Kinetics of chemical reactions: decoding complexity

571 Pages·2019·16.08 MB·English

by  Constales, D., I︠A︡blonskiĭ, Grigoriĭ Semenovich, Marin, Guy B

Table of Contents
Cover
Preface to First Edition
Preface to Second Edition
1 Introduction
1.1 Overview
1.2 Decoding Complexity in Chemical Kinetics
1.3 Three Types of Chemical Kinetics
1.4 Challenges and Goals. How to Kill Chemical Complexity
1.5 What Our Book is Not About. Our Book Among Other Books on Chemical Kinetics
1.6 The Logic in the Reasoning of This Book
1.7 How Chemical Kinetics and Mathematics are Interwoven in This Book
1.8 History of Chemical Kinetics
References
2 Chemical Reactions and Complexity
2.1 Introduction
2.2 Elementary Reactions and the MassAction Law
2.3 The Reaction Rate and Net Rate of Production of a Component – A Big Difference
2.4 Dimensions of the Kinetic Parameters and Their Orders of Magnitude
2.5 Conclusions
Nomenclature
References
3 Kinetic Experiments: Concepts and Realizations
3.1 Introduction
3.2 Experimental Requirements
3.3 Material Balances
3.4 Classification of Reactors for Kinetic Experiments
3.5 Formal Analysis of Typical Ideal Reactors
3.6 Kineticmodelfree Analysis
3.7 Diagnostics of Kinetic Experiments in Heterogeneous Catalysis
Nomenclature
References
4 Chemical Bookkeeping: Linear Algebra in Chemical Kinetics*
4.1 Basic Elements of Linear Algebra
4.2 Linear Algebra and Complexity of Chemical Reactions
4.3 Concluding Remarks
BookKeeping Support in Python/SymPy
Nomenclature
References
5 SteadyState Chemical Kinetics: A Primer
5.1 Introduction to Graph Theory
5.2 Representation of Complex Mechanisms as Graphs
5.3 How to Derive the Reaction Rate for a Complex Reaction
5.4 Derivation of SteadyState Kinetic Equations for a SingleRoute Mechanism –
Examples
5.5 Derivation of SteadyState Kinetic Equations for Multi Route Mechanisms:
Kinetic Coupling
Nomenclature
References
6 Steadystate Chemical Kinetics: Machinery
6.1 Analysis of Rate Equations
6.2 Apparent Kinetic Parameters: Reaction Order and Activation Energy
6.3 How to Reveal Mechanisms Based on Steadystate Kinetic Data
6.4 Concluding Remarks
Nomenclature
References
7 Linear and Nonlinear Relaxation: Stability
7.1 Introduction
7.2 Relaxation in a Closed System − Principle of Detailed Equilibrium
7.3 Stability – General Concept
7.4 Simplifications of Nonsteadystate Models
Nomenclature
References
8 Nonlinear Mechanisms: Steady State and Dynamics
8.1 Critical Phenomena
8.2 Isothermal Critical Effects in Heterogeneous Catalysis: Experimental Facts
8.3 Ideal Simple Models: Steady State
8.4 Ideal Simple Models: Dynamics
8.5 Structure of Detailed Mechanism and Critical Phenomena: Relationships
8.6 Nonideal Factors
8.7 Conclusions
Nomenclature
References
9 Kinetic Polynomials
9.1 Linear Introduction to the Nonlinear Problem: Recap
9.2 Nonlinear Introduction
9.3 Principles of the Approach: QuasiSteadyState Approximation. Mathematical
Basis
9.4 Kinetic Polynomials: Derivation and Properties
9.5 Kinetic Polynomial: Classical Approximations and Simplifications
9.6 Application of Results of the KineticPolynomial Theory: Cycles Across an
Equilibrium
9.7 Critical Simplification
9.8 Concluding Remarks
Appendix
Nomenclature
References
10 Temporal Analysis of Products: Principles, Applications, and Theory
10.1 Introduction
10.2 Characteristics of TAP
10.3 Position of TAP Among Other Kinetic Methods
10.4 Qualitative Analysis of TAP Data: Examples
10.5 Quantitative TAP Data Description. Theoretical Analysis
10.6 Kinetic Monitoring: Strategy of Interrogative Kinetics
10.7 Theoretical Frontiers
10.8 Conclusions: What Next?
Nomenclature
References
11 Joint Kinetics
11.1 Events and Invariances
11.2 Single Reaction
11.3 Multiple Reactions
Nomenclature
References
12 Decoding the Past
12.1 Chemical Time and Intermediates. Early History
12.2 Discovery of Catalysis and Chemical Kinetics
12.3 Guldberg and Waage's Breakthrough
12.4 Van't Hoff's Revolution: Achievements and Contradictions
12.5 PostVan't Hoff Period: Reaction is Not a Singleact Drama
12.6 Allinall Confusion. Attempts at Understanding
12.7 Out of Confusion: Physicochemical Understanding
12.8 Towards Mathematical Chemical Kinetics
Nomenclature
References
13 Decoding the Future
13.1 A Great Achievement, a Great Illusion
13.2 A New Paradigm for Decoding Chemical Complexity
References
Index
End User License Agreement
List of Tables
Chapter 01
Table 1.1 Important events in the development of chemical kinetics in the nineteenth
and twentieth century.
Chapter 02
Table 2.1 Elementary steps in the oxidation of hydrogen.
Table 2.2 Elementary steps in steam reforming of methane.
Table 2.3 Dimension of the rate coefficient k for homogeneous reactions.
Table 2.4 Rate coefficients for firstorder homogeneous reactions.
Table 2.5 Activation energies for firstorder homogeneous reactions.
Chapter 04
Table 4.1 Catalytic cycle, Horiuti numbers, and overall reaction for the twostep
WGS reaction.
Table 4.2 Catalytic cycle, Horiuti numbers, and overall reaction for the model
isomerization reaction.
Table 4.3 Catalytic cycle, Horiuti numbers, and overall reaction for the synthesis of
vinyl chloride from acetylene.
Table 4.4 Catalytic cycle, Horiuti numbers, and overall reaction for the synthesis of
ammonia according to the dissociative mechanism.
Table 4.5 Catalytic cycle, Horiuti numbers, and overall reaction for the oxidation of
carbon monoxide.
Table 4.6 Catalytic cycle, Horiuti numbers, and overall reaction on a catalyst with two
types of active sites.
Table 4.7 Catalytic cycle, Horiuti numbers, and overall reactions for steam reforming
of methane.
Table 4.8 Use of Horiuti's rule to determine the number of reaction routes.
Chapter 05
Table 5.1 Catalytic cycle, Horiuti numbers, and overall reaction for the Michaelis–
Menten mechanism.
Table 5.2 Catalytic cycle, Horiuti numbers, and overall reaction for the WGS reaction.
Table 5.3 Catalytic cycle, Horiuti numbers, and overall reaction for a liquidphase
hydrogenation.
Table 5.4 Catalytic cycle, Horiuti numbers, and overall reaction for the model
isomerization reaction.
Table 5.5 Catalytic cycle, Horiuti numbers, and overall reaction for the oxidation of
hydrogen.
Table 5.6 Catalytic cycle, Horiuti numbers, and overall reaction for the synthesis of
vinyl chloride from acetylene.
Table 5.7 Catalytic cycle, Horiuti numbers, and overall reactions for the reaction of
NO with CO.
Table 5.8 Catalytic cycle, Horiuti numbers, and overall reactions for the
dehydrogenation of butane.
Table 5.9 Catalytic cycle, Horiuti numbers, and overall reactions for steam reforming
of methane.
Table 5.10 Catalytic cycle, Horiuti numbers, and overall reactions for the catalytic
a b
reforming of nhexane. ,
Table 5.11 Sequences of reactions in catalytic reforming of nhexane.
Table 5.12 Catalytic cycle, Horiuti numbers, and overall reaction for the twostep
Temkin–Boudart mechanism.
Table 5.13 Catalytic cycle, Horiuti numbers, and overall reaction for the twostep
mechanism for the oxidation of SO .
2
Table 5.14 Catalytic cycle, Horiuti numbers, and overall reaction for a hypothetical
isomerization mechanism.
Chapter 08
Table 8.1 Parallel and consecutive adsorption mechanisms; A and B are gaseous
m n
reactants, A B and A B are gaseous products, Z is a free active site and AZ, BZ,
p q p+q q
and ABZ are surface intermediates.
Table 8.2 Parallel adsorption mechanism for the oxidation of CO over platinum.
Table 8.3 Example of an impact mechanism; A and B are gaseous reactants, A B is a
m n
gaseous product, and Z and AZ are surface intermediates.
Table 8.4 Impact mechanism for the oxidation of CO over platinum.
Table 8.5 Impact mechanism for the WGS reaction.
Table 8.6 Parallel adsorption mechanism for reaction of A with B.
2
Table 8.7 Steadystate reaction rates.
Table 8.8 Steady states of the parallel adsorption mechanism.
Table 8.9 Characteristics of “realistic” parallel adsorption mechanisms: necessary
conditions for steady states (ss) and number of steady states (for ); bss,
boundary steady state; iss, internal steady state.
Table 8.10 Mechanisms explaining the multiplicity of steady states.
Table 8.11 Simplest consecutive adsorption mechanism exhibiting multiple steady
states, with m = n = q = 1 and p = 2.
Table 8.12 Possible adsorption mechanism, with a buffer step, for the overall reaction
.
Table 8.13 Adsorption mechanism with a buffer step.
Table 8.14 Representation of the Turner–Sales–Maple mechanism for CO oxidation
[41, 101–103].
Table 8.15 Representation of the mechanism for CO oxidation proposed by Ertl et al.
[56–59].
Table 8.16 Representation of the mechanism for CO oxidation proposed by Vishnevskii
and Savchenko [63, 152].
Table 8.17 Catalytic cycle, Horiuti numbers, and overall reaction for the oxidation of
hydrogen.
Chapter 09
Table 9.1 Catalytic cycle, Horiuti numbers, and overall reaction for an impact
mechanism.
Table 9.2 Catalytic cycle, Horiuti numbers, and overall reaction for an adsorption
mechanism.
Table 9.3 Catalytic cycle, Horiuti numbers, and overall reaction for a tworoute
mechanism.
Table 9.4 Catalytic cycle, Horiuti numbers, and overall reaction for the oxidation of
carbon monoxide.
Chapter 10
Table 10.1 Position of the TAP approach among other kinetic approaches.
Table 10.2 Applications and theory of the TAP reactor including the corresponding
catalytic materials tested. Updated from Gleaves et. al 2010 [30].
Table 10.3 Catalysts, mechanisms, and parameters derived for various oxidation
reactions.
Table 10.4 Catalysts, mechanisms, and parameters derived for NOx abatement
reactions.
Table 10.5 Basic kinetic coefficients for different detailed mechanisms.
Table 10.6 Possible measurement scenarios for the reaction of A to product B.
Table 10.7 Average moments and reactivities at different temperatures.
Chapter 11
Table 11.1 Time invariances for some single nonlinear reversible reactions.
Table 11.2 Conditions of occurrence and time values for possible events in the
concentration versus time plot in the BR.
Table 11.3 Conditions of occurrence and time values for possible events in the rate
versus time plot in the BR.
Table 11.4 Conditions of occurrence and time values for possible events in the
concentration versus time plot in the CSTR.
Table 11.5 Conditions of occurrence and time values for possible events in the rate
versus time plot in the CSTR.
Table 11.6 Color guide for the occurrence of events in the barycentric plots of Figures
11.2 and 11.3.
List of Illustrations
Chapter 01
Figure 1.1 Building blocks of this book.
Chapter 03
Figure 3.1 Reactors for kinetic experiments: (a) batch reactor; (b) continuous stirred
tank reactor; (c) continuousflow reactor with recirculation; (d) plugflow reactor;
(e) differential plugflow reactor; (f) convectional pulse reactor; (g) diffusional pulse
reactor or TAP reactor; and (h) thinzone TAP reactor.
Figure 3.2 Temporal kinetic dependences in a batch reactor for the reaction
with
.
Figure 3.3 Temporal kinetic dependences in a batch reactor for the reversible reaction
(lower curve) compared with the irreversible reaction
(upper curve); k = k + = 1 s−1, k − = 0.7 s−1.
Figure 3.4 (a) Parallel reactions and (b) consecutive reactions.
Figure 3.5 Qualitative temporal kinetic dependences in a batch reactor for the parallel
mechanism.
Figure 3.6 Qualitative temporal kinetic dependences in a batch reactor for the
consecutive mechanism.
Figure 3.7 Typical temperature and axial concentration profiles for an exothermic
consecutive reaction
in a tubular reactor; T , T , and T are the inlet, peak, and outlet temperatures,
in peak out
respectively.
Figure 3.8 Interphase and intraparticle reactant concentration and temperature profiles
for an exothermic reaction. The resistances against mass and heat transfer are
completely located in a stagnant gas film surrounding the pellet; δ is the film thickness;
subscripts b and s denote bulk fluid and catalyst surface, respectively.
Figure 3.9 Diagnostic test for external concentration gradients.
Figure 3.10 Dependence of the observed reaction rate on the diameter of the catalyst
pellet.
Chapter 05
Figure 5.1 Map of Königsberg in Euler's time showing the actual layout of the seven
bridges, highlighting the river Pregel and the bridges (left) and abstracted case (right).
Figure 5.2 The “badneighbors” problem.
Figure 5.3 (a) Mechanism and (b) King–Altman graph of a singleroute enzyme
catalyzed reaction.
Figure 5.4 Graphs of linear mechanisms. (a) Michaelis–Menten mechanism; (b) WGS
reaction; (c) liquidphase hydrogenation; (d) model isomerization reaction; and (e)
hydrogen oxidation.
Figure 5.5 Catalytic cycle and Horiuti numbers (a) and graph (b) for the modified
Michaelis–Menten mechanism.
Figure 5.6 Graphs of tworoute linear mechanisms – (a) with a common intermediate:
synthesis of vinyl chloride; (b) with a common step: reaction of NO with CO; (c) with
a common step: dehydrogenation of butane; and (d) with a common intermediate: steam
reforming of methane. Roman numbers indicate the different routes.
Figure 5.7 Survey of single and tworoute mechanisms; singleroute mechanism (a)
without buffer step and (b) with buffer step X  Y ; tworoute mechanism (c) with a
common intermediate X, (d) with a common step, (e) with buffer step Y  Z , and (f)
with “bridge” step X  Y connecting two cycles. Roman numbers indicate the different
routes.
Figure 5.8 Catalytic reforming of nhexane over a supported Pt catalyst: (a) graph and
(b) simplified graph. The accompanying consumption or production of hydrogen is not
shown.
Figure 5.9 Catalytic reforming of nhexane over a supported Pt catalyst: (a) the seven
independent simple cycles and (b) examples of dependent simple cycles.
Figure 5.10 (a) Mechanism and (b) King–Altman graph of the model isomerization
reaction.
Figure 5.11 Spanning trees of the model isomerization reaction of Figure 5.10: (a)
forward; (b) reverse; and (c) combined.
Figure 5.12 (a) Michaelis–Menten mechanism and (b) graph.
Figure 5.13 (a) Mechanism and (b) graph of the WGS reaction.
Figure 5.14 (a) Mechanism and (b) graph of a liquidphase hydrogenation.
Figure 5.15 (a) Possible mechanism and (b) graph for the oxidation of SO .
2
Figure 5.16 (a) Possible mechanism and (b) graph for a coupling reaction.
Figure 5.17 (a) Possible mechanism and (b) graph for steam reforming of methane.