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Dmitry Yu. Murzin
Engineering Catalysis
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Dmitry Yu. Murzin

Engineering
Catalysis

2nd Edition
Authors
Prof. Dmitry Yu. Murzin
Åbo Akademi University
Process Chemistry Centre
Biskopsgatan 8
20500 Turku/Åbo
Finland
[email protected]

ISBN 978-3-11-061442-8
e-ISBN (PDF) 978-3-11-061443-5
e-ISBN (EPUB) 978-3-11-061469-5

Library of Congress Control Number: 2019955320

Bibliographic information published by the Deutsche Nationalbibliothek

The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie;
detailed bibliographic data are available on the Internet at http://dnb.dnb.de.

© 2020 Walter de Gruyter GmbH, Berlin/Boston

Cover image: zorazhuang / E+ / Getty Images
Typesetting: Integra Software Services Pvt. Ltd.
Printing and binding: CPI books GmbH, Leck

www.degruyter.com
To the memory of Elena Murzina
Preface to the first edition
If you do not stay the road will lead you
Andrei Platonov

I wrote this book – devoted to the engineering of heterogeneous catalysts and

reactions – in the reverse order of chapters. The last chapter on the technology of
industrial catalytic reactions was written first, with the intention that the needs of
technological implementations will define the reactions and reactors, the reactors set-
ting the requirements for catalytic materials, their preparation and characterization,
and so on. It is up to the readers to decide if this approach was successful. In any
case, the book is based on many literature sources, reflecting my experience as a re-
searcher, chemical engineer, manager and educator, first in a governmental research
institute, then in industry and finally in academia, while always maintaining very
close ties to industrial catalysis and catalytic engineering.

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Preface to the second edition
Apparently, this book devoted to the engineering aspects of heterogeneous catalysis
found its readership, as the publisher suggested to prepare the second edition. One
of the reasons was that the author, with experience in both industry and academia,
tried to combine both perspectives on catalysis, which are sometimes antagonistic
as illustrated in a somewhat provocative slide

Industrial perspective: Academic perspective: publish

should work in practice in high-impact factor journals
Real feedstock Model feedstock
Continuous reactors Often batch reactors
Simple and reliable catalysts Fancy catalysts
Detailed mass balance and adequate anlaytics Do not spent too much time on analytics
Deactivation: an issue to consider Deactivation better not to discuss
Kinetic and reactor modeling Kinetic and reactor modeling: What is this?

presented by the author at the International Congress on Catalysis in Beijing, 2016.

The first edition of the book was corrected and expanded in scope with more cover-
age of industrial preparation of catalysts and their technological implementations.

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Contents
Preface to the first edition VII

Preface to the second edition IX

About the author XI

1 The basics 1
1.1 Catalytic concepts 1
1.1.1 Definitions 1
1.1.2 Length and time scales in catalysis 5
1.1.3 Catalytic trinity: activity, selectivity, stability 7
1.1.4 Composition of catalysts 13
1.2 Reactivity of solids 16
1.2.1 Physisorption and chemisorption 17
1.2.2 Basics of chemisorption theory 20
1.2.3 Surface crystallography 21
1.2.4 Mechanisms of some catalytic reactions 24
1.3 Catalysis in industry and for environmental protection 30
1.4 Fuel cells and electrocatalysis 45
References 47

2 Engineering catalysts 49
2.1 Catalyst design 49
2.1.1 Being in shape 50
2.1.2 Catalysis informatics and high-throughput experimentation 57
2.2 Toolbox in catalysis 59
2.2.1 General overview of the characterization methods 59
2.2.2 Adsorption methods 62
2.2.3 Physisorption methods 63
2.2.4 Chemisorption 74
2.2.5 Temperature-programmed methods 77
2.2.6 Calorimetry 82
2.2.7 X-ray diffraction 83
2.2.8 X-ray photoelectron spectroscopy and X-ray fluorescence 84
2.2.9 Infrared and Raman spectroscopies 87
2.2.10 Catalyst particle size measurements 93
2.2.11 Electron paramagnetic/spin resonance 94
2.2.12 Mössbauer spectroscopy 96
2.2.13 X-ray absorption spectroscopy 98
2.2.14 Nuclear magnetic resonance 99
XIV Contents

2.2.15 Imaging of catalysts 101

2.2.16 Catalytic reactions: product analysis 110
2.2.17 Theory as a part of a toolbox 114
2.3 Preparation of catalytic materials 117
2.3.1 General overview 117
2.3.2 Unsupported metals 132
2.3.3 Preparation of bulk oxides by precipitation 135
2.3.4 Heteropoly acids 145
2.3.5 Catalyst supports 146
2.3.6 Supported catalysts 180
2.3.7 Catalyst forming operations 202
References 224

3 Engineering reactions 229

3.1 Introduction 229
3.2 Thermodynamics 229
3.3 Kinetics 232
3.3.1 Definitions 232
3.3.2 Reaction mechanism 237
3.4 Kinetics of complex reactions 247
3.4.1 Theory of complex reactions kinetics 247
3.4.2 Relationship between thermodynamics and kinetics 256
3.4.3 Non-ideal surfaces 257
3.4.4 Kinetic aspects of selectivity 261
3.4.5 Structure sensitivity 266
3.4.6 Mechanism-free kinetics – kinetic polynomial 268
3.4.7 What is behind a rate constant? 269
3.4.8 Apparent activation energy of complex reactions 272
3.4.9 Dynamic catalysis and deactivation 274
3.4.10 Mathematical treatment of experimental data 280
3.5 Mass transfer 284
3.5.1 Diffusion effects in heterogeneous catalysis 284
3.5.2 Reactor dependent external diffusion (interphase mass transfer,
film diffusion) 286
3.5.3 Calculation of diffusion coefficients 295
3.5.4 Size dependent internal (pore) diffusion 298
3.5.5 Non-isothermal conditions 307
3.5.6 Multiple reactions and diffusional limitations 311
3.5.7 Diffusion in micropores 314
3.5.8 Criteria for the absence of diffusional limitations 315
3.6 Catalytic reactors 320
3.6.1 Laboratory reactors 320
 Contents XV

3.6.2 Industrial reactors 328

3.6.3 Two-phase reactors 328
3.6.4 Three-phase catalytic reactors 336
3.6.5 Reactor modeling 365
3.6.6 Catalyst handing in a plant 377
References 386

4 Engineering technology 391

4.1 General structures of chemical processes 391
4.1.1 Safety in design 393
4.1.2 Conceptual process design: examples 394
4.1.3 Conceptual process design: general comments 404
4.1.4 Reactor selection 406
4.2 (Petro)chemical industry 423
4.3 Fluid catalytic cracking 423
4.3.1 Feedstock 424
4.3.2 Reactions/mechanism 426
4.3.3 Kinetics/process variables 431
4.3.4 Catalysts 433
4.3.5 Technology 437
4.4 Hydrocracking 441
4.4.1 Overview of hydrocracking 441
4.4.2 Hydrocracking catalysts 444
4.4.3 Hydrocracking technology 448
4.5 Steam reforming of natural gas 454
4.5.1 General 454
4.5.2 Process conditions for sulfur removal and primary reforming 457
4.5.3 Kinetics and mechanism 459
4.5.4 Technology 463
4.5.5 Catalysts 465
4.6 Ammonia synthesis 468
4.6.1 General 468
4.6.2 Thermodynamics 469
4.6.3 Kinetics 471
4.6.4 Catalysts 474
4.6.5 Reactors and process design 480
4.7 Oxidation 483
4.7.1 General 483
4.7.2 Epoxidation of olefins 485
4.7.3 Oxidation of alkanes to anhydrides 491
4.7.4 From alcohols to aldehydes: oxidative dehydrogenation of
methanol to formaldehyde 507
XVI Contents

4.7.5 Ammoxidation 512

4.8 Oxychlorination 518
4.8.1 Overview 518
4.8.2 Catalysts and reactors 520
4.8.3 Reaction network and kinetics 524
4.8.4 Technology 525
References 527

Acknowledgments 533

Recommended reading 535

Index 539
Acknowledgments
I would like to express my gratitude to very many colleagues who shared their ex-
perience on various aspects of catalysis, in particular to the late Prof. M.I. Temkin
and Dr. N.V. Kul’kova, as well as Dr. A.K. Avetisov (all from Karpov Institute of
Physical Chemistry), Dr. R. Touroude (University of Strasbourg), Dr. E. Schwab
(BASF) and Dr. I.L. Simakova (Boreskov Institute of Catalysis). The everyday inter-
actions with colleagues from the Laboratory of Industrial Chemistry and Reaction
Engineering at Åbo Akademi University (Dr. K. Eränen, Dr. N. Kumar, Prof. J.-P.
Mikkola, Dr. P. Mäki-Arvela and Prof. J. Wärnå) and collaboration with numerous
colleagues and PhD students from Åbo Akademi University and other institutions
are gratefully acknowledged. Please, forgive me for not mentioning you all. Very
special thanks go to my colleague, friend and brother-in-science Prof. T. Salmi,
who has influenced me through the decades in very many ways.
The moral support of my family was very important in writing the first and
the second edition of this book. I am especially grateful to E. Murzina for her techni-
cal and spiritual contribution and especially endless patience and tolerance.

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About the author
Dmitry Yu. Murzin studied Chemical Technology at the Mendeleev University of Chemical Technology
in Moscow, Russia (1980–1986) and graduated with honors. He obtained his PhD (advisor
Prof. M.I. Temkin) and DrSc degrees at Karpov Institute of Physical Chemistry, Moscow in 1989 and
1999, respectively. He worked at Universite Louis Pasteur, Strasbourg, France and Åbo Akademi
University, Turku, Finland as a post-doc (1992–1994). In 1995–2000 he was associated with BASF,
being involved in research, technical marketing and management. Since 2000 Prof. Murzin holds the
Chair of Chemical Technology at Åbo Akademi University. He serves on the editorial boards of several
journals in catalysis and chemical engineering field. He is an elected member of Academia Europaea
and the Finnish Academy of Science and Letters.
Prof. Murzin is the coauthor with Prof. T. Salmi of a monograph Catalytic Kinetics (Elsevier,
2005, second edition in 2016), and author of Chemical Reaction Technology (de Gruyter, 2015) and
Chemical Product Technology (de Gruyter, 2018). He holds several patents and is an author or coauthor
of approximately 750 journal articles and book chapters.

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1 The basics

1.1 Catalytic concepts

1.1.1 Definitions

Catalysis is a phenomenon related to the acceleration of rates of chemical reactions.

Such acceleration was recognized long time ago and put into practice even before
the concept of catalysts was formulated. For example, a German chemist Döbereiner
discovered that oxidation of hydrogen can occur in the presence of Pt already in 1823.
Such invention resulted in substantial utilization of Döbereiner lamps just within few
years after the discovery.
The available data on the 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, were summarized by a
Swedish scientist J. J. Berzelius in 1836 [1], 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”.
Catalytic power or force, according to Berzelius, meant that “substances (cata-
lysts) are able to awaken affinities which are asleep at this temperature by their
mere presence and not by their own affinity”.
This concept was immediately criticized by Liebig, as this theory was placing
catalysis somewhat outside of other chemical disciplines [2]. A catalyst was later
defined by Ostwald as “a compound that increases the rate of a chemical reaction,
but which is not consumed by the reaction” [3]. This definition allows for the possi-
bility that small amounts of the catalyst are lost in the reaction or that the catalytic
activity slowly declines.
From these definitions, a direct link between chemical kinetics and catalysis is
apparently clear as, accordingly, catalysis is a kinetic process. There are, however,
many issues in catalysis that are not directly related to kinetics, such as mech-
anisms of catalytic reactions, elementary reactions, surface reactivity, adsorption of
reactants on solid surfaces, synthesis and structure of solid materials and catalytic
engineering.
An important issue in catalysis is selectivity towards a particular reaction. For
example, transformation of synthesis gas (a mixture of CO and hydrogen) can lead
either to methanol (on copper) or high alkanes (on cobalt). For consecutive reac-
tions it could be desirable to obtain an intermediate product. In the oxidation of
ethylene such target is ethylene oxide, but not CO2 and water.
+ O2 +O2
CH2=CH2 CH2– CH2 CO2 + H2O
O

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2 1 The basics

Although formaly catalysts remained unchanged during a reaction, they are in-
volved in chemical bonding with the reactants during the catalytic process in a
cyclic process: the reactants are bound to one form of the catalyst, and the prod-
ucts are released from another, regenerating the initial state (Fig. 1.1).

R (reactant)

Catalyst Catalyst-R

P (product) Fig. 1.1: Catalytic cycle.

It should be also noted that although it is usually assumed that a catalyst participates
in the process but remains unchanged at the end, there could be major changes in its
structure and composition.
Potential energy diagrams for the catalytic and non-catalytic reactions presented
in Fig. 1.2 indicate that in both cases the reactions should overcome a certain barrier,
which is lower in the presence of a catalyst.

G x‡

Uncatalyzed

Catalyzed

A+B

A+B C+D
C+D

Reaction coordinate

Fig. 1.2: Potential energy diagram for catalytic and non-catalytic reactions. Changes of Gibbs
energy along the reaction coordinate.

As follows from Fig. 1.2, the change in the Gibbs free energy between the reactants
and the products ΔG is the same, independent of the presence or absence of a cata-
lyst, but providing, however, an alternative reaction path.

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 1.1 Catalytic concepts 3

A lower value of activation energy implies higher reaction rates, which could
be expressed through the rate constant k dependence on temperature:
− Ea
k = AT m e RT (1:1)

where A is the pre-exponential factor, Ea is the activation energy related to the po-
tential energy barrier and m is a constant. Equation (1.1) was proposed by Kooij and
van’t Hoff [4] to explain the temperature dependence of reaction rates and could be
derived from the transition state theory of Eyring and Polanyi [5]. Arrhenius [6] ap-
plied a slightly simplified form:
− Ea
k = ko e RT (1:2)

A decrease in activation energy and an increase in temperature lead to an increase

of the rate constant and thus of the reaction rate. Catalysts substantially accelerate
chemical reactions, enabling them to be carried out under the most favorable ther-
modynamic regime, and at much lower temperatures and pressures.
Equation (1.2) corresponds to an elementary reaction. In the case of complex re-
actions, it is appropriate to discuss the so-called apparent activation energy, which
can be expressed through the reaction rate r according to

∂ ln r ∂ ln r
Eact, apparent = −R = RT 2 (1:3)
∂1=T ∂T

Figure 1.3 also shows that if a catalyst is active in enhancing the rate of the forward
reaction it will do the same with a reverse reaction. As mentioned above, the catalyst

Gas-phase reaction

Ea
Energy

ΔH
Adsorption
E‡a
Product
Reaction Desorption

Reaction coordinate

Fig. 1.3: Potential energy diagram with catalyst binding.

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4 1 The basics

affects only the rate of the reaction, but not the thermodynamics (for example,
the Gibbs energy of the reaction is the same), the approach to equilibrium or
the equilibrium composition. Thus, in the case of a thermodynamically unfa-
vorable process, there is no hope of finding an active catalyst that will beat
thermodynamics.
Instead, as a first step the reaction conditions (temperature, pressure and re-
actant composition) must be optimized to maximize the equilibrium concentration
of the desired product. Once suitable reaction conditions are identified the cata-
lyst screening is performed with the aim of finding a suitably active and selective
material.
The statement – that thermodynamics frequently limits the concentration of
a desired product and that a catalyst search will not help – sounds very straight-
forward and obvious. The author knows, however, a case where modern methods
of high throughput experimentation were used in industry to find an active cata-
lyst for a reaction with a maximum conversion allowed by thermodynamics of
only 1%.

Several years ago I started to be involved in a project related to the synthesis of dimethyl car-
bonate from methanol and CO2. The literature was full of papers describing various catalytic
systems and the mechanisms behind their catalytic action. Unfortunately, explicit data on
conversions and thermodynamics were absent from the literature. The PhD student doing the
experiments was initially very frustrated when, after a couple of months of catalyst screening,
very low conversions in the range of 0.1% were obtained. After repeated advises finally ther-
modynamics was calculated and it became clear that the reaction is heavily thermodynami-
cally limited. This switched the strategy from catalyst screening to finding a means of shifting
reaction equilibrium, in that case by in situ water removal.

Figure 1.2 represents a simplified situation, not taking into account the binding of
the reactant to the catalyst (called adsorption in heterogeneous catalysis), which is
illustrated in Fig. 1.3. The energy barrier between the catalyst-substrate and the
transition state should be lower than between the substrate and the transition state
in an uncatalyzed reaction (Fig. 1.3).
If the energy is lowered too much when the substrate is bound to the reactant
during adsorption, and the activation energy in the catalytic reaction is still rather
high compared to non-catalytic reactions, then the reaction rate is slow and catalysis
is not effective. In addition, if the binding of the products is too strong they will not
be desorbed (released) from the catalyst. At another extreme, if the binding is too
weak then the catalytic cycle could not proceed as effectively. It is thus intuitively
clear that bonding between a catalyst and a reactant should not be too strong. This
principle was first put forward by Sabatier [7], who proposed that a catalytic reaction
has an optimum (maximum) rate as a function of the heat of adsorption, and then
further developed by Balandin [8], who introduced volcano plots, relating catalytic
activity with adsorption energy (Fig. 1.4).

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 1.1 Catalytic concepts 5

1,000 450 °C
100 bar
100 3:1 H2/N2

3
NH
%
10
01
0.
1 Ru
3
NH
Os
TOF (s–1)

1%

0.1
0.

0.01 Fe
3
NH

Co
1%

0.001

0.0001
3
NH

0.00001 Mo Ni
%
10

0.000001
–150 –100 –50 0 50 100
Relative nitrogen binding energy (kJ/mol)

Fig. 1.4: Activity (turnover frequency) in ammonia synthesis with different catalysts as a function of the
relative nitrogen binding energy, 450 °C, 100 bar, H2/N2 =3. (Reproduced with permission from [9]).

Sabatier is known for his experimental work on hydrogenation of organic com-

pounds, for which he was awarded the Nobel Prize in 1912. Together with Senderen,
he discovered that traces of nickel catalyze methanation of CO2:

400  C
CO2 + 4H2
! CH4 + 2H2 O
Pressure

This reaction is witnessing now a renaissance associated with a strong desire to di-
minish CO2 emissions. This reaction has also a special application, as it can be ap-
plied to produce water from exhaled CO2 in confined spaces (e.g., submarines or
the International Space Station). An important issue related to the latter applica-
tions is efficient and rather small-scale generation of hydrogen.

1.1.2 Length and time scales in catalysis

Heterogeneous catalysis covers a wide scale, from a molecular scale (nm) of an

active site (Fig. 1.5A) to a catalytic reactor (m) scale (Fig. 1.5B). Catalysis occurs
on the surface of solid materials, representing the chemistry in two dimensions.
Active sites of heterogeneous catalysts are related to a molecular or atomic level
arrangement of atoms, responsible for catalytic properties (Fig. 1.5A). At this sub-
nanometer level, chemical reactions proceed that involve the rupture and

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6 1 The basics

1–2 m

H2 (g)

10–20 m
Attractive interaction H2 (adsorbed on Pt)
2H (adsorbed
on Pt)

Re-face adsorption

(A) (B)

Fig. 1.5: Length scales in catalysis ranging from (A) an active site to (B) a reactor.

formation of chemical bonds. The reactivity of solids and mechanisms of cata-

lytic reactions will be briefly reviewed here in Chapter 1.
Catalytically active particles are typically between 1 and 10 nm in size (Fig. 1.6A)
and are located inside the pores of a support material (μm level, Fig. 1.6B). Chemical
composition, texture of materials and pore structure are very important issues, re-
lated not only to catalysis, but also to the transport of molecules through the pores
to the active sites. Of particular interest are the size, shape, structure and composi-
tion of the active particles.

1 cm
(A) (B) (C)

Fig. 1.6: Different levels in catalysis. (A) active site level (subnanometer scale), (B) catalyst particle
powder (μm) level), (C) shaped catalyst (mm) level. Photos courtesy of Dr. E. Toukoniitty.

Catalysts in the form of powders can be used in industrial processes only in limited
cases. Shaped catalysts, in the form of extrudates, pellets and tablets on a mm scale
(Fig. 1.6C), are introduced into industrial reactors. Engineering of such materials

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 1.1 Catalytic concepts 7

requires addressing porosity, mechanical strength, and attrition resistance in addi-

tion to activity, kinetics and mass transfer.
The engineering of catalytic materials through tailor-made preparation and the
understanding of kinetic and transport phenomenon will be discussed in Chapters 2
and 3. Chapter 3 also covers the modeling of catalytic reactors.
It should be noted that in industrial reality the mass and heat transport through
the catalyst bed can be as important as intrinsic kinetics.
Finally, the performance of a catalyst should be viewed as part of an overall
process that includes feed treatment, separation, etc., in addition to chemical re-
actions. For example, issues such as catalyst mechanical stability, sensitivity to
trace impurities in the reactant feed (as industrial feeds are rarely pure) and
leaching of the active phase can be very crucial to industrial operation. Basic
principles of designing catalytic processes (plant level, Fig. 1.5B) will be described
in Chapter 4, with examples for several catalytic processes, representing different
type of materials (supported metals, oxides, zeolites), catalyst shapes (powder, extru-
dates, tablets, irregular grains) and different type of reactors (with fixed and moving
catalysts).
The time scale of catalytic events varies from the picosecond level of bond
breaking and formation to the seconds/minutes level for completion of a catalytic
cycle. Pore diffusion may take seconds and minutes, while the residence times of
molecules in reactors may vary from seconds (fluidized catalytic cracking) upwards
(coke can stay for months or years on the catalyst before eventual regeneration or
disposal).

1.1.3 Catalytic trinity: activity, selectivity, stability

The main requirements of a catalyst for an industrial process depend on the trinity
of catalysis: activity, selectivity and stability. Activity refers to the ability to conduct
a process within a reasonable contact time, which influences the reactor dimensions
and process capacity. Insufficient activity in principle could be compensated by
higher catalyst amounts or some other means, such as higher temperature. Catalyst
selectivity is probably the most important characteristics of a catalyst, which should
be also sufficiently stable under operation conditions.
The reaction rate is calculated as the converted amount of the substance with
time relative to the amount of catalyst (mass or volume), specific surface area or to
the amount of active sites. In cases when the rate is defined per catalyst mass, the
unit of measurement is mol g–1 h–1.
The rate per amount of sites available for the reaction (exposed sites) is denoted
in heterogeneous catalysis as the turnover frequency (TOF) [or turnover number
(TON)], which is defined as the number of molecules reacted per site per unit time:

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TOF = Amount of reacted substrate=ðactive site x timeÞ = mol mol − 1 s − 1 = s − 1 (1:3)

Even if the TOF concept is widely applied, its application is not straightforward,
because TOF depends on kinetics, i.e., the concentration of reagents and temper-
ature, and thus strictly speaking should be referred to particular conditions.
Typical values of TOF for industrially relevant reactions are in the range 10–2 ÷
102 s–1.

Exercise 1.1: Fig. E1.1 displays a fixed-bed reactor where there is a certain molar flow in the reac-
tor n_ Ain and out of the reactor n_ Aout . In such reactors, during catalyst screening conversions at
constant space velocity [volume flow rate (m3 s–1) relative to catalyst (kg)] are compared.
mcat

n•A n•A
in out

• •
n = cA V

Fig. E1.1. Fixed-bed reactor.

Calculate:

1. The conversion rates per catalyst volume

2. Weight
3. Surface
4. TOF (metal density 1,015 sites cm−2)

for a continuous reaction of benzene hydrogenation over 5 cm3 5 wt% Pd on a support with the
catalyst density of 0.9 g cm−3 and the catalyst surface area of 250 m3 g−1 (5% of which is cov-
ered by Pd) when the molar flow of benzene in the reactor is 4 mol h−1 and the outlet flow is
3.7 mol g−1.

Hints: The rates are defined in the following way:

– per volume rA = –dnA/(Vcatdt) = − dn_ A =Vcat

– per weight rA = –dnA/(mcatdt) = –dnA/Vcat ρcatdt)
– per surface rA = –dnA/(Scatdt) = –dnA/(Srel mcatdt)
– per atom of Pd rA = –dnA/(npddt)

The number of mols of Pd should be calculated using the following strategy. From the overall sur-
face, the surface of Pd atoms could be computed. This in turn gives the number of atoms of Pd if
the surface density is known. Finally the number of moles of the metal can be easily calculated.

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 1.1 Catalytic concepts 9

Exercise 1.2: Lilja et al. [10] investigated esterification of propanoic acid with methanol over a hetero-
geneous fiber catalyst. The temperature dependence is presented in Fig. E1.2.
1

0.9

0.8

0.7
c/c0

0.6
55 °C
0.5
60 °C

0.4
63 °C

0.3
0 50 100 150
Time (min)

Fig. E1.2: Esterification kinetics of propanoic acid with methanol (the initial molar ratio 1:1) as a
function of temperature.

Calculate:
1. The activation energy, based on initial rates (10 min).
2. Gibbs energy of the reaction at 60 °C based on experimentally recorded equilibrium data.
3. Reaction enthalpy at 60 °C, assuming that the entropy change during the reaction is negligible.
Hints:

– Initial rates (ΔC/dt) should be calculated from the slopes for the initial period when the rates
are not changing with time.
– Composition at equilibrium defines equilibrium constant (Keq = Cproducts/Creactants) and subse-
quently Gibbs energy (ΔG = –RTlnK).
– Enthalpy of the reaction is defined through Gibbs energy: ΔG = ΔH – TΔS.

Exercise 1.3: Steam reforming of heptane was performed over a 6 wt% cobalt catalyst supported on
γ-alumina. The amount of catalyst was 15 cm3. Knowing conversion and specific activity calculates
the molar feed rate, the rate per catalyst volume and catalyst weight, and apparent activation
energy.

o
C Conversion of heptane (%) Specific catalytic activity (mol/(mol(Co) s))
  .

  .

  .

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10 1 The basics

The turnover number is a useful concept, but is limited by the difficulty of determin-
ing the true number of active sites. The situation is somewhat easier for metals, as
chemisorption, which will be discussed further (Chapter 2, Section 2.2.4), could be
used to measure the exposed surface area.
For some reactions (structure insensitive) the rate is independent on size, shape
and other physical characteristics, while for structure-sensitive reactions the rate de-
pends on the detailed surface structure.
In order to increase turnover number it is obvious that the number of exposed
sites should be increased, which is possible with small sizes of active particles pro-
viding high surface area per unit volume (Fig. 1.7). This can be achieved with the
catalyst particles in the nanoscale range, thus placing catalysts in the domain of
nanomaterials.

1.0
NS/NT

0
1 1,000 Fig. 1.7: Ratio of surface (NS) to total (NT) atoms as a
dcluster (Å)
function of cluster size dcluster.

It should be noted that many granting agencies are somewhat reluctant to con-
sider heterogeneous catalysis as a part of nanoscience and nanotechnology, espe-
cially in comparison with some emerging applications. This is probably because
catalysis is a more established concept, with many dozens of decades of experi-
ence in synthesis of such materials as supported metals and zeolites.
Small particles of the active catalyst alone cannot provide thermostable highly
active catalysts because of sintering of them at conditions of catalyst preparation
and catalysis. Moreover, the separation of reaction products from nanosized cata-
lysts is far from being trivial, in many cases even impossible. Therefore an active
phase (responsible for activity and selectivity) is usually deposited on a thermosta-
ble support (Fig. 1.8), which also provides the required shape, mechanical strength
and pore structure.
Expensive active compounds (such as precious metals) are typically prepared
with the objective of maximizing the active surface area per unit weight of the ac-
tive compound, which is achieved at low loadings and rather small metal clusters.

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 1.1 Catalytic concepts 11

Without support

With support,
no sintering

Fig. 1.8: Supported active phase. (Reproduced with permission from [11]).

For the less expensive active phase (supported base metal catalysts) the target is
maximum active surface area per unit volume, thus allowing higher loading of the
support with the active phase.
Fig. 1.8 depicts a simplified view on the catalyst nanocluster. In fact, the cluster
can contain different types of sites (Fig. 1.9A), with different binding to neighbor
atoms and thus differences in the ability to bind (adsorb) reacting molecules. As a
consequence, we can observe notable differences between the reactivity of different
surface atoms and active sites (edges, corners and faces as shown on Fig. 1.9B).

Face Corner Edge

atom atom atom

Adatom
Adatom
Corner
atom Edge
Corner

Edge
atom Corner
atom
Face
Corner Face
atom atom
Adatom Edge
(A) atom (B)

Fig. 1.9: Different types of sites in a nanosized catalyst.

By controlling the amount of different surface sites (atom) we can, in principle, con-
trol catalyst reactivity and selectivity. There are however practical challenges in the
preparation of a cluster with a desired size and a narrow cluster size distribution.

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12 1 The basics

Relative amounts of surface atoms with different reactivity vary as a function of

metal particle size, thus leading to structure sensitivity (TOF dependence on the
cluster size, Fig. 1.10).

III 6

TOF (s–1)
TOF

I 4
II

Diameter 2 4 6 8
(A) (B) Cluster size (nm)

Fig. 1.10: (A) I, II correspond respectively to structure sensitivity, while III represents a structure
insensitive reaction and (B) ethene hydrogenation on Pd/TiO2 (data from [12]).

The temperature dependence of heterogeneous catalytic reactions was partially ad-

dressed above with the point that, in general, activity increases with temperature.
Increasing the temperature, however, shortens the life span of the catalyst and typi-
cally increases the rate of undesirable reactions. Moreover, a catalyst with an extremely
high reaction rate will certainly exhibit large mass- and heat-transfer limitations.
Although the catalyst must possess high activity and long-term stability, the most
important characteristic is selectivity, the ability to direct transformation of reactants
to the desired product along one specific pathway. For many reacting systems, various
reaction paths are possible, and the catalyst type often determines the path that will
be followed. A catalyst can increase the rate of one reaction without increasing the
rate of others. In general, selectivity depends on pressure, temperature, reactant com-
position, conversion and the nature of the catalyst. Therefore, selectivity should be re-
ferred to specific conditions.
There are two definitions of selectivity that are commonly used. Integral selec-
tivity is defined as the ratio of the desired product per consumed reactant, while
differential selectivity corresponds to the ratio of the desired product formation rate
to the rate of reactant consumption.
Although there is always a desire to have a stable catalyst for a particular reac-
tion, strong catalyst deactivation does not necessarily mean that in such a case a
particular catalyst cannot be applied at all. In fact, it is only in theory that the cata-
lyst remains unaltered during the reaction. Actual practice is far from this ideal, as
the progressive loss of activity could be associated with coke formation, attack of

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 1.1 Catalytic concepts 13

poisons, loss of volatile agents and changes of crystalline structure, which cause a
loss of mechanical strength. There are industrial examples, discussed in Chapter 4,
that show successful industrial implementation of catalytic reactors in combination
with continuous regeneration, when the catalyst life is merely few seconds.
Because of the extreme importance of catalyst deactivation, the kinetic aspects of
this phenomenon will be treated in a separate section (Section 3.4.5).
In summary, it can be concluded that the target priorities in catalyst develop-
ment and applications are typically: selectivity > stability > activity.

1.1.4 Composition of catalysts

The catalytic properties of activity, selectivity and stability are closely related to the
composition of the catalyst. Typical catalytic materials are shown in Fig. 1.11. Most
catalysts are multicomponent and have a complex composition. Components of the
catalyst include the active agent itself and may also include a support, a promoter,
and an inhibitor.

Dispersed Pt/Al2O3, Ni/Al2O3, Pd/Al2O3

Metals Porous Raney nickel
Bulk Pt, Pd, Ag gauze

Single Al2O3, Cr2O3, V2O5

Oxides Dual, complex SiO2/Al2O3, CuCr2O4
Catalytic materials

Dispersed NiO/Al2O3, MoO3/Al2O3

Sulfides MoS2/Al2O3, WS2Al2O3

Acids SiO2–Al2O3; zeolites; natural clays

Base CaO, MgO, K2O, Na2O

Fig. 1.11: Catalytic materials.

For example, metal catalysts are not in their bulk form but they are generally dis-
persed on a high surface area insulator (support) such as Al2O3 or SiO2. Many het-
erogeneous catalysts need supports, which, from an economic viewpoint, are a
means of spreading expensive materials and providing the necessary mechanical
strength, heat sink/source, help in optimization of bulk density and in dilution
of an overactive phase. The supports also provide geometric functions (an

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14 1 The basics

increase in surface area, optimization of porosity, crystal and particle size)

and chemical functions (improvement of activity, minimization of sintering,
and poisoning, as well as the beneficial effect of spillover, which will be dis-
cussed later).
Sintering of supports can start at a temperature substantially lower than the
melting point, thus supports with high melting points are applied, such as alumina
or silica. In particular, alumina is mainly preferred because of favorable bulk density,
thermal stability and price. It is applied in the form of γ-alumina in many reactions,
such as hydrotreating, hydrocracking, hydrogenation, reforming, oxidation, and so
on. Another phase of alumina (α-alumina) that stable at very high temperatures is
used for steam reforming of natural gas.
Silica has a lower bulk density, which means that more reactor volume is needed
for the same active phase loading on the support. Silica is more liable to sintering
above 900 K than alumina and is volatile in the presence of steam and elevated pres-
sures. There are still several applications (polymerization, oxidation, hydrogenation)
where silica is used, and a very specific example is the oxidation of sulfur dioxide to
trioxide (Fig. 1.12).

20 mm 12 mm 10 mm 9 mm 6 mm
rings daisy rings daisy cylinder

Fig. 1.12: Vanadium-based catalysts supported on silica for sulfur dioxide oxidation.

Although there were catalyst formulations using silica synthesized from water glass
(sodium silicate), the catalyst manufacturers predominantly use kieselguhr. More
details of the manufacturing are provided in Section 2.3.5.4. This diatomaceous
earth (diatomite) is a form of silica composed of the siliceous shells of unicellular
aquatic plants of microscopic size. Kieselguhr is heat resistant and, in addition to
catalytic applications, has been used as an insulator, a component in toothpaste
and an abrasive in metal polishes. The specific features of the diatomaceous earth
(surface area 20–40 m2) are related to small amounts of alumina and iron as part
of the skeletal structure and a broad range of pore sizes. The main components of
the sulfur dioxide oxidation catalyst include SiO2 as a support, vanadium, potas-
sium and/or caesium and various other additives. The reaction actually occurs
within a molten salt consisting of potassium/caesium sulfates and vanadium sul-
fates, coated on the solid silica support. Vanadium is present as a complex sulfated
salt mixture and not as vanadium pentoxide (V2O5).

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 1.1 Catalytic concepts 15

Aluminosilicates, either amorphous or crystalline (zeolites), can be used as

supports and catalysts (as zeolites) because of their acidic properties: Active car-
bon is another support that is often applied, mainly for the synthesis of fine
chemicals in various hydrogenation reactions. Other supports include clays,
ceramic (cordierite), titania (for selective oxidations and selective catalytic re-
duction of NOx) as well as magnesium aluminate (steam reforming of natural
gas).
While selecting a support for a particular reaction, various physical and chemical
factors should be carefully considered. The physical factors are the desired surface
area and porosity, thermal conductivity, mechanical stability, resistance to coking,
and the possibility of applying a desired geometrical shape; while the chemical fac-
tors are the activity of the support, chemical interactions between the active catalyst
phase or the products/reactants and the support, and the resistance to poisoning.
Details on the various supports used in catalysts and their preparation will be given
in Chapter 2.
Sometimes both the metal and the support act as catalysts, which is called bi-
functional catalysis. An example of this is platinum dispersed on alumina used in the
gasoline reforming. Platinum is active in dehydrogenation reactions of linear alkanes
to linear alkenes which further undergo skeletal isomerization on alumina. Formed
branched olefins are hydrogenated on platinum. The active agent, discussed above is
the component, which causes the main catalytic action, while a promoter (being in-
active, when added into the catalyst in small amounts) improves activity, selectivity
or stability, prolonging the catalysts lifetime.
There are various types of promoters that improve the catalyst in different ways.
Textural promoters are inert substances, which inhibit sintering of the active catalyst
by being present in the form of very fine particles. Usually they have a smaller parti-
cle size than that of the active species, are well-dispersed, do not react or form a solid
solution with the active catalyst and have a relatively high melting point. Oxides
(with melting points in parentheses) such as Al2O3 (2,027 °C), SiO2 (1,700 °C), ZrO2
(2,687 °C), Cr2O3 (2,435 °C), CeO2 (2,600 °C), MgO (2,802 °C) and TiO2 (1,855 °C) can be
used as textural promoters.
Structural promoters change the chemical composition, produce lattice defects,
change the electronic structure and the strength of chemisorption. For example, Pb,
Ag, or Au can be used as structural promoters for palladium catalysts applied in se-
lective hydrogenation of acetylene to ethylene.
An inhibitor is the opposite of a promoter. When added in small amounts, it
diminishes activity, selectivity or stability. Inhibitors are useful for reducing the
activity of a catalyst for an undesirable side reaction. For example, silver sup-
ported on alumina is an excellent oxidation catalyst, widely used in the production
of ethylene oxide from ethylene. However, under the same conditions complete ox-
idation to carbon dioxide and water also occurs, resulting in mediocre selectivity

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16 1 The basics

to C2H4O. It was found that the addition of halogen compounds to the catalyst in-
hibits this complete oxidation and results in satisfactory selectivity [13].
Metal oxides usually consist of bulk oxides. As semi-conductors, metal oxides
catalyze the same type of reactions as metals but are used in processes that require
higher temperatures. Often a multicomponent mixture of various oxides is used to
increase the catalytic activity.
For example: transition metals such as MoO3 and Cr2O3 are good catalysts for
the polymerization of olefins; a mixture of copper on chromium oxides, called cop-
per chromite, is used for hydrogenation; and a mixture of iron and molybdenum
oxide, called iron molybdate, is used for formaldehyde formation from methanol.

1.2 Reactivity of solids

Heterogeneous catalysts in industrial applications have a variety of different geo-

metrical shapes and porosity. Therefore, understanding of mass and heat transfer
in heterogeneous catalysis is essential for the description of the processes involved
in transporting the reactants to the catalyst surface and the transfer of energy to
and from catalyst particles.
The following steps are usually followed:
1. External diffusion: transfer of the reactants from the bulk fluid phase to the
fluid-solid interface (external surface of the catalyst particle).
2. Internal diffusion (if the particle is porous): transfer of the reactants into the
pores of a catalyst particle.
3. Adsorption: physisorption and chemisorption of the reactants at the surface sites
of the catalyst particle. During adsorption the reactants become attached to the
surface either by physical (van der Waals) or chemical forces, thus significantly
decreasing the entropy compared to the gas- or liquid-phase. This leads to nega-
tive ΔS, thus for the Gibbs energy (ΔG = ΔH – TΔS) to be negative, the heat of
adsorption (ΔH) should be negative and adsorption should be exothermic.
4. Surface reaction: the chemical reaction of adsorbed species to produce ad-
sorbed products. It can proceed by formation of precursors on the catalyst sur-
face, and surface diffusion of these as well as of other adsorbed species to the
reaction sites.

Langmuir advanced the first kinetic approach in catalysis based on physico-

chemical understanding of the underlying processes [14], by applying the mass ac-
tion law to reactions on solid surfaces. This was done by supposing that the rate of
an elementary reaction is proportional to the surface concentration (coverage) of
reactive species adsorbed on the surface. The Langmuir model of uniform surfaces
assumes that all the surface sites are identical, binding energies of the reactants are
the same independent of the surface coverage, and interactions between adsorbed

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 1.2 Reactivity of solids 17

species may be neglected. This ideal adsorbed layer is considered to be similar to

ideal solutions with fast surface diffusion, thus allowing an application of the mass
action law.
Typically two main types of mechanisms are considered for a bimolecular reac-
tion. Either one reactant (A) is adsorbed and the other (B) approaches from the fluid
phase (the Eley-Rideal mechanism, see Fig. 1.13A) or a reaction occurs because of
the interaction of two adsorbed reactants A and B (the Langmuir-Hinshelwood
mechanism, see Fig. 1.13B). The products are then released either directly into the
fluid phase or first through adsorbed product species followed by desorption.

A* A* B*

(A) (B)

Fig. 1.13: (A) the Eley-Rideal and (B) the Langmuir-Hinshelwood mechanisms of catalytic reactions.

Detailed analysis of catalytic kinetics for various reaction mechanisms, including

Eley-Rideal and Langmuir-Hinshelwood ones, will be provided in Chapter 3.
Further steps in heterogeneous catalysis are:
5. Desorption: the release of adsorbed products by the catalyst.
6. Internal diffusion: the transfer of products to the outer surface of the catalyst
particle.
7. External diffusion: the transfer of products from the fluid-solid interface into
the bulk fluid stream.

1.2.1 Physisorption and chemisorption

Adsorption in heterogeneous catalysis takes place before surface reactions and thus
deserves special consideration.
In the case of chemisorption of a molecule (adsorbate), a chemical bond is
formed between the molecule and the surface (adsorbent). For chemisorption, the
adsorption energy is comparable to the energy of a chemical bond. The molecule
may chemisorb intact or it may dissociate with breaking chemical bonds. The chem-
isorption energy is 30–70 kJ mol–1 for molecules and 100–400 kJ mol–1 for atoms.

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18 1 The basics

In physisorption, the bond is a van der Waals interaction and the adsorption
energy is typically 5–10 kJ mol–1, which is much weaker than a typical chemical
bond. As a consequence the chemical bonds in the adsorbing molecules remain in-
tact. As the van der Waals interactions between the adsorbed molecules are similar
to the van der Waals interaction between the molecules and the surface, many
layers of adsorbed molecules may be formed. Some other features of physisorption
and chemisorptions are presented in Tab. 1.1.

Tab. 1.1: Comparison between chemisorption and physisorption.

Features Chemisorption Physisorption

Adsorbent Sorbent and crystallographic plane Independent on the surface

specificity dependent structure
Type Can be dissociative and irreversible Non-dissociative and reversible
Temperature A wide range Near or below boiling point of
adsorbate
Heat of A wide range (– kJ mol–) Close to heat of liquefaction
adsorption (– kJ mol–)
Saturation Monolayer coverage Multilayers are formed
Kinetics Can be activated, for example, slow Fast, non-activated

Fig. 1.14 shows potential energy diagrams of chemisorption and physisorption.

When approaching the surface a molecule encounters the weak van der Waals inter-
actions. If the molecule loses energy upon interactions with the surface, it may be
trapped in the weak attractive potential at a distance corresponding to the sum of
the van der Waals radii of the molecule and the surface atom, and thus become phys-
isorbed on the surface. Moving even closer to the surface will result in repulsion.

E (d)

Physisorption

d (nm)

Chemisorption

Fig. 1.14: Potential energy curves for chemisorption and physisorption.

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 1.2 Reactivity of solids 19

After rearranging its electronic configuration and interacting with the electron
clouds of the metal, the molecule, however, may become chemisorbed.
The equilibrium position of this new chemisorbed state is at a shorter distance
than for physisorption, Moreover, for chemisorption the potential energy curve is
dominated by a much deeper chemisorption minimum. The chemisorption curve in-
tersects with the physical adsorption curve at a value close to zero in the energy
axes. For a clean surface this barrier between physisorption and chemisorption is
below zero, thus chemisorption on clear surfaces is usually fast and non-activated.
Dissociative chemisorption can occur for a diatomic molecule.
The structure of solid surfaces is fairly complicated (Fig. 1.15) as they are usu-
ally complex and rough, and consisting of high Miller index (to be discussed later)
planes with different energetics.

Fig. 1.15: Surface structure.

Moreover, adsorbed species can form different types of complexes on the surfaces
(some examples are given in Fig. 1.16), which might interact with each other (lat-
eral interactions).
As a result, the heat of adsorption might decrease with coverage, with the mini-
mum of adsorption energy decreasing in magnitude. This leads to a situation when
such a decrease of the adsorption heat will lead to an activation energy of adsorp-
tion (Fig. 1.17).
Physisorption at low temperatures is a standard method for determination of
the surface area of a catalyst, pore size and volume, and pore size distributions;
this will be discussed in detail in Chapter 2 along with the application of chemi-
sorption measurements for active surface area, surface site energetics and deter-
mination of catalytic sites.

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20 1 The basics

O
C C C C C C
H C C
M M M M M M M M M M M M

C O
M M
M C C
C C C M M M M H
M M M M M M M M M M

C C M

C C O O M
M
C C M M M
M M M

Fig. 1.16: Examples of the complexes that could be formed on the solid surfaces. M, metal site.

E (d)

d (nm)

Fig. 1.17: Chemisorption proceeding with activation.

1.2.2 Basics of chemisorption theory

Chemisorption of catalytically active metals that have 6–10 d electrons is usually

considered for analyzing the behavior of d electrons. There is an overlapping of or-
bitals, when, if large, gives a broad band and strong interactions. Such band is a
collection of a large number of molecular orbitals that form a continuum when they
are close to each other. In metals the bands are filled with valence electrons up to
the Fermi level or to the highest occupied state (Ef) analogously to the highest occu-
pied molecular orbital (HOMO). If an empty level exists below Ef it will be filled in-
stantaneously. A band behaves like a molecular orbital, in a sense that lower levels
are bonding, upper levels are antibonding and middle levels are non-bonding.

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 1.2 Reactivity of solids 21

Behavior of d orbitals is important in understanding catalytic activity of the tran-

sition metals. Details on the reactivity of transition metals on the basis of d-band
analysis are provided in specialized textbooks [15].
When an atom is chemisorbed, bonding and antibonding chemisorption orbitals
should be considered. The strength of chemisorption depends on the position of the
bonding orbital. If interactions of an atomic orbital and a d-band are strong then
there is substantial splitting between the bonding and antibonding orbitals. The anti-
bonding orbitals are unoccupied, leading to strong chemisorption (Fig. 1.18A). In the
opposite case of weak interactions, small splitting can result in an antibonding or-
bital falling below E. Such an orbital is occupied, leading to repulsive interactions
and thus no chemisorption (Fig. 1.18B).

Evac Evac

Antibonding Antibonding

EF EF
d-Band d-Band

Bonding Bonding
s-Band s-Band No bonding

d-Metal Adsorbed Free d-Metal Adsorbed Free

(A) atom atom (B) atom atom

Fig. 1.18: Chemisorption of an atom. (A) strong chemisorption, (B) no bonding. (From [15]).

In the case when a molecule is chemisorbed, chemisorption orbitals are formed from
both bonding and antibonding molecular orbitals of a molecule (Fig. 1.19).
Filling of the orbital of the molecule, which was originally antibonding, makes
interactions with the surface stronger, while at the same time weakening the intra-
molecular bond of the adsorbed molecule and facilitating, for example, dissociation
of a molecule.
Filling of the bonding orbital is called donation, favoring “on-top” adsorption
(discussed in Section 1.2.3). Filling of the antibonding orbital, which binds a mole-
cule additionally to the surface, is called “back donation”.

1.2.3 Surface crystallography

The crystallographic structure of the metals that are most important for catalysis is
presented in Fig. 1.20(A).

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22 1 The basics

σ-Orbitals σ*-Orbitals

Evac Antibonding

σ*
Antibonding
EF 1s 1s
Bonding

Bonding

d-Metal
Adsorbed molecule Free molecule

Fig. 1.19: Chemisorption of a molecule. (Reproduced with permission from [15]).

Fig. 1.20B shows three most important metal crystal structures: face-centered
cubic (fcc), hexagonally close-packed (hcp) and body-centered cubic (bcc). Other
structures can exist for more complex materials such as oxides, the bulk structures
of which can be represented by positive metal ions (cations) and negative O ions
(anions).
For catalysis, which is a surface phenomenon, it is not the bulk structure that is
important, but the exposed surface. As energy is required to cleave the surface, the
total energy is higher and the surface free energy is always positive.
Reactivity of the surface depends on the number of surrounding atoms, or in
other words, on packing. Dense regular packing (Fig. 1.21) has lower energy.
In order to discuss surface crystallography – the two-dimensional analogue of
bulk crystallography – the nomenclature of various metal planes (Fig. 1.20) should
be explained. The assignment of indices is done using the following approach. A
particular surface plane of a crystal is considered and is shown in Fig. 1.22.
Firstly the intercepts on the x-, y- and z-axes are identified. In Fig. 1.22 the inter-
cept on the x-axis is at x = a [at (a,0,0)], corresponding to the unit cell distance. The
surface is parallel to the y- and z-axes, thus there are no intercepts on these two axes
and they are considered to be at infinity (∞). The intercept coordinates on the x-, y-
and z-axes (a, ∞,∞) are converted to fractional coordinates by dividing by the respec-
tive cell-dimension (a) to give the fractional intercepts: (1, ∞,∞). The reciprocal values
of the fractional intercepts are 1, 0 and 0, yielding the Miller indices (100), which is
specified without being separated by any commas or other symbols (Fig. 1.23).
The surfaces in Fig. 1.23 are different in terms of their coordination or number of
neighbors. The most stable solid surfaces are those with a high surface atom density

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 1.2 Reactivity of solids 23

bcc hcp fcc

(A)

bcc hcp fcc

(100) (110) (111)

(B)

Fig. 1.20: (A) Crystallographic structure of some catalytically active metals. (B) Metal crystal
structures.

that contains surface atoms with a high coordination number. For face-centered
cubic structures (representative of Ni, Cu, Pt, Pd, Ir, Au, Ag, etc.) the following order
of stability is valid: fcc (111) > fcc (100) > fcc (110). The most stable surface is then the
most closely packed. At the same time, the more open the surface is the more reactive
it is. It should be mentioned that surfaces of real catalysts are usually rough and con-
sist of high Miller index planes.
Figure 1.24 shows the most common adsorption sites: on-top, bridge (long or
short) and hollow (three-fold or four-fold).
From the discussion above it is apparently clear that the classical treatment of
adsorption and kinetics, which assumes the same adsorption strength for all sites, is
an oversimplification. In addition to different energetics of adsorption an adsorbed
molecule can bind to several metal sites and there could be interactions between

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24 1 The basics

Energy
Typical neighbor
bond length

r
Typical neighbor
bond energy

(A)

Energy
Typical neighbor
bond length

r
Typical neighbor
bond energy

(B)

Fig. 1.21: (A) Dense, regular packing. (B) Non-dense, random packing.

(x,0,0)
x Fig. 1.22: Assignment of indices.

adsorbed species. This complicates the mathematical treatment of adsorption and ki-
netics, which will be addressed in detail in Chapter 3.

1.2.4 Mechanisms of some catalytic reactions

There are countless heterogeneous catalytic reactions with very many different
types of catalysts. It is thus impossible in a textbook focused on engineering rather
than on mechanisms of catalysis to describe even a small fraction of these, there-
fore only a few generic examples for some typical reactions will be mentioned here.

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 1.2 Reactivity of solids 25

(100) (110) (111)

Fig. 1.23: Various metal surface planes.

(100) (110) (111)

1 2 1 2 1 2

6
5
4
3 4

1 On top 2 Bridge 3 Long bridge

Threefold Threefold
4 Fourfold hollow 5 6
hollow FCC hollow BCC

Fig. 1.24: Adsorption sites. (From [15]).

1.2.4.1 Oxidations
In industry, typical oxidation reactions over heterogeneous catalysts are usually
partial or selective oxidations, such as:

– ethylene epoxidation

Ag2O
C C C C
O

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26 1 The basics

– oxidation of propene to acrolein

O
C C C C
Bi2O3–MoO3
C C C C

– oxidation of benzene or butane to maleic anhydride

O O

V2O5–MoO3 [cat.]
O + CO2 + H2O + 3.5 O2 O + 4 H2O
+ O2 400 °C

O O

In terms of carbon use, butane oxidation is much more efficient than benzene oxi-
dation, as according to stoichiometry in benzene oxidation two moles of CO2 are
formed per one mole of reacting substrate.
In the selective oxidation reactions, CO2, CO and even water are undesirable
products.
Partial oxidation reactions (and selective catalytic reduction, Fig. 1.25) are typi-
cally carried out using such oxides as, for example, V2O5, MoO3, or molybdates. They
proceed through changes in oxidation states following the Mars-van Krevelen redox
mechanism.

Reduction

V=O Standard SCR V – OH

Oxidation

½ H2O ¼ O2 Fig. 1.25: Mechanism of selective catalytic reduction.

In this mechanism (kinetics will be presented in Chapter 3) reduction of the oxide is

dependent on the organic reactant (NO and ammonia in the case of selective cata-
lytic reduction (SCR), or CO in Fig. 1.26) and takes place in the absence of gas-phase
oxidants (O2, H2O). Isotope labeling studies were used to confirm that oxygen in the
product comes from the lattice oxygen (Fig. 1.26A), but not directly from the gas-
phase species.
Re-oxidation of oxide happens independently of the reduction step (Fig. 1.26B).
Dissociative adsorption of oxygen often occurs at a site different from an oxidation
site, followed by diffusion through the bulk in order to refill the surface vacancy.

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 1.2 Reactivity of solids 27

O
|
CO C CO2
|
O
M O M O M M M O M M M O M Interface

Oxide Oxide Oxide

(A)

O2

M M O M M O M O M Interface

Oxide Oxide
(B)

Fig. 1.26: The Mars-van Krevelen redox mechanism. (A) oxide reduction and (B) re-oxidation.

For oxidations not involving changes in oxidation state, such as oxidation of CO

on metals, a different mechanism could operate. For example, the substrates can co-
adsorb on the surface, which is followed by a reaction between the adsorbed species
according to the Langmuir-Hinshelwood mechanism (Fig. 1.27).

O
|
CO O2 C
— O— O CO2
| | |
Interface

Oxide Oxide Oxide

Fig. 1.27: Oxidation following a Langmuir-Hinshelwood mechanism.

Alternatively one reactant is adsorbed and the other reacts from the fluid phase.

1.2.4.2 Hydrogenation
From the fundamental as well as an industrial viewpoint, hydrogenations can be con-
sidered to be the most advanced field of catalysis. Various hydrogenation reactions
are employed in industry, such as hydrogenation of double, triple and aromatic
bonds, and C=O bonds to name a few. Different mechanisms were proposed for the
hydrogenation of olefinic double bonds [16]. The Horiuti-Polanyi mechanism as-
sumes that both the alkene and hydrogen must be activated by being adsorbed on
the surface (see Fig. 1.28).

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28 1 The basics

1. H2 + 2 * 2H
*

2. C C + 2* C C
* *

3. C C + H C C + 2*
* * * * H

4. C C + H C C + 2*
* H * H H

Fig. 1.28: The Horiuti-Polanyi mechanism.

It should be noted that double-bond hydrogenation is stereo selective (Fig. 1.29),

corresponding to addition to the less crowded face of the double-bond (syn addition
of both H atoms).

H
CO2CH3 CO2CH3
H2, Pt

CO2CH3 CO2CH3
H
(100%)

Fig. 1.29: Syn addition to the double-bond.

The mechanism, which addresses stereo selectivity and is consistent with liquid-phase
hydrogenation kinetics, assumes the addition of hydrogen to the adsorbed organic
molecule, followed by isomerization in the adsorbed state of the formed olefin-
hydrogen complex (Fig. 1.30). The adsorbed product is displaced from the surface by
the incoming substrate. See [17] for a detailed discussion on the mechanism.

B
H2
ZA

ZB ZAH2

Fig. 1.30: Mechanism of catalytic hydrogenation. (From [17]).

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 1.2 Reactivity of solids 29

1.2.4.3 Catalysis by solid acids

Crystalline aluminosilicates-zeolites can be used in catalysis because of the pres-
ence of acidic sites, which are generated by the substitution of silicon by aluminum
in the framework of silica. A detailed discussed on the properties of zeolites and
their preparation will be given in Chapter 2. Here we can mention that differences
in charges between Si+4 and Al+3 are balanced by protons, which is the reason for
strong Brønsted acidity of zeolites, caused by the presence of these protons.
The mechanism of acid-catalyzed reactions is thus connected to the presence of
protons and Lewis acid sites; the Lewis acid sites can act as solid acids by accepting
electrons. For example, double-bond isomerization in olefins such as butene starts
with the proton addition to the double-bond, forming a secondary butyl cation:

H2 C = CH − CH2 − CH3 + H +
!

H3 C − C H − CH2 − CH3
¯

This is followed by an internal hydride shift:

H3C–CH–CH2–CH3 H3C–CH2–CH–CH3
+ +

and the subsequent proton elimination:

H3 C − CH2 − C H − CH3
!

H3 C − CH = CH − CH3 + H
+
¯

Skeletal isomerization of olefins also proceeds with the addition of proton and fur-
ther rearrangement of carbenium ions because of their different stabilities:
CH3 CH3
H H2 H2 H2
R C C C R' R C C C R'
+ +
H
Thus, tertiary carbenium ions are more stable than secondary ones, with primary
ions the least stable. Because of the different mechanisms of proton addition, the
skeletal isomerization of alkanes is more difficult than that of olefins, requiring
stronger acid sites.
Catalytic cracking of heavy organic compounds is an industrially important re-
action in oil refining that will be covered in detail in Chapter 4. During cracking,
secondary carbenium ions are formed at random followed by cracking at the bond
at the beta position to the charged carbon atom, giving an olefin and a primary car-
benium ion:

RCH2CHCH2–CH2CH2R' RCH2CH=CH2 + CH2CH2R'

+ +

The primary ion undergoes a hydride shift to secondary ions, as discussed above. A
detailed account of the mechanism of catalytic cracking is provided in Section 4.3.

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30 1 The basics

1.3 Catalysis in industry and for environmental protection

The immense importance of catalysis in the chemical industry is demonstrated by

the fact that roughly 85–90% of all chemical products have seen a catalyst during
the course of production. The number of catalytic processes in industry is very large,
with the catalysts coming in many different forms, such as heterogeneous catalysts
in the form of porous solids (Fig. 1.31), homogeneous catalysts dissolved in the liquid
reaction mixtures and biological catalysts in the form of enzymes. In fact, enzymes
could either be in the same phase as the liquid reactants or in their solid form (either
poor soluble enzymes or immobilized ones).

Fig. 1.31: Shapes of heterogeneous catalysts. (Reproduced with permission from [18]).

In theory, catalysts are not consumed in a chemical reaction, thus in an ideal sce-
nario for cost calculations only the cost of the initial catalyst should be considered.
In practice many industrial catalysts deactivate, requiring gradual replacement.
Nonetheless, the contribution of catalysts to the overall cost of a product is on aver-
age not very high (~3%) and subsequently a part of catalyst sales in relation to the
gross domestic product (GDP) is marginal (~0.1%). However, the share in GDP of
products made by catalysts could be as high as 25%. The global catalyst market was
estimated to be worth 27.7 billion dollars in 2015 and is projected to increase to

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 1.3 Catalysis in industry and for environmental protection 31

33.5 billion USD in 2019. The main contribution to the global demand for catalysts
is associated with environmental applications (Fig. 1.32), while the second most im-
portant contribution is related to сrude oil refining (Fig. 1.33).

41%

17%
Refining Fine chemicals and intermediates
13% Petrochemicals Environmental
5%
Polymers

Fig. 1.32: Global catalyst value. (From [19]).

Gas

Desulfurization Isomerization
Light
naphtha
Gasoline
Heavy
naphtha
Reforming

Petrol Kerosene

Catalytic cracking

Gas oil Diesel

Fuel oil

Asphalt
Residues bitumen

Fig. 1.33: Future perspectives in catalysis. (From [20]).

Most growth in catalyst demand is outside the Organization for Economic Co-
operation and Development and is driven to a substantial extent by environmental air
quality and fuel specifications. The annual growth rate of emission control catalysts
(~12%) is higher than the average for the catalyst manufacturing industry (~8%).

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32 1 The basics

In addition to tightening the regulations for mobile emissions and for fuel
quality, other trends driving future demand for catalysts are: improving process
efficiency by more efficient use of feedstock and higher yields; and increasing en-
ergy efficiency, expanding simultaneously the feedstock base to include coal, nat-
ural gas and biomass.
The contribution of catalysts to improving the environment is not only related
to end-of-pipe technologies (for example, the cleaning of wastes), but also to the
prevention of pollution by avoiding the formation of waste and unwanted by-
products through improving processes and selectivity in the existing ones.
Tab. 1.2 gives some examples of catalytic processes in oil refining for the pro-
duction of gasoline, diesel, kerosene, heating oils, while a photo of catalysts used
in refining as well as in the synthesis of petrochemicals is presented in Fig. 1.34.

Tab. 1.2: Major catalytic processes in oil refining.

Process Catalyst Conditions

Hydrodesulfurization NiS/WS/AlO – °C,  bar H

CoS/MoS/AlO
Hydrocracking MoO/CoO/AlO – °C, – bar H
Ni/aluminosilicate
Catalytic cracking of heavy fractions zeolites – °C, – bar
Catalytic reforming of naphtha Pt(+other metal)/alumina – °C, – bar H
Isomerization of light gasoline Pt/alumina – °C, – bar

Fig. 1.34: Refining and petrochemical catalysts (photo of the author).

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“Yes; and if I were in your place I’d raise another. There’s nobody in
sight, and how is the owner of the cattle going to know who did the
shooting? Knock one of ‘em over! I dare you to do it!”
Ned hesitated. He had talked bravely enough, when in the presence
of his cousin, about doing this very thing, but since that time he had
seen a fight, had heard the reports of firearms and the yells of
excited and angry men, and thought he had some faint conception
of the scenes that had been enacted during that neighborhood row,
and which would, no doubt, be repeated if another should arise. But
here was his fine field of wheat so nearly destroyed that it would not
pay for the harvesting; within easy rifle shot of him were some of
the cattle which had done the mischief and which probably belonged
to one of the neighbors who wouldn’t visit with him or his father
because they wore good clothes and claimed to be gentlemen; and
there was no one in sight.
“Knock one of them over,” repeated Gus, “and perhaps it will teach
their owner to keep his stock out of the way of your field, the next
time you plant wheat in it. Hand me your gun, and I’ll show you that
I am Gus Robbins yet, and not afraid to do anything.”
The boy leaned forward in his saddle as he said this, and taking the
rifle out of his friend’s grasp, rode toward the cattle (there were
probably a dozen of them in all) which were dashing along the fence
and trampling down the wheat that had escaped destruction during
their former raids. As Gus approached them, they charged in a body
in the direction of the gap; but instead of going through it they ran
on by, kicking up their heels and shaking their heads as if they
enjoyed the sport. While Ned galloped through the field to head
them off, Gus dismounted, and taking his stand near the gap, cocked
the rifle in readiness to shoot one of the herd the next time they
went by.
Ned succeeded in turning the cattle after a short race, and, as
before, they took no notice of the gap, but dashed by it and started
for another gallop around the field. At that moment the rifle cracked,
and one of the finest steers in the herd threw his head and tail
higher in the air, galloped faster for a short distance, then sank to
his knees and rolled over on his side. By the merest chance, Gus had
sent a bullet smaller than a buckshot into some vital part, and there
was one less steer in somebody’s herd to break down fences and
destroy wheat crops.
“What do you think of that?” cried Gus, in great glee.
“It was a splendid shot,” replied Ned, who just then rode up and
extended his hand for the rifle. “You did it, didn’t you? Since we
have begun the work, we’ll do it up in shape. If they won’t go out
they can stay in; but they’ll stay dead!”
The horse that Gus rode, having been broken to stand fire, was not
at all alarmed by the report of the rifle. He allowed the boy to catch
and mount him again, and by the time he was fairly in the saddle,
Ned had placed a fresh cartridge in his rifle. “You head them off and
drive them back,” said he, “and I’ll wait here at the gap to salute
them as they go by.”
In accordance with this request Gus rode off, and in a few minutes
the herd came dashing along the fence again. They must have been
growing tired of the sport by this time, for they headed straight for
the gap, and all got through; but one of them carried a bullet
somewhere in his body, the effects of which very soon became
apparent. The rest of the herd began to leave him behind, and when
he followed them over a ridge, which lay about a quarter of a mile
from the field, he was staggering about as if he could scarcely keep
his feet.
While the work of driving the cattle out of the field was in progress,
a horseman appeared on the ridge of which we have spoken, riding
slowly along, with his eyes fastened on the ground, as if he were
following a trail. Just as he reached the top, he heard the report of a
rifle, and looked up to discover that the cattle of which he was in
search, were running about a wheat field, and that two persons
were engaged in shooting them down. One of the cattle fell just as
he raised his eyes. When he saw this, he placed his hand on one of
the revolvers he carried in his belt, and seemed on the point of
dashing forward to take satisfaction for the loss he had sustained;
but he evidently thought better of it a moment later, for he backed
his horse down the swell until nothing but his own head could be
seen over it, and there he sat and saw all that Ned and Gus did.
When the wounded steer came over the swell, staggering from the
effects of the bullet Ned had shot into him, the man shook his
clenched hand in the direction of the wheat field, muttered
something to himself, and galloped off in pursuit of the uninjured
cattle, leaving the wounded one to take care of himself.
“There!” exclaimed Ned, when the laggard of the drove had
disappeared over the swell, “it’s done, and I am glad of it. If the
owner of those cattle finds out that we did it and has anything to
say about it, I shall tell him that this is my land—it may be mine
some day, you know, and before long, too—and that no cattle except
my own have any right on it.”
“I wish that steer had got over the fence before he died,” said Gus.
The boys seemed to be highly elated over what they had done. They
had performed the same feat which, not so very many months ago,
had set the whole settlement together by the ears, and no one was
the wiser for it. Of course some rancheman would some day find out
that one of his fattest steers had been killed and another badly
wounded, but how was he going to find out who did the shooting?
Ned fully expected that there would be trouble about it; that there
would be threats and inquiries made, and that he and Gus, being
safe from discovery, would have many a hearty laugh in secret over
the storm they had raised.
“Remember one thing,” said he. “No matter what is said or done, we
don’t know anything about it. They can’t crowd us into a corner tight
enough to make us own up. That would only make matters worse.”
Gus readily agreed to this, and the boys shook hands on it. In order
to make assurance doubly sure they rode around the rancho and
approached it, just at dark, from a direction opposite to that they
had taken when they rode away from it in the morning. When the
events of the afternoon became known nobody could fasten the guilt
upon them by saying that they had been seen coming from the
direction of the wheat field. They found supper waiting for them,
and when they had eaten it they went into the office to spend the
evening in reading and conversation.
While they were thus engaged inside the house, a proceeding which
looks strange at the first glance, but which will be plain enough
when all the circumstances connected with it are known, was going
on outside of it. A horseman, who was riding rapidly along the road
toward the rancho, turned off just before he reached it, and made
his way to the corral that was located a short distance to the right of
the shed in which Ned had taken refuge on the night of the fight. He
stopped in front of the gate and uttered an exclamation of
disappointment when he found that it was secured by a heavy
padlock. After looking about him for a moment, as if he were turning
some problem over in his mind, he dismounted, pulled the bridle
over his horse’s head and hung it upon the horn of the saddle;
whereupon the animal turned and galloped toward a watering-
trough a short distance away, where he was joined by a small, dark-
colored mule which had followed the horseman down the trail. The
horseman himself moved toward the house, pausing every now and
then to listen and reconnoiter the ground before him, and presently
reached the steps leading to the porch. These he mounted with
cautious tread, and was about to place his hand upon the door when
it was suddenly opened from the inside, a flood of light streamed out
into the darkness, and the horseman was confronted by a stalwart
herdsman who started back in surprise at the sight of him.
Arresting by a hasty gesture the cry of amazement that arose to the
herdsman’s lips, the visitor stepped into the hall, and, closing the
door behind him, uttered a few short, quick sentences in a low tone
of voice which the other received with subdued ejaculations of
wonder. When he ceased speaking the herdsman hastened away,
and the visitor, who seemed to be perfectly familiar with the internal
arrangements of the house, moved quickly along the hall, turning
several corners, and finally opening a door which gave entrance into
Mr. Ackerman’s office.
There was a happy party gathered in that office, if one might judge
by the ringing peal of laughter which echoed through the hall, when
the door was opened; but it was quickly checked at the sight of the
boy who entered as though he had a perfect right to be there, and
whose appearance was so sudden and unexpected that it brought
two of the three persons in the room to their feet in an instant.
“Why, George!” they both cried in a breath—and a quick ear would
have discovered that there was more surprise than cordiality in their
tones—“Is this you? Where in the world have you been so long? We
have been worried to death about you!”
“Yes it is I,” answered George Ackerman, for he it was. “I have come
back safe and sound, and that is all I can say to you now about
myself. I want to talk to you about yourselves, and especially to you
Ned. By the way, I suppose this is the friend from Foxboro’ whom
you have so long been expecting.”
Ned replied that it was, but he forgot to introduce the two boys to
each other, and so did Uncle John. There was something about
George that made them forget it. When they came to look at him
they saw that he was very much excited, and that his face wore an
expression they had never seen there before. They could not tell
whether he was frightened or troubled.
“Why, George!” exclaimed Uncle John, in some alarm. “What is the
matter? Any bad news? Are the Indians or Mexicans——”
“Yes, I have bad news,” interrupted George, almost impatiently, “and
but little time to tell it in. Ned, you and your friend must pack up and
leave this rancho, and this county, too, without the loss of an hour’s
time. You are in danger, and I have placed myself in danger by
coming here to tell you of it!”
The boy’s words produced the utmost surprise and consternation
among those who listened to them.
 CHAPTER XII.
A NARROW ESCAPE.

G eorge found his herdsman eager for news from the settlement,
as he always was, but he had nothing to tell him that was very
interesting. He could have given him some information that would
have made him open his eyes and put him in fighting humor at
once; but he thought it best to avoid that subject altogether. If he
told Zeke that Uncle John had threatened to take his herd of cattle
away from him, under the plea of reducing expenses, but really as
George believed, for the purpose of turning it over to Ned, the old
man would have been as angry as George was when he first learned
of the fact. But the boy didn’t want to let Zeke know how mean his
uncle was, and so he said nothing about his plans. They never could
be carried out while Zeke was there to protect his stock, and George
could afford to be magnanimous.
George and his herdsman made an early start on the following
morning, and the third night found them at Catfish Falls. They now
felt perfectly safe, for the raiders had never been known to
penetrate so far into the country. Their depredations were principally
confined to the counties bordering on the river, it being their object
to stampede all the stock they could find in one night’s raid, and
drive it across the river into Mexico, before the settlers could gather
in sufficient numbers to pursue them. They tried as hard to avoid a
fight as the ranchemen did to overtake them.
George made the camp and cooked the supper, and when they had
satisfied their appetites, the former laid down on his blanket in front
of the fire with his saddle for a pillow, and listened to Zeke, who
talked and smoked incessantly. Their work for the day was over now.
The cattle were always brought close in to camp at dark, the horses
and mule were staked out, and the campers went to bed at an early
hour. If they awoke during the night, they replenished the fire with
some of the fuel that was always kept close at hand, and walked
around the herd to see if there were any restless ones in it who felt
inclined to stray away. George performed this necessary duty twice
on this particular night making the first round about twelve o’clock.
To his surprise, he found the most of the cattle on their feet, and
saw that some of them were exhibiting unmistakable signs of
uneasiness and alarm. They stood snuffing the air eagerly, carrying
their heads high and their ears thrown forward, and now and then
they would walk a few steps out of the herd, lower their horns and
paw the ground as if challenging the object that had excited them,
whatever it was, to come out and give them battle. The rest of the
cattle were lying down, chewing their cuds contentedly, and
apparently not at all disturbed by the antics of their nervous
companions.
George threw himself flat upon the ground and swept his eyes
around the horizon. In this position, he could distinctly see any
object that might be approaching the camp (provided, of course,
that it was taller than the grass) for it would be clearly outlined
against the sky. But he could see nothing. He arose to his feet again
and listened intently, but could hear nothing calculated to excite his
alarm. The wolves which serenaded them every night were holding a
concert a short distance away, and that made George believe that if
there was any danger approaching, it was yet a long distance off; for
he knew that the wolves would be the first to discover it, and that
they would then bring their concert to a close and take to their
heels.
“There’s something up,” thought George, once more turning his eyes
toward the cattle. Some of the uneasy ones, reassured by his
presence, were walking about among their companions, as if they
were looking for a good place to lie down, while the others remained
in a defiant attitude and snuffed the air as before. “There’s
something up,” repeated George, “and I have been expecting it. I
have felt very nervous and timid for two or three days, and I don’t
know how to account for it. If there is anybody within hearing or
smelling distance who has no business here, I can find it out.”
George walked back to the camp, picked up his rifle, and after
unfastening the lasso with which his horse was confined, he jumped
on the animal’s back without saddle or bridle and rode away in the
darkness, paying no heed to a bray of remonstrance from Bony who
followed as far as the length of his lariat would allow him to go. He
rode out on the prairie for a hundred yards or more, and then
stopped his horse and listened again. The animal stood perfectly
quiet for a few seconds, looking first one way and then another, and
turning his ears toward all points of the compass, and apparently
satisfied with the result of his reconnoissance, he put down his head
and began cropping the grass.
“Hold up, here!” exclaimed George, seizing the horse by the mane
and tapping him gently on the side of his head with the muzzle of
his rifle to make him turn around. “We have nothing to be frightened
at yet—that’s evident. Now, old fellow, I shall leave you loose. Keep
your ears open and wake us up if you hear anything!”
George rode back to camp and sought his blanket feeling a little
more at his ease. He had as much faith in his horse as he had in
Zeke (the latter used to say that he could smell an Indian or a
Greaser at night as far as he could see him in the daytime), and
since the animal could not discover anything suspicious, it was as
good evidence as he wanted that there was nothing to fear. No
doubt some of the wild members of the herd felt as nervous and
uneasy as he did, and took their own way to show it.
Although George brought back to his blanket a most refreshing
feeling of security, he did not sleep as soundly as he usually did. He
went through all sorts of terrible things in his dreams, and started
every time the fire snapped. He was wide awake again at one
o’clock, and set out on his second tour of inspection. The moon, now
nearly half an hour high, had brought up with it a cooling breeze
which gently rustled the long grass of the prairie, and sent the
sparks from the camp-fire circling high in the air. The wolves had
closed their concert and gone off to find a more appreciative
audience, and there was an air of peaceful quiet brooding over the
scene. George forgot all his fears and continued his round with a
light heart. He found the cattle quiet, but some of them had begun
feeding and were straying away from the rest of the herd. While
George was engaged in driving them back, and forcing the
remainder of the herd into a more compact body, a yell, so sudden
and startling that it made the cold chills creep all over him, arose on
the air, and out from a little thicket of willows that grew a short
distance from the belt in which the camp was located, dashed a
party of horsemen who charged toward the herd at the top of their
speed. They were Mexicans; George could see that at a glance. They
had doubtless been hovering about the camp all night, and it was
while they were working their way around to the leeward of the herd
that their presence had been detected by the wakeful cattle.
George stood for an instant as if he were rooted to the ground; and
then with a wild cry of alarm he dashed forward, running diagonally
across the front of the herd, hoping almost against hope that he
might succeed in passing them, and thus avoiding the rush which he
knew would come in a moment more. It was the only way in which
he could escape being trampled to death. He ran as he had never
run before, but he had made scarcely half a dozen steps when a
rumble like that of an avalanche sounded close at his side, telling
him that the cattle were coming. The strongest fence that was ever
built would not have stopped them now, and George, had he
attempted to drive them back or turn them aside, would have been
trampled under their feet like a blade of grass. He saw and fully
realized his danger, but could not escape it. Even Zeke, who was as
light of foot as an antelope, could not have saved himself by his
speed; and George, giving himself up for lost, fell flat upon the
ground, clasped his hands over his head and awaited his fate. By the
merest chance he threw himself into a little excavation in the prairie,
which, in the years gone by, had doubtless served as a wallow for
some old patriarch of a buffalo; but now it was covered with grass,
and there were two or three little willows growing out of the bottom
of it.
This protection, slight as it was, saved the boy’s life. He had barely
time to crowd himself close against the frail stems of the willows
before the frantic cattle were upon him. The roar of their hoofs on
the hard ground was almost deafening. It was louder than the roar
of all the northers he had ever heard crowded into one; but even
while he was wondering why some of the cattle did not jump upon
him the roar subsided, and George, looking up through the willows
which had been bent over his head, saw the moon shining down
upon him. Every steer had jumped the wallow, and George had
escaped with nothing more than a terrible fright. While he was
congratulating himself upon his good fortune, a clatter of hoofs
sounded near, and he ducked his head just as two horsemen, riding
side by side, dashed over the wallow in pursuit of the flying herd.
The boy’s first thought, after he had satisfied himself that he had
escaped without injury, was of Zeke. What had become of him?
There was one thing certain—George knew it now as well as he did
a few minutes later—and that was that the herdsman had made a
fight, and a good one, too. Although the old fellow appeared to be a
sound sleeper, he would jump to his feet the instant he heard any
unusual noise, and he was wide awake the moment he opened his
eyes. More than that, he kept his Winchester close at hand, and
could discharge it with a rapidity and accuracy that George had tried
in vain to imitate. Zeke was probably on his feet before the yell that
frightened the cattle was half uttered, and as soon as he got there
he was ready to begin shooting. Of course George had not heard the
report of his rifle, for the rumble of that multitude of hoofs about his
ears would have drowned the roar of a cannon.
“But I know, all the same, that he did shoot, and that some of those
raiders didn’t get away,” thought George, as he once more raised his
head and looked over the grass in the direction of the camp. “I think
I had better stay here. Zeke will know when the danger is over, and
then he will call to me. I wonder if he is there now? Somebody is
punching up the fire, sure!”
The old buffalo wallow into which George had thrown himself, was
about a hundred yards distant from the willows, and the grass was
so high that he could not see the camp; but he could see the smoke
of the fire as it arose through the tops of the trees that hung over it.
Just now the fire was blazing brightly, and the sparks were rising
from it in volumes. This was what led George to believe that there
was somebody in the camp. It couldn’t be one of the raiders, he told
himself, for they never stopped. They stampeded the cattle and
dashed on after them to get out of reach of the bullets in the
herder’s rifles.
“Of course Zeke is there,” thought George as he arose from his place
of concealment; but he had scarcely placed himself fairly upon his
feet before he dropped back among the willows again. There were
several figures moving about the fire, and there were riderless
horses and mounted men near by. The men were all dressed in
Mexican costume—the wide brims of their sombreros were plainly
visible in the moonlight—and there were at least a dozen of them in
sight. One of them seemed to be poking up the fire for the purpose
of making as bright a light as possible, while the others were going
into the willows with blazing fire-brands in their hands. Some of their
companions had already gone in there armed in the same manner,
for George could see the lights dancing about among the trees.
The boy saw all this during the instant of time he was on his feet,
and when he dropped back into his concealment again, his fear had
given place to a feeling of exultation. The raiders were searching the
woods in the vicinity of the camp, and of course they could be
looking for nobody but Zeke. Probably the old fellow had given them
a very warm reception. No doubt he had tumbled three or four of
them out of their saddles, and the survivors were hunting him up
with the intention of taking vengeance on him if they caught him.
“But they’ll never catch him,” chuckled George, “because he’s too old
a ‘coon. He has fought Indians too long to be beaten by a lot of
lubberly Greasers.”
George drew the tops of the willows closer together, confining them
in that position by twisting their branches, and having thus formed a
screen that was large enough to cover his head, he raised himself
upon his knees, so that he could look over the grass and watch the
motions of the raiders. They were certainly looking for somebody,
and they seemed resolved to find him, too, for they did not grow
discouraged and go away, as George hoped they would. Their failure
only seemed to make them the more determined. First one and then
another seized fire-brands and joined their companions in the
woods, and finally those who were mounted, swung themselves out
of their saddles and went in too, leaving the camp to take care of
itself.
“I wonder what Zeke has done to make them so persistent!” said
George to himself. “Perhaps they’ve got an old grudge against him.
They might as well go away, for they’ll not find him. He’s safe long
before this time, and if I could only make my horse hear me, I’d
soon be safe too.”
George could always find something to feel happy over, no matter
how unpleasant the situation in which he might be placed, and he
found something now. He had lost his fine herd of cattle, but Zeke
was left to him, and so were his horse and pack-mule. The former
had been stampeded with the cattle, but George knew he would not
run far before he would leave them and strike a straight course for
home. The two Mexicans who had followed the herd to head it off
and turn it away from the settlements toward the river, would not
bother their heads about him, for while they had three hundred fat
cattle to look out for, they could not afford to waste time in pursuing
a single horse. Bony was still staked out near the camp, and so was
Zeke’s nag. They both made the most desperate efforts to escape
with the herd, but the lariats with which they were confined were
too strong to be broken, and the picket-pins were driven so firmly
into the ground that they could not be easily pulled up. The
Mexicans, when they were ready to leave the camp, would probably
turn these animals loose, expecting them to follow their own horses,
just as Silk Stocking had followed off the raiders who made the
attack on the rancho; but that was something Bony would not do.
He was very much afraid of strangers, and when left to himself he
would make the best of his way home.
The search for Zeke was continued? until broad daylight, and all this
while George lay in his concealment watching the motions of the
raiders and wondering what his herdsman had done to make the
thieves so anxious to find him. When day began to dawn he
discovered something that seemed to explain it all: there were five
wounded men sitting and lying beside the fire. George knew that
they were wounded, for he could see that they wore bandages, and
that one who limped considerably and used a stick to walk with,
would now and then get up to bring a cup of water from the bayou
to two of his companions who kept their blankets. Probably one of
these men was the leader of the band, and that was the reason why
the others were so determined to find Zeke. But they had to give up
the search and go away without him, as George knew they would.
Shortly after daylight they began to come into camp by twos and
threes, and when they were all assembled George counted eighteen
of them. They talked earnestly together for a few minutes and then
set about preparing a hasty breakfast, helping themselves bountifully
to the contents of the pack-saddle, and using the cooking utensils
which George had provided for his own use and Zeke’s.
George waited with no little impatience to find out what they were
going to do when they made an end of the bacon and coffee, and
was very glad to see that they were preparing for an immediate
departure. When all was ready the wounded members of the band
were assisted into their saddles, Zeke’s horse and George’s pack-
mule were set at liberty, and the raiders moved slowly along the
willows in the direction the cattle had taken when they were
stampeded. It was a wonder that their suspicions were not aroused
by the actions of the mule which, foolish as mules generally are, ran
at once to the buffalo wallow in which George was concealed, and
not content with shying at the sight of it and giving it a wide berth,
as Zeke’s horse did, Bony circled around it two or three times, and
finally stopping, thrust out his neck, threw his long ears forward and
looked suspiciously at the crouching form of his master.
George, who had been in a fever of suspense for long hours, and
who began to breathe more freely when he saw the raiders moving
away, was frightened again; but, as it happened, the thieves paid no
attention to the mule’s actions. Better than that, Zeke’s horse kept
on his way without stopping, and Bony, seeing that he was going to
be left behind, started in pursuit. The danger was over now, but
George was much too wary to run any risks. He saw the raiders
disappear over the nearest swell, but he allowed another hour to
pass before he left his hiding-place. Then he moved very cautiously,
crawling along on his hands and knees, stopping every few feet to
look over the grass and listen, and examining the ground about the
camp very thoroughly before he ventured into the woods.
He found the camp in the greatest confusion. His rifle and revolvers
were gone, so were his blankets and poncho, and also a good
portion of the contents of the pack-saddle; but there was still a little
of the bacon and hard-tack left, and the raiders had forgotten to
take his haversack and frying-pan. He replenished the fire at once,
and while waiting for it to get fairly started, employed himself in
cutting up the bacon with an old rusty hunting-knife which one of
the thieves had probably left in exchange for his own new one.
While he was thus engaged he did not neglect to keep an eye open
for any straggling raiders who might have fallen behind the main
body; but there were none in sight. He placed the bacon in the
frying-pan, and when it was done to his satisfaction he put it into his
haversack, together with the small supply of hard-tack that was left,
extinguished the fire and set out for home.
“I am glad the thieves left me provisions enough to last me until I
can get more,” said George, to himself. “If I have to travel all the
way on foot, it will take me four or five days to reach the nearest
rancho, and I have no fears of getting hungry during that time. What
brought those raiders so far from the river? That’s what I can’t
understand.”
During the two days that followed, while the young cattle-herder
was trudging painfully over the lonely prairie, he had ample leisure
to turn this question over in his mind. He travelled early and late,
but his progress was necessarily slow, for one who spends the most
of his time in the saddle, finds it hard work to go on foot, and soon
grows weary. He kept a bright lookout for Zeke, and stopped on the
top of every swell to scan the prairie before and on both sides of
him, in the hope of discovering his horse or pack-mule; but Zeke was
miles ahead of him, hastening toward the settlement, intent on
alarming the ranchemen in time to cut the raiders off from the river,
while Bony and Ranger were making the best of their way toward
home.
“They are all safe, I know, for they are able to take care of
themselves. So am I; but there’s no fun in looking forward to three
days more of such walking as I have had. I shouldn’t mind it so
much if I hadn’t lost my cattle,” said George, with a long-drawn sigh.
“Those lazy Greasers have robbed me of years of hard work, and
now I must begin all over again, or else go to herding cattle for
Uncle John. Of course I can’t loaf about the house all the time and
do nothing, as Ned does. Hallo!”
While George was talking to himself in this way he came to the top
of a ridge, and found before him a long line of willows which fringed
the banks of a water-course. A solitary horse was feeding near the
willows, and this it was that attracted the boy’s attention and called
forth the exclamation with which he finished his soliloquy. The sight
of the animal alarmed him, for it was not at all likely that a horse,
wearing a saddle and bridle, would be feeding contentedly in that
wilderness, so far from all signs of civilization, unless there was
some one with him. George dropped to the ground, and ran his eyes
along the willows in search of a camp. If there was one in the
neighborhood he could not find it. There was no smoke to be seen,
nor were there any other indications of the presence of human
beings.
“But there’s somebody here all the same,” thought the boy, shifting
his position a little, so that he could obtain a better view of the
willows, “for that horse never came here without a rider. Somebody
has stopped in the willows to rest, and he’s a Mexican, too. I know it
by the silver ornaments on the saddle. I wish I could think up some
way to capture that horse. Shall I try it?”
Not knowing what else to do just then, George lay there in the grass
and considered the matter. Weary and footsore as he was, the
thought of finishing his journey on horseback was a most agreeable
one. The animal was loose—when he raised his head, George could
see that he was not confined by a lariat—but if he attempted to
creep up to him the horse would doubtless take fright and run off;
and that would excite the suspicions of his owner, who might be
tempted to send a bullet from his carbine in that direction. There
was too much danger in it George found when he came to think it
over. He sighed regretfully, thought almost with a shudder, of the
long, weary miles that lay between him and the nearest rancho, and
was about to crawl back down the swell again, when he was
astonished almost beyond measure, to hear his own name
pronounced in a weak and trembling, but still distinct voice.
“George! George Ackerman!” came the hail from the willows.
George jumped to his feet, and looking in the direction from which
the voice sounded, saw a sombrero waved in the air, and could dimly
discern the figure of a man, dressed in Mexican costume, who was
sitting on the ground, with his back against one of the willows.
“George!” repeated the man.
“Hallo!” was the reply.
“Come here, will you? I am badly hurt and in need of help!”
George grew more and more astonished. The man was a Mexican
beyond a doubt, but the voice sounded strangely familiar.
“Don’t be afeared, George!” continued the man, in a pleading tone.
“I couldn’t hurt you if I wanted to! I’ve got something to tell you!”
“Who are you?” asked the boy.
“Why, don’t you know Springer, who used to herd cattle for your
father?”
Yes, George knew him, and he didn’t know anything good of him
either.
“If you are Springer,” he shouted “what are you doing there with
those clothes on?”
“Come here, an’ I’ll tell you all about it!” was the answer. “I’ll tell you
something else, too—something that’ll make you open your eyes. Do
come, George, and give me a drink of water! I’ve got a chunk of
lead through each leg!”
“Aha!” said George, who thought he understood the matter now.
“You were with the raiders, and Zeke got two pulls at you with his
Winchester!”
As he said this he ran down the swell, and in a few minutes more
was standing beside the wounded man. It was Springer, sure
enough, but he was so much changed that George could scarcely
recognise him. His face was very pale and his strong frame was
convulsed with agony. The sash he usually wore around his waist
had been cut in two, and the pieces were bound tightly about his
legs above the knee to stanch the flow of blood from the wounds
made by the herdsman’s rifle. He was a hard-looking fellow, and any
one would have taken him for just what George knew him to be—a
cattle-thief.
Without stopping to ask any more questions George seized the
man’s hat, and hastening to the bayou presently returned with the
crown filled with water. The wounded raider drank eagerly and sank
back against his tree with a sigh of great satisfaction.
 CHAPTER XIII.
GEORGE HAS COMPANY.

G eorge knew Springer well. The latter had once been in his
father’s employ; but being of no use as a herdsman or anything
else, he had been discharged, to make room for a more industrious
and pains-taking man. This enraged Springer, who threatened
vengeance, and followed up his threats by attempting to fire the
rancho. He had been detected in the act and almost captured; but
he succeeded in making his escape, and since then George had
never met him until this particular day. He had often heard of him,
however, as a member of a band of cattle-thieves, who now and
then made a raid through the country farther down the river. There
were a good many others just like Springer, on the opposite side of
the Rio Grande—renegade Americans—who, having left their country
for their country’s good, had taken refuge among the Mexicans, and
joined with them in raiding upon the well-stocked farms and ranches
of their Texan neighbors.
 George returns Good for Evil.

“You needn’t be afeared, George,” repeated Springer, seeing that the

boy cast uneasy glances about him, as if half expecting to see the
rest of the band start up from some ambush among the willows.
“Thar’s nobody here but me.”
“Where are your friends?” asked George.
“They’ve gone on, an’ I s’pose they’re acrosst the river by this time.”
“Did they leave you here to take care of yourself?” inquired George,
who found it difficult to believe that men could be so heartless.
“What else could they do?” asked Springer, wincing a little, as he
tried to move one of his wounded legs into a more comfortable
position. “A man who is fool enough to get hurt, must take his
chances. If he can keep up with the rest, well an’ good; if he can’t,
he must fall behind an’ look out fur himself. I’m glad I ain’t in the
settlement. I’d rather stay here an’ starve, fur want of grub an’
water, than have the ranchemen catch me. I ain’t had a bite to eat
fur two days.”
“You haven’t!” exclaimed George. “I’ll divide with you.”
He opened his haversack, as he spoke, and producing from its
capacious depths a goodly supply of bacon and cracker, placed it in
the hands of the wounded man, whose eyes brightened as he
received it. George stood by and saw him eat it, and was glad to see
that he enjoyed it, although he knew that by thus diminishing his
store he put himself in a fair way to go hungry for many a weary
mile of his journey. The man was a scoundrel—no one except
himself could tell what deeds of violence he had been guilty of
during his raids—but for all that George was glad that it was in his
power to relieve his distress.
“I am sorry to see you in this situation, Springer,” said he, when the
bacon and cracker had disappeared.
“Are you, though?” exclaimed the man, wiping his mouth with the
back of his hand, and looking up in surprise. “I didn’t s’pose you
would be.”
“Well, I am; and I hope that when you get well, you will behave
yourself and live among white men.”
“That’s unpossible; ‘kase why, white men won’t have nothing to do
with me,” replied Springer, almost fiercely. “Would you hire me to
herd cattle fur you?”
“Yes, I would. I know you threatened that you would be revenged
on my father for discharging you, but I don’t see why you should
follow me up. I haven’t done anything to you. How did you get shot?
And how came you here?”
“Wal, you see, we made the dash on your camp, kalkerlatin’ to take
you by surprise; but Zeke, he allers sleeps with his rifle in his hand
an’ one eye open, an’ I was the fust feller he got a crack at. He took
two pulls at me, an’ this yere is the consequence,” said Springer,
pointing with both forefingers toward his bandaged legs. “When we
left your camp, the fellers put me on my hoss, an’ I kept up with ‘em
fur a few hours; but the pace was too fast fur me—I couldn’t stand
the joltin’; so I had to pull up. When I reached this bayou, I thought
I’d get a drink of water; but when I got down I fell, lettin’ go my
bridle, an’ my hoss walked away. I was too weak an’ bad hurt to
crawl to the water; I couldn’t ketch my hoss, an’ I reckoned I’d got
to stay right here. I happened to see you when you come to the top
of the ridge, an’ called to you, thinkin’ mebbe you wouldn’t refuse to
give me the drink I was a’most ready to die fur. But you wouldn’t a
done it, if you knowed as much as I do!”
“Yes, I would. I don’t bear you any ill-will because you stole my
cattle.”
“But that aint all!” exclaimed Springer.
“I know it isn’t! You tried to burn my home over my head; but I
don’t bear you any ill-will for that, either; and I’ll prove it to you by
putting you on your horse and giving you a chance to save yourself!”
“But that aint all!” said Springer. “How do you reckon we knowed
whar to look for you?”
“I’m sure I can’t tell! I never knew raiders to venture so far from the
river before!”
“An’ they never did, nuther! Whar was you when we was in your
camp?”
“I was lying in a buffalo wallow about a hundred yards away!”
“Did you see the fellars while they was a pokin’ around in the
willows with their fire-brands? What do you reckon they was a
lookin’ for?”
“I supposed they were looking for Zeke!”
“Wal, they wasn’t lookin’ for Zeke, nuther! They didn’t care nothing
about Zeke! You was the fellow they wanted to find!”
“I was!” exclaimed George. “What did they want of me?”
“They wanted you ‘kase there’s a thousand head of fat steers
wrapped up in you, ‘sides them three hundred we stole from you the
other night!”
The boy was greatly astonished, and he was certain, too, that he
knew what Springer was trying to get at. He seated himself on the
ground with his back against a neighboring tree, and said as calmly
as he could:
“You must speak plainer than that if you want me to know just what
you mean!”
“I mean jist this yere,” said Springer; “an I’ll tell you ‘cause you was
good enough to come here an’ give me the drink of water I was
starvin’ fur, an’ feed me outen your grub when you haint got enough
to eat yourself. George, you are in danger every day you spend at
your rancho! Your uncle and cousin don’t want you there, an’ they
aint goin’ to let you stay nuther!”
George thought from what Springer said before that he had some
such revelation as this to make, but when it came it almost took his
breath away. He had long been of the opinion that his relatives
didn’t want him at the rancho, but how could this cattle-thief, who
lived miles away on the other side of the river, have found it out?
The man talked in a positive tone, as though he knew all about it,
and this was what surprised George. There was one thing certain,
however: He was not going to discuss family matters with any such
fellow as Springer.
“I’ll tell you what it is,” said he, as he arose to his feet and slung his
haversack over his shoulders. “I’ll not stay here if you are going to
insult my uncle and cousin!”
“Say, George, whar you goin’?” demanded Springer.
“I am going to start on again. Shall I put you on your horse before I
go?”
“You needn’t go off mad,” said the man, earnestly, “‘cause every
word I’m tellin’ you is the gospel truth. We got it all through Philip!”
“Got all what through Philip?” asked George.
“I mean we done all our business through him; an’ if I was in your
place, I’d go home an’ bundle him outen the house, neck an’ heels.
He’s makin’ mischief thar, I tell you. He told us we’d find you in that
grove on Brown’s Run; an’ when we didn’t find you thar, we follered
your trail to Catfish Falls.”
“But how did Philip know I was going to that grove?” demanded
George, growing more and more bewildered.
“What’s the use of me tellin’ you when you’ll get mad?” asked
Springer in reply. “The under-standin’ atween us, was, that arter we
had drove off your three hundred head of stock, we was to come
over agin, in a week or two, an’ we would find a thousand more
head whar we could get ‘em easy.”
“Who was going to put them where you could get them easy?”
“If I tell you, you’ll get mad at me. But mind you, we wasn’t to get
them thousand head unless we gobbled you. The fellers done their
level best, but couldn’t find you!”
“What were you going to do with me if you found me?”
“That’s something I can’t tell. Nobody but Fletcher knows that.”
“Who’s Fletcher?”
“He’s the boss—the cap’n.”
“Who told you to gobble me?”
“What’s the use of me tellin’ you when you’ll be sartin to go off
mad? You see, we kalkerlated to make twenty-six thousand dollars
clear by two night’s work, but that didn’t satisfy us. Philip, he told us
that thar was a whole bit of gold and silver in your uncle’s office, an’
we wanted that too; so we slipped down thar, an’ Philip, he opened
the door an’ let us in.”
“Into our house!” cried George, who now learned for the first time of
the attack that had been made upon the rancho.
“Yes, into your house; but we didn’t get nothing but bullets an’ one
hoss fur our pains.”
“It served you just right,” said George, indignantly. “They are not all
traitors in that house, I tell you.”
“Not by no means they ain’t,” said Springer, with a knowing shake of
the head. “One of the herders, who was awake, aroused the others
by firing his revolver, an’ it’s the biggest wonder in the world that
any of us got out. We tried to cut down the doors, but they drove us
off, and then we made a strike fur Brown’s Run, whar we allowed to
find you. On the way we run into about five hundred head of stock,
an’ thinkin’ that a bird in the hand was worth a dozen in the woods,
we drove ‘em off. We got ‘em across the river all right, an’ dodgin’
the rangers who follered us, we came back arter you. We found you
too, an’ some of us got more’n we wanted,” added Springer, looking
down at his bandages and groaning faintly.
George listened to all this in the greatest amazement. He
remembered now, that just before he left home with his supplies, his
uncle had questioned him closely about some things in which he had
previously shown no interest whatever, and that he seemed
particularly anxious to know where his nephew expected to find his
herd, and which way Zeke would probably drive it after George
joined him. The boy never would have thought of the circumstance
again, if it had not been for this interview with his father’s old
herdsman; but now it was recalled very vividly to his mind, and he
was obliged to confess to himself that the half-formed suspicions he
had long entertained were not without foundation. His Uncle John
was at the bottom of all his troubles, and Philip, the Mexican cook,
was his confidential assistant. The boy’s heart sank within him while
he thought about it. He didn’t know what to do, and there was only
one man in the settlement to whom he could go for advice.
“Well, Springer,” said George, suddenly, “we have wasted time
enough. I have a long journey to make, and so have you. I hope you
will succeed in getting safely over the river, and that the lesson you
have received will be the means of making you an honest man. I will
put you on your horse and divide my provisions with you, and that is
all I can do for you.”
“An’ it’s a heap more nor any body else would do for me,” said
Springer, gratefully. “You won’t tell none of the settlers that you seed
me, will you?”
“I’ll not put any of them on your trail,” replied the boy. “I may be
obliged to say something about you; but if you have good luck, you
ought to be safe across the river before I reach Mr. Gilbert’s house,
and that is where I am going.”
After bringing Springer another hatful of water from the bayou, and
dividing with him the small supply of bacon and crackers he had left,
George brought up his horse, and with infinite difficulty assisted the
man to mount. Springer groaned a little and swore a great deal
during the operation, and being a heavy man and almost unable to
help himself, it required the outlay of all George’s strength to put
him into the saddle. After thanking the boy over and over again for
what he had done, he rode slowly away, and George feeling as
though there was nothing in the world worth living for now, once
more turned his face toward the settlement. He looked back now
and then to see how Springer was getting on. The last time he saw
the man he was standing on the top of a high swell holding his hat
in his hand. When he saw George looking at him he waved it in the
air and rode down the swell out of sight.
“If he can keep in his saddle for forty-eight hours—and he would
have no trouble at all in doing it if it were not for his wounds—and
can dodge the rangers who are probably out looking for the raiders,
he will be all right,” thought George; “but if he is compelled to
dismount, I don’t know what will become of him. He can’t possibly
get on his horse again without help. Now, what shall I do? I am
going back to a home where I am not wanted.”
This was the burden of the boy’s thoughts all the rest of the day. He
could not make up his mind to any course of action, for he was so
stunned and bewildered by what he had heard that he could not
think clearly. The only thing he determined upon was, that he would
lay the case before Mr. Gilbert, and be governed by his advice. Mr.
Gilbert was a wealthy cattle-raiser and a prominent man in the
settlement, who had gained his start in life through the assistance of
George’s father. He was a firm friend of the family, and the boy knew
that he could trust him. Toward his rancho he directed his course,
making all the haste he could. He would have been glad to travel all
night, but his weary limbs demanded rest, and when it grew dark
George was obliged, much against his will, to go into camp. He built
a fire in the edge of a belt of post-oaks that ran across his path, and
after gathering fuel enough to last all night, he ate a very light
supper and sat down to think over the situation. When eight o’clock
came he scraped a few leaves together for a bed, and was about to
throw himself down upon it, when he was brought to his feet by the
clatter of hoofs, which sounded a short distance away.
George seized his haversack and waited with a beating heart for the
horsemen, who he knew were approaching his camp, to come in
sight. They came a moment later, and to the boy’s intense relief the
light from his fire shone not upon silver buttons, gaudy sashes and
wide trowsers, but upon a couple of red shirts and slouch hats. With
a long-drawn sigh, indicative of the greatest satisfaction, George
threw down his haversack and stepped forward to greet the new
comers.
“Good-evening, stranger,” said the foremost horseman. “Have you
any objections to good company to-night?”
“None whatever,” answered George, readily. “I shall be only too glad
to have it, for it is lonely work keeping house all by one’s self.”
“We saw the light of your fire,” said the other, “and as we have got a
little out of our reckoning, we made bold to come here, thinking that
perhaps you could set us right.”
“I am glad to see you,” answered George; “but I hope you have
brought your supper with you, for it is little I can offer you.”
“O, that’s nothing. It is no uncommon thing for ranchemen to go
supperless to bed, you know. Where did you stake out your horse,
my lad?”
“I haven’t any, sir. He was stampeded when the Greasers stole my
cattle, and I haven’t seen him since.”
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