failed not to labour for the good cause which lay at the heart of
every true monk, the multiplication of books, and the
encouragement of learning. Thus among his letters we find one
addressed in 1149 to the scholasticus of Corby, in which he
enumerates among the writers to be studied in the school,
Pythagoras, Plato, Sophocles, and Simonides, a sufficient proof that
Greek literature was then cultivated in certain seminaries, and that
the knowledge of that language was not confined, as Hallam
suggests, to the occasional singing of a Greek Kyrie or Sanctus.
There are other letters addressed to the superiors of monasteries
whom he engaged to assist him in the collection of books. Among
these was the abbot of Hildesheim, from whom he hoped to obtain a
complete copy of the Offices of Cicero. His petition for these is in a
certain sense apologetic, for, from the days of St. Jerome, religious
men were wont to be a little sensitive, lest too great a love of the
Latin orator should expose them to the charge of being a Ciceronian
rather than a Christian student. Something of this sort had been
playfully hinted at by the abbot of Hildesheim, and Wibald replies:
“We do not serve the dishes of Cicero at the first or principal table;
but when replenished with better food we partake of them as of
sweetmeats that are served for dessert.” Sometimes his letters are
addressed to friends who have visited his library, and who shared in
his literary tastes. “I wish,” he writes to the Archbishop of Bremen,
“that you would come again and remain longer with us, and, as you
promised, turn over the volumes on our shelves. I wish we might
have this pleasure together in peace and quiet; there is surely no
greater happiness to be enjoyed in life.”
It is, perhaps, superfluous to multiply illustrations of this kind, but
I cannot resist adding to the names already cited that of Marianus
Scotus, whom some call an Irishman, and some a Scot, while others
affirm him to have been an honest Northumbrian, and a member of
the family of Bede.[159] He died towards the end of the eleventh
century, having been successively monk in the abbeys of Cologne,
Fulda, and Mayence, and professor of theology some years in that of
Ratisbon. He was a poet, and the author of a Chronicle frequently
quoted as one of the best mediæval histories, and continued by later
writers. His biographers say of him that his countenance was so
beautiful, and his manners so simple, that no one doubted he was
inspired in all he said and did by the Holy Ghost. A most
indefatigable writer, he transcribed the whole Bible with sundry
commentaries, and that not once but repeatedly. Moreover he drew
out of the deep sea of the holy Fathers, certain sweet waters for the
profit of his soul, which he collected in prolix volumes. With all this
he found spare moments which he devoted to charitable labours on
behalf of poor widows, clerks, and scholars, for whose benefit he
multiplied psalters, manuals, and other pious little books, which he
distributed to them free of cost for the remedy of his soul. Who will
refuse to believe that such loving toils as these were found worthy to
receive the miraculous token of favour related in the old legend?
“One night,” says the annalist, “the brother whose duty it was,
having forgotten to give him candles, Marianus nevertheless
continued his work without them; and when the brother, recollecting
his omission, came late at night to his cell, he beheld a brilliant light
streaming through the chinks of the door, and going in softly, found
that it proceeded from the fingers of the monk’s left hand, and he
saw and believed.”
In some writers of this time there are indications of increased
attention being paid to natural phenomena, and the geographical
notices introduced into the chronicle of Otto of Frisingia are praised
by the authors of the Histoire Littéraire for their exactness and
intelligence. A very singular and interesting fact is recorded in the
chronicle of Marianus (or rather in its later continuation), which,
though of a supernatural character, may perhaps be admitted among
the scientific notices of the time. I allude to the vision seen and
described by the Blessed Alpais of Cudot, who saw in rapture the
earth hanging suspended in space shaped like a globe, or rather a
spheroid, for she calls it not perfectly round, but egg-shaped. It was
surrounded by water, and the sun appeared of a vastly greater size.
Equally remarkable in another branch of science are the speculations
of Ithier, a monk of Limoges, on the faculties of the mind
corresponding to different parts of the brain, in which we catch a
first glimpse of the modern theory of phrenology. Nor must it be
supposed that the classical and scientific studies, which excited so
much interest, caused the cultivation of the vulgar dialects to be
forgotten. Abbots and bishops often preached in Romance, like St.
Vital of Savigny and Hildebert of Mans, though the latter is said to
have succeeded better in Latin. St. Bernard delivered his
exhortations to his brethren not in Latin but Romance, for the
benefit of the lay-brothers who were ignorant of the learned
tongues, as Mabillon labours to prove. A vast number of translations
were likewise made into the popular dialects, and about the end of
the eleventh century the monk Grimoald published a version in
Romance of the entire Bible; this translation being made nearly a
century before that of the Waldenses, though the latter is very
generally represented to be the earliest known version of the
Scriptures in any vulgar tongue.[160]
It is evident, then, that all the learning of the eleventh and twelfth
centuries was not swallowed up by the new race of scholastics, nor
was every scholastic a Berengarius. Yet there is a certain change
perceptible in many of those who at this time attained to literary
eminence, and a greater predominance of the philosophic element,
consequent in some degree from the nature of the studies rendered
popular in the school of Bec. We begin more frequently to meet with
tales of scholars who, in the midst of their learned pursuits, were
overtaken with a dread of the perils which beset their course, and
sought to escape them by flying into the desert. The cloisters were
peopled with such refugees from the schools, who, like Lanfranc,
often reappeared after a while to resume the weapons of human
science, which they had thought to fling aside for ever, and use
them in the service of their Master.
Of these converts were St. Bruno, the founder of the Carthusians,
and Odo of Tournai. Bruno is said to have studied at Tours under
Berengarius, though this appears doubtful. In 1056 the scholasticus
of Rheims having resigned his charge, that he might devote himself
exclusively to the affairs of his own salvation, Gervase, Archbishop of
Rheims, promoted Bruno to the office, which by this time had
become associated to that of Chancellor of the diocese, and gave its
holder a certain superiority over the other diocesan schools. Bruno
continued to fill this responsible post for twenty years, during which
time he numbered among his pupils Odo, afterwards Pope Urban II.,
and many of the greatest prelates of the time. He was reckoned the
first philosopher, theologian, and poet of France, and by writers of
his own day is extolled as “the doctor of doctors, the glory of the
Church, the model of good men, and the mirror of the whole world.”
The romantic story which ascribes his conversion to religion to the
horror caused by the voice which came from the dead body of a
certain eminent doctor, proclaiming his damnation, is now universally
rejected as the production of a later age. In fact, St. Bruno has
himself related the manner in which his resolution was first formed
in a letter addressed to Raoul, provost of Rheims, wherein he
reminds him of a certain day when they were walking with another
canon named Fulcius, in the garden adjoining his house, conversing
together of the vanities of the world. “Then it was,” he says, “that
the Holy Spirit moved us to renounce all perishable things, and
embrace the monastic life that we might merit life eternal.” It would
also appear that a grievous case of simony, which had scandalised
the diocese, powerfully wrought on Bruno’s mind, and moved him to
fly from a world so hedged about with temptations. He was followed
into his retreat by a number of his former scholars; but it was not
until 1084 that they at last determined on the way of life they should
choose, and, receiving the monastic habit from the hands of St.
Hugh of Grenoble, laid the foundation of the Carthusian Order, which
took its name from the desert they had chosen for their abode. In
after years the order continued to be largely recruited from the same
class whence their first founder had been drawn. Many a fine scholar
came to the wild rocks of the Chartreuse to seek in obscurity for a
peace which he found by experience the world of intellect could
never give; and Bulæus informs us that no order of monks received
among their ranks so many members of Paris University as did these
austere and penitential recluses.
Odo, or Oudart, the other convert to whom allusion has been
made, first attracted notice as a teacher at Toul, a city which had
always been rich in schools and schoolmasters, and which had felt a
special pride in keeping up its learned reputation, since 1048, when
it had sent its bishop to fill the chair of St. Peter in the person of St.
Leo IX. Odo’s fame reached the ears of the canons of Tournai, who
entreated him to take charge of their cathedral school, which he
accordingly governed for five years. A skilful teacher, and a devourer
of books, Odo possessed extraordinary powers of labour, and when
any literary work was in hand, he rested neither day nor night till it
was accomplished. He was also a great friend of method and good
moral discipline, but as yet he had been too exclusively taken up
with the cares and pleasures of his profession to give much thought
to spiritual things. Or perhaps we might rather say that he hardly
knew of their existence. Like other busy, hard-working men, he was
swept along in the tide of daily life, and thought it much to preserve
a character of stainless honour and respectability. His success as a
teacher was so great, that disciples came to him from all parts of
France, as well as from Flanders, Italy, and Saxony. The city of
Tournai became literally filled with students, who might be seen
disputing together in the public streets: and as you drew near the
school you would see them walking with the master, or seated
around him; or, in the evening, standing with him at the church door,
while he taught them the various constellations, and explained to
them the course of the stars.
Odo was as remarkable for his virtue as his learning. He took all
his disciples to the church with him daily. They never numbered
fewer than two hundred; but he made them walk two-and-two
through the streets, he himself bringing up the rear, and enforcing a
discipline as strict as would have been observed in the most regular
monastery. No one ventured to speak to his companion, or to look
right or left, and in choir they might have been taken for monks of
Cluny. He did not allow them to frequent the company of women, or
to wear any kind of finery; and if they transgressed his orders in
these respects, he turned them out of his school. At the hours when
he gave his lectures no layman was allowed to enter the cloisters,
which were at other times the resort of the public. So strict was he
in this, that he did not hesitate to exclude Everard, the Castellan of
Tournai, a nobleman of power and influence; for it was Odo’s
principle that a man must not deviate a hair’s-breadth from his duty
from the motive of human respect. By these means he won the love
and esteem of every one: canons and people alike spoke well of
him, though some were found to say that his regularity of life sprang
rather from philosophy than religion.
He had directed his school for about five years, when one day, a
certain clerk having brought him St. Augustine’s “Treatise on Free-
will,” he purchased it, merely with the view of increasing his library,
and threw it into a coffer among some other books without looking
at it, for his taste inclined him rather to the study of Plato than of
the Fathers. About two months afterwards, however, as he was
explaining Boëthius to his disciples, he came to the fourth book of
the “Consolations of Philosophy,” in which the author treats of Free-
will. Remembering the book he had lately purchased on the same
subject, he sent for it, and having read two or three pages, was
struck with the beauty of the style; and calling his pupils, said to
them, “I own that until now I was ignorant how agreeable and
eloquent are the writings of St. Augustine;” and that day and the
following he read to them from this work, explaining its difficulties as
he proceeded.
In this way he came to that passage in the third book, wherein St.
Augustine compares the soul of the sinner to a slave condemned to
some vile and disgusting labour. Odo sighed as he read the powerful
words of the writer, exclaiming, “How striking is this comparison! it
seems as if written expressly for us men of science. We adorn the
corrupt world with the little stock of learning which we possess, and
after death, perhaps, are not found worthy of eternal happiness,
because we have done God no service; but have used our intellects
for vanity and worldly glory!” With these words he rose from his
chair, and going into the church, remained there in floods of tears,
his scholars meanwhile remaining astonished and perplexed. From
that day he gradually discontinued his lectures, and began to
frequent the church more diligently, and to distribute in alms all the
money he received from his pupils. He also fasted so rigorously that
his appearance soon completely changed, and he became so thin
and attenuated as scarcely to be recognised.
The rumour soon ran through the town that Odo, the famous
doctor, was about to abandon the world. Four of his disciples
resolved never to quit him, and made him promise to do nothing
except in concert with them. Monks and abbots from every religious
house in the neighbourhood of Tournai, wanted Odo to join their
communities, but his disciples preferred the rule of the canons as
being easier than that of the monks. Rabod, the Bishop of Tournai,
accordingly made over to them an old church, part of an abbey
which had been destroyed by the Normans, and they took
possession of it in 1092. Two years later they resolved on embracing
the monastic rule, and the bishop giving his consent, Odo was
elected first abbot of the restored abbey of Tournai. Though he had
fled to the cloister to escape from the pride of the schools, he did
not neglect the cause of learning. Like most of the religious
superiors of his day, he gave much time and trouble to the formation
of a good library and scriptorium, and used to make an innocent
boast of the many good writers whom the Lord had given him. Had
you gone into his scriptorium, says his successor, you would have
seen twelve youths, sitting in silence, most diligently engaged in
copying manuscripts, at tables made for the purpose. And he
enumerates among the books so transcribed the works of St. Jerome
and St. Gregory, and all that he could collect of Bede, Isidore,
Ambrose, Austin, and the Lord Anselm of Bec.
About this time the rival philosophical sects known as the Realists
and Nominalists began to attract attention. The questions in dispute
between them regarded the validity and existence of universal ideas.
The expression requires explanation. An idea is the representation in
the mind of some impression made on the senses by an external
object. These ideas may be either particular or universal. They are
particular when they correspond to some individual object, as John
Smith, or that tree. They are universal when we separate them from
any individual object, and conceive them as corresponding to
something which is to be found in many individuals, whereby these
may be classified together, as when we speak of men or trees.
According to the scholastics, there are five kinds of such universal
ideas, namely, species, genus, difference, property and accident. The
species includes many individuals, as sheep, oak. The genus includes
many species, as animal, tree. Difference is something which
distinguishes one species from another belonging to the same
genus. Property, or essential attribute, is what necessarily belongs to
the essence of a thing; as when we say of a globe that it is round.
Accident is some attribute to be found in a thing which is not
necessary to its existence, as if we were to say of the same globe
that it is green. We are able to hold these ideas in our mind,
abstracted from any object, and so we come to have the abstract
ideas of men, animals, trees, roundness, or whiteness, without
connecting them with any particular individual. But the Nominalists
denied the existence of such ideas, and declared the above
distinctions to be mere sounds of the voice, corresponding to no
external reality. They knew what was meant by a wise man, or a
white horse, but professed themselves unable to comprehend what
was meant by wisdom or whiteness. The Realists, on the other
hand, appealing to the authority of Boëthius, contended that these
ideas were real and existent.
Both parties numbered great names in their ranks. Odo of Tournai
was a partisan of the Realists, as was also the Blessed Robert of
Arbrisselles. At the head of the Nominalists appeared his fellow-
student and professor in the Paris schools, Roscelin, a canon of
Compeigne, and a man whose character too closely resembled that
of Berengarius. He seems to have adopted novel and startling
opinions as a means of drawing the eyes of men on himself, and the
manner in which he applied his philosophical method of reasoning to
revealed doctrines, specially that of the Holy Trinity, resulted in
actual heresy, and brought on him in 1092 the condemnation of the
Council of Soissons. Taking refuge in England, he there met with a
vigorous opponent in the person of St. Anselm, who, whilst freely
admitting, and even advocating the exercise of the intellectual
powers on the mysteries of faith, marked out the limits between
faith and reason, and severely condemned the presumption of those
who would attempt to make reason the test of faith. He declares
that we must seek the intelligence of those things that we already
believe; that reason is not the means by which we attain to faith,
but rather that by which we enjoy the evidence and contemplation
of the mysteries which we already believe: and that right order
demands that we should first receive the profound truths of faith
before we dare to exercise our reason upon them.[161] As time went
on, and both sects pushed their philosophical views to extremes,
grave errors were charged against both, and the foundations were
laid of many forms of modern Rationalism.
Paris was now rapidly becoming the centre of scholastic activity.
The fame of her masters spread over Europe, and among them were
Lambert, a disciple of Fulbert of Chartres; Manegold, whose very
daughters were learned, and opened a school for the education of
their own sex, Anselm of Laon and Bernard of Chartres. John of
Salisbury, whose favourite master, William de Conches, had himself
been a pupil of Bernard’s, has left us an interesting account of the
method of this last-named teacher. He explained all the best authors,
not confining himself to grammar strictly so called, but making his
pupils observe all the refinements of rhetoric. He pointed out the
propriety of certain terms and metaphors, and the best order and
arrangement of a subject; and showed the variety of styles to be
used according to the different matters treated of by a writer. If any
passage occurred in their reading referring to other sciences, he
took pains to explain it, according to the capacity of his hearers. He
was careful to cultivate their memory, making them learn and recite
choice passages from the classic historians, poets, and philosophers;
requiring them one day to give an exact account of what they had
heard or read the day previous. He was always exhorting them to
read much in private, but not indiscriminately, directing them to
avoid what was only fit to feed curiosity, and to content themselves
with the works of standard authors. For, he used to say, quoting
Quinctilian, “it is a great weakness to read all that every miserable
writer has to say on every subject, and only loads the memory with
superfluous and worthless things.”
As he knew that it is to very little purpose to hear or study
examples unless we accustom ourselves to reproduce the treasures
thus stored up in the memory, he was anxious that his pupils should
every day compose something both in prose and verse, and he
established conferences among them wherein they mutually
questioned and answered one another, the utility of which exercise
John of Salisbury speaks of very highly; “provided,” as he observes,
“that charity govern the emulation displayed in such encounters, so
that while we make progress in letters we still preserve humility. For
a man should not serve two masters so opposed one to the other as
learning and vice.”
This was also the rule observed by Bernard, who maintained that
the first and principal key to knowledge was Humility, to which he
assigned Poverty as a companion. The subjects on which he
exercised his scholars were always fitted to cherish both faith and
good morals. And the work of each day was finished with the
recitation of the “Our Father,” and a brief prayer for the dead.
Anselm of Laon was a teacher of much the same character, and, if
possible, of greater renown. He and his brother Radulph were called
by Guibert de Nogent the two eyes of the Latin Church, and by their
knowledge of the Scriptures converted many heretics. Some of their
pupils were as famous as themselves, such as Hugh Metellus, a
great lover of the classics, whose flow of language was so great that
he dictated to two secretaries at once, and could improvise a
thousand verses, standing on one leg, and who was induced by the
teaching of his pious masters to exchange a life of worldly vanity,
the love of dress and delicate diet, for the austere regimen of a
canon regular of Toul. Another of Anselm’s scholars was William de
Champeaux, under whom the Paris schools first attained that pre-
eminence which they maintained in the world of letters down to the
period of the Revolution. After studying successively under Manegold
and Anselm, he was appointed archdeacon of the Church of Paris,
and master of the Cathedral school, where he taught logic, rhetoric,
and theology, with great success. And about the year 1100 his
reputation attracted one disciple whose name is indelibly associated
with the literary history of the period,—the celebrated Peter Abelard.
Abelard’s choice of a scholar’s life is said to have been influenced
in the first instance by his dislike of the profession of arms. Nature,
while it had given him an insatiable desire for fame and worldly
glory, had denied him the gift of personal courage, and he himself
made no secret of the feeling which, as he said, had moved him to
enrol himself under the banners of Minerva, rather than those of
Mars. His subtle mind was very early devoted to the study of logic,
but not satisfied with the teaching to be found in his own diocese of
Nantes, he led a wandering life for some time, passing from school
to school; and at last found his way to Paris, where William de
Champeaux was then at the height of his reputation as a teacher of
dialectics. The brilliant qualities of his new pupil at first won the
heart of his master, but erelong Abelard began to show signs of that
presumption and contempt of every one’s attainments except his
own, which kept him at war with all his contemporaries. He came to
the lecture rooms less with the view of learning than with the secret
hope of outshining his fellow-students and perplexing his master. He
was perpetually proposing vexatious questions, for the purpose of
entrapping the latter in some logical subtlety; and affecting to
consider that William had shown himself unable to answer these
difficulties, he disdained any longer to be the scholar of one whom
he considered his inferior, and determined on setting up a school for
himself.
Unable to do this in Paris, where the influence of William de
Champeaux was at that time all-powerful, he established himself
first at Mélun, and then at Corbeil, which was nearer to the capital.
He was but twenty-two when he first appeared before the world as
an independent professor, and soon made himself talked of for his
brilliancy, his fluency, and the vehemence with which he attempted
to make the art of logic supersede all the other liberal arts, which he
was accustomed to treat with contempt. His passion for glory soon
brought him back to Paris, where William de Champeaux was now
archdeacon, and head of the cathedral school. Abelard renewed his
attacks on his old master, and that with such success, that the
cloisteral schools became deserted, and the fickle audience flocked
to the lectures of the new professor. The circumstance seems to
have touched the heart of William with a contempt for intellectual
renown which was so easily won and lost, and resigning his school,
he retired among the canons regular of St. Victor, a religious house
destined to play a great part in the history of the future university.
This was in 1109, and, by the advice of Hildebert, Bishop of Mans,
who wrote to the new canon, congratulating him on “the step by
which he had at last become a true philosopher,” William opened a
school within his monastery, which afterwards produced several
illustrious theologians, who are all distinguished by the surname of
St. Victor.
It is unnecessary to pursue the rivalries of the two professors
through all their windings; in 1113 William was raised to the see of
Châlons, a circumstance which seems to have first induced Abelard
to study theology, with the hope of attaining similar honours.
Accordingly, we next find him at Laon, attending the school of
Anselm, now dean of that church, whom, however, he very soon
declared to be altogether unworthy of his great renown. “His
learning was,” he said, “nothing but foliage without fruit; long
custom, rather than any real merit, had acquired him a name. If you
consulted him on any difficulty, you came away just as wise as you
went. There was nothing but abundance of fine words, without a
grain of sense or reason.” So, in despair of finding a master wise
enough to teach one of his genius, he resolved to do without one,
and, with the help of a commentary, began to give lectures on the
prophet Ezechiel. His wit, his fluency, and his singular charms of
voice and manner, veiled the real shallowness of his theological
attainments, and, on returning to Paris, he succeeded in gaining
what had been for so many years the great object of his ambition,
the direction of the cathedral school. Then began the period of his
extraordinary popularity; disciples flocked to him from all parts of
France and Germany, as well as from Rome and England. His vanity
easily persuaded him that he was not merely the greatest, but the
only philosopher of his time; all the world hung on his eloquence,
but amid the long catologue of his admirers, none was to be found
so bewitched with his merits as he was himself.
Abelard’s teaching bore the character of his own restless and
impatient genius. Disdainful of anything which did not promise quick
results, he aimed at presenting his disciples with a philosophy which
professed to lead them to the possession of wisdom by a royal road.
The trivium and quadrivium were to be consigned to oblivion; the
classics and the Fathers might alike grow dusty on the shelves, logic
was to be all in all, and the philosopher and the theologian might
abandon every other study, provided they perfected themselves in
the art which St. Bernard characterised with caustic wit, as “that of
ever studying, and never reaching the truth.” Abelard’s
condemnation of the classics is worth noticing, as showing the
similarity of mind which existed between him and Berengarius,
whom Guitmond describes as “making no account of the opinions of
his masters, and despising the liberal arts.” In neither of them did
this condemnation arise from a preponderance of the Christian
sense; but from their repugnance to objective realities.[162] Their
philosophy was in short that of which the apostle speaks, when he
condemns the “vain babblings” of those who “desire to be teachers
of the law,” which differed little from the “foolish questionings” of the
sophists. The effect of these new doctrines was to inaugurate a
scholastic revolution. One by one the fair branches of the tree of
science were severed from the trunk, till at last nothing remained
but the exercise of subtle and captious argumentation, wherein logic
came to be used not as a means but an end, and the scholar was no
longer led to seek for truth as his object, but to rest content with the
search after it.
Thus passed several years, during which Abelard had earned a
fame, brilliant indeed beyond that of any of his contemporaries, but
unhappily one which left his moral reputation far from stainless. In
1117 we find him in the abbey of St. Denis, where he had taken
refuge from the disgrace entailed on him by his connection with
Heloïsa. Even here his insupportable vanity was not long before it
betrayed itself in the criticisms he passed on his abbot and his
brother monks, among whom he seems to have aspired to act as the
reformer. The abbot longed to get rid of so troublesome a subject,
and the opportunity of doing so soon presented itself. Crowds of
students began to clamour at the gates of St. Denis for their old
master, and to implore him to reopen his school. He therefore
resumed his lectures, but unable to rest contented with teaching
only what had been taught before him, he began to introduce logical
subtleties into his theological views, and put forth certain
explanations on the doctrine of the Holy Trinity, which raised a storm
of opposition. His chief opponents were Alberic and Lotulf, two
former disciples of Anselm of Laon, and William of Champeaux. They
not only attacked his opinions as heterodox, but complained that he
had no right to teach at all. His position as a professor was, they
said, altogether irregular, for, contrary to the established usages of
the Paris schools, he taught sine magistro.
This term requires a little explanation; and shows us the germ of
what soon afterwards developed into the system of university
graduation. According to established custom, no scholar could be
licensed to teach publicly who had not previously gone through a
regular course of study under some approved doctor. But Abelard
had had no master in theology, except himself; for, as we have seen,
he gave up his attendance in Anselm’s school through contempt for
his inferiority, and had at once begun to teach a science which in
reality he had never studied. At a Council assembled at Soissons, his
Treatise on the Holy Trinity was condemned, and he himself required
to cast it into the fire, and to make public profession of the faith by
reciting the creed of St. Athanasius, which he did with many tears
and sighs, after which he was sent back to the monastery of St.
Denys. He had not been there long, however, when a controversy
which he thought fit to raise on the question of the identity of St.
Denys, the Areopagite, with the patron of the abbey, got him into
fresh trouble, and he fled from the monastery to the territory of the
Count of Champagne, where he fixed his residence in a beautiful
solitude near Nogent, which was soon found out by his disciples.
“They came crowding to me,” he writes, “from all parts, and leaving
the towns and cities, were content to dwell in the wilderness.
Instead of spacious houses, they set up for themselves little tents,
and put up gladly with wild herbs instead of delicate viands. People
said one to another, ‘Behold the world is gone after him.’ At last, as
my little oratory would not hold them, they enlarged it, building it of
wood and stone.” To this new building he gave the name of the
Paraclete, and it might truly have been his consolation could he have
learnt wisdom from the past, and bowed his erratic genius under the
yoke of faith. But the school of the Paraclete soon resounded with
new errors; to the former opinions put forth regarding the Holy
Trinity, were now added equally heterodox views on the subject of
grace and original sin, which were at once discerned and denounced
by two saints who then illuminated the church with their doctrine
and their virtue—St. Norbert, and St. Bernard of Clairvaux. Abelard,
whose natural cowardice shrank from the prospect of new dangers,
endeavoured to escape the consequences of his own imprudence by
abandoning the Paraclete, and accepting the government of St.
Gildas’ abbey; but the uncouth manners and language of the monks
filled him with repugnance, or perhaps it would be truer to say, the
monastic routine proved insufferable to one who had nothing of the
real monk about him. In 1126, therefore, we find him once more
teaching in the schools of St. Geneviève. He was never really at
home save in the Professor’s chair, but unhappily he never filled it
without betraying himself into some of the audacities of unorthodox
philosophy. Soon his old errors were reproduced, and called forth the
zeal of St. Bernard, who protested with all the force of his nervous
eloquence against the strange assemblage of heresies to be found
united in the teaching of a single man. “When he speaks of the Holy
Trinity,” he says, “it is in the style of Arius; he is a Pelagian when he
treats of grace, and a second Nestorius when he speaks of the
Person of Jesus Christ. His vanity,” continues the saint, “is such that
he brags as if there were nothing in heaven and earth he did not
know; and in truth he knows a little of everything except himself.” In
his 190th Epistle, addressed to Pope Innocent II., St. Bernard sums
up all the errors of Abelard, who had ventured to deny, and even to
ridicule, the doctrine of Redemption, which he presumptuously
declared illogical, declaring that our Lord came only to instruct us by
His Word and Example. His final condemnation took place at the
Council of Sens, which imposed silence on him for ever, a sentence
confirmed by the authority of Pope Innocent II. This condemnation
might possibly have had no better result than that of Soissons, had it
not been for the charity of the Venerable Peter of Cluny, at whose
monastery Abelard stopped on his way to Rome, where he purposed
to appeal against his sentence. The holy abbot succeeded in drawing
from him a recantation of his errors; he induced him to renounce the
scholastic career, which had been the source of so many
temptations, and frankly to submit to the judgment of the Council
and the Pope. More than this, he exerted himself to effect a personal
reconciliation between Abelard and St. Bernard, and lastly, he
offered to the wounded spirit of the unhappy scholar a secure and
sheltered retreat in his own community, where, under the habit of
religion, the Professor of St. Geneviève spent the last years of his life
in the exercise of piety and penance.
There then, let us leave him, in his poor cell with its wooden
candlestick and its crucifix, with the Holy Scriptures and a few
treatises of the Fathers for his only library; defeated, as some might
say, put to silence, and extinguished—but with his heart, at last, at
peace. Well might he have exclaimed with the Psalmist, “It is good
for me that Thou hast humbled me!” A change was wrought in him
so great, that, as we read the words in which his good abbot
describes it, we can scarcely recognise the old Abelard of former
years. “Never did I see a man more humble,” writes Peter the
Venerable, “whether in gesture, habit, or countenance. He read
continually, prayed often, and kept silence at all times, unless when
forced to speak; and after his reconciliation with the Holy See,
offered the Holy Sacrifice almost daily, and occupied himself only
with meditating or teaching me truths of religion or philosophy.” A
marvellous change indeed; and happy were it if all who incurred the
same censures could follow in the same course.
We have seen that the rationalistic errors of Abelard found their
ablest opponent in St. Bernard, who had conceived a distrust of the
new philosophy when studying as a mere boy in the canon’s school
at Chatillon, where the fashionable scholasticism was just then
beginning to be introduced. He seems to have felt an instinctive
dread of its ultimate tendencies, and to have preserved during his
whole life the sentiments resulting from his early experience of what
his biographer Geoffery of Igny designates as the “wisdom of the
world.” Closely united to him in their theological views, were the
great scholars of St. Victor’s, Hugh, Richard, and Adam. Hugh of St.
Victor, the third prior in succession from William de Champeaux, was
styled the second Augustine, from his devoted admiration of that
Father. Brought up in a house of canons regular in Saxony, he bore
testimony in after life to the care they bestowed on his education. “I
do not fear to certify,” he says, “that they neglected no means of
perfecting me in the sciences, and even instructed me in many
things which might be thought trifling and extraordinary.” These
words occur in his Didascalion, or Treatise on Studies, which he drew
up with the view of remedying the disorderly and unmethodical
manner in which most scholars then pursued their academic labours.
In it he gives an interesting account of his own early life as a scholar.
“I never despised anything that belonged to erudition,” he says;
“when I was a scholar I studied the names of everything I saw. I
committed to memory all the sentences, questions, replies, and
solutions I had heard and learnt during the day; and I used to
describe the figures of geometry on the floor with charcoal. I do not
say this to boast of my knowledge, which is nothing, but to show
that he proceeds best who proceeds with order. You will find many
things in histories and other books, which taken in themselves seem
of little profit, but which nevertheless are useful and necessary when
taken in connection with other things.” Hugh, like all the disciples of
this school, advocated the old system, according to which all the
parts of knowledge stood in mutual relation to one another, and
theology dominated over the whole. In his Treatise De Vanitate
Mundi, he describes an imaginary school, in which is no doubt
depicted that of his own monastery. The students are described
divided into groups, according to the different subjects on which
they are engaged. All the liberal arts are cultivated in turn, and while
the fingers of some are employed in designing or colouring an
illuminated page, others are studying the nature of herbs, or the
constitution of the human frame. As a spiritual writer, Hugh of St.
Victor is considered to be surpassed by his disciple Richard of St.
Victor, a Scotchman by birth, and one of the greatest mystic
theologians of the Church. The special doctrines insisted on by this
school were those which put forth faith, and not reason, as the
ground of certainty, and maintained that reason was to be exercised
only to demonstrate the truths that were held by faith. Abelard, in
his extravagant exaltation of the claims of reason, had gone so far in
his “Introduction to Theology,” as to define faith as an opinion, and
to depreciate a too ready belief, praising that cautious philosophy
which does not yield its faith till it has subjected all things to the test
of reason. To believe without doubting, according to this view of
things, was the religion of women and children; to doubt all things
before we believe them was alone worthy of the dignity of man. The
scholars of St. Victor not only vindicated the true claims of faith, but
they sought to prove that faith itself must rest on the foundation
stone of charity. They loved to remind their disciples of those words
of Our Lord, “If any man will do the will of God he shall know of the
doctrine.” Charity, they said, is then the foundation, and Humility the
key, to all true science, and we can understand the Truth of God only
in proportion as we obey it. They did not seek to set aside the just
use of the reason, but to assign it limits, and to prohibit the search
after things confessedly above the grasp of human intellect. “What is
it to be wise,” asks Hugo of St. Victor, “but to love God? for love is
wisdom.” He complains of the cavilling spirit of the dialecticians who
would fain turn the simplest precepts of the Gospel into matter of
dispute. If they read that we are to love our neighbour as ourselves,
they begin to argue, saying, “If I love one man as myself, then I
must love three or four men more than myself;” and this they style
seeking truth. Again, he blames the conceit of those who, ignorant
of the very first elements, will condescend to study nothing but the
sublimest matters, forgetting that the beginning of all discipline is
humility. Neither would he endure that presumptuous spirit which
gloried in the subtlety of its own powers, but, like a true disciple of
St. Augustine, desired that reliance on Divine Grace should be the
foundation of the whole spiritual and intellectual edifice.
Perfectly in accordance with this teaching was that of John of
Salisbury, who exposed the vain pretensions of those who ought to
make philosophy consist in a barren exercise of the reasoning
powers. “Philosophy,” he says, “is nothing else but the love of God,
and if that love be extinguished philosophy vanishes away. All
studies worthy of that end must tend to the increase of charity, and
he who acquires or increases charity has gained the highest object
of philosophy. This, therefore, is the true rule of philosophy, that all
learning and all reading should be made conducive to truth and
charity, and then the choir of virtues will enter into the soul as into a
temple of God. They most impudently err who think that philosophy
consists in mere words, who multiply phrases and propose a
thousand ridiculous little questions, endeavouring to perplex their
hearers that they may seem more learned than Dædalus. But
though eloquence is a useful and noble study, this loquacity of vain
disputation is a most hateful thing.” Truth, as all agreed, was the
only object of science; but whilst Abelard and his followers sought
this truth in the subjective reasonings of their own minds, the
mystics of St. Victor’s school declared that it was not to be sought by
the understanding alone, but by the heart and will. For what is
Truth, they asked, but God Himself? Who is to be sought by love
rather than by science. He therefore who seeks God, seeks the
highest truth, and embraces it when it finds Him. It knows all things
in proportion as it knows more of God, Whom not to know is
darkness. And it knows all things in Him, for, in the words of St.
Gregory, “what does not he see, who sees Him Who sees all things?”
Such was the sublime teaching which St. Bernard and the
contemplatives of his time opposed to the growing spirit of
philosophic rationalism. The Cistercian cloisters and the disciples of
the school of St. Victor everywhere propagated the same spiritual
maxims, and thus provided a wholesome antidote to the baneful
spirit of the age. But the very existence of the antidote bears
witness how wide-spread was the poison which it sought to nullify,
how greatly the mind of Christendom had broken away from the old
landmarks of thought, and how rapidly it was sweeping onward to
what threatened to cause the wreck of faith and philosophy together.
The actual state of the schools at the middle of the twelfth
century may best be gathered from the description given by our own
country man, John of Salisbury, of his own course of studies. He
appears to have come to Paris for the first time in 1136, being then
a youth of sixteen, and, like thousands of the same age, was
launched into the world of the great capital, to complete his
education under the many wise professors who were contending for
popular favour. Here we catch a glimpse of the new system which
was gradually establishing itself. Education was no longer given
exclusively in cloistered schools, but in great cities, where the young
aspirant after science, instead of being sheltered under law and
discipline, was cast abroad to shift for himself, and only required to
attend the lectures of some licensed master. No doubt it was an
excellent way of teaching him a knowledge of the world, but this had
not hitherto been included in the branches of a noble youth’s early
education. However, at sixteen John had to take care of himself in
the great world of Paris, which exercised over him the fascination of
which all were conscious who passed from the semi-barbarous isle of
Britain to the brilliant capital, and beheld the gay vivacity of its
citizens, the gravity of its religious ceremonials, the splendour and
majesty of its many churches, and the busy life of its schools.[163]
“Happy banishment,” wrote the young scholar, “that is permitted
here to find a home!” His first care was to choose what Professor he
would attend. It was just the time when Abelard’s fame was at its
greatest height, and the English youth was naturally enough led to
join the crowds that thronged the school of St. Geneviève. His first
impression was one of delight, but soon his English good sense
revolted at the shallowness which he detected under the showy
outside, while the contemptuous neglect with which Abelard was
wont to treat the ancient learning, was unendurable in the eyes of
one who, young as he was, already had a thoroughly-formed taste
for the classics. So bidding adieu to St. Geneviève, he placed himself
under the two English masters, Robert de Mélun and William de
Conches; by the first of whom he was initiated into the art of logic.
He praises the disinterestedness shown by Robert, who, in his
conduct as Professor, despised worldly gain and sought only the
benefit of his scholars. Robert afterwards became Bishop of
Hereford, and in that capacity acquired a very unenviable notoriety
as one of the chief opponents of St. Thomas of Canterbury. Under
William de Conches, John next passed three years with very great
profit, studying grammar, which was then understood to include the
explanation of good authors. He never regretted the time he
devoted to this study. William was a disciple of the old school, a
stout champion of the liberal arts, and warmly opposed to the new
system introduced by Abelard. He liked to exercise his pupils in
prose and verse, and required not only good prosody, but also good
sense from his scholars. It was doubtless a fine thing to hear the
warm-hearted, testy Englishman speak of the schools in which he
had been brought up half a century ago, when boys were taught to
behave like boys, and to listen to their masters in silence. Things
were much altered now; and it was no longer the custom to follow
the wholesome rule which Pythagoras taught his disciples, namely,
to listen in silence for seven years, and only begin to ask questions
in the eighth. On the contrary, these new scholars would come into
your school with a supercilious air, and propose you their doubts and
quibbles before they were well seated. They seemed to fancy that
they knew everything when they had followed the schools for a year,
and as if their business was to instruct their masters by their
amazingly clever questions. On all these abuses Master William was
wont to expend his honest indignation, but he certainly could not
complain that John of Salisbury exhibited any of these marks of
reprobation. Far from seeming to think he knew everything after a
year’s study, John, after spending twelve years in the schools,
regarded himself as still a learner. After his three years of grammar,
he spent seven years more in successive courses of rhetoric,
mathematics, and theology. Among the masters whose lectures he
attended were Robert Pullus, or Pulleyne, and Gilbert de la Poiree.
The latter afterwards became Bishop of Poitiers, in which dignity he
was accused of teaching certain heterodox opinions on the Holy
Trinity, which were condemned at the Council of Rheims, in 1148.
His errors, like those of Abelard, appear to have arisen out of an
abuse of that scholastic method of argumentation so popular among
the professors of the time, and which too often proved dangerous
weapons in the hands of men whose theological studies by no
means kept pace with the cultivation of dialectics. Robert Pullus, the
English master of theology, and restorer of sacred studies at Oxford,
was a man of far more solid learning. “He knew,” says his great
disciple, “how to be wise with sobriety.” The soundness of his
doctrine was evinced by his “Sum of Theology,” and his
disinterestedness, by his refusal of a bishopric offered him by Henry
I. Robert declined abandoning a life of study for the precarious
honours of a dignity which exposed its owner to the almost certain
contingency of a struggle with the crown. He desired nothing more
honourable than the life of a master; nevertheless, he was unable to
avoid the dignities thrust on him by Celestine II., who created him
cardinal and chancellor of the Roman Church.
During the whole time of his residence at Paris, John of Salisbury
enjoyed a scholar’s honourable state of poverty, and supported
himself by giving lessons to younger students, much after the
fashion of a modern college tutor. His tutorship was, however, by no
means a very profitable post, and supplied him with little beyond the
bare necessaries of life. Happily, however, the threadbare gown of

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DMITRY YU. MURZIN AND TAPIO SALMI

AMSTERDAM • BOSTON • HEIDELBERG • LONDON • NEW YORK • OXFORD

© 2016, 2005 Elsevier B.V. All rights reserved.

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Tapio Salmi and Dmitry Yu. Murzin

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Diversity of catalysts, for example, catalysis by mineral acids, complexes of transition

Dmitry Yu. Murzin

Setting the Scene

Catalytic Kinetics © 2016 Elsevier B.V.

Jöns Jakob Berzelius Wilhelm Ostwald and Svante Arrhenius

Fig. 1.1 Catalytic cycle.

Worldwide merchant catalyst markets

2.0 2.2 Polymer

* Toll manufacturing fees only

A comparison between homogeneous and heterogeneous catalysts from the view-

Fig. 1.9 Images of heterogeneous catalysts.

Fig. 1.10 A schematic view on an enzyme structure. (From https://upload.wikimedia.org/wikipedia/

Peptide bond acting

Fig. 1.11 Specificity of enzyme catalysis. (From http://csls-text3.c.u-tokyo.ac.jp/large_fig/fig04_05.html.

1.3. FORMAL KINETICS

Fig. 1.12 Representation of reaction kinetics of different orders.

with the reaction order corresponding to the slope (Fig. 1.13).

1.4. ACQUISITION OF KINETIC DATA

Fig. 1.14 Different types of stirred tank reactors.

Fig. 1.15 Tubular reactors.

Fig. 1.16 Approach to kinetic analysis in batch reactors.

1.4.1 Batch Reactors

Fig. 1.18 A volume element.

In fact, treatment of heterogeneous, homogeneous and enzymatic reactions is basically

Batch stirred Continuous stirred

Substituting concentration and volumetric flows for molar flows:

1.4.3 Plug Flow Reactors

Fig. 1.20 A tubular reactor.

Fig. 1.21 Multitubular reactor.

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