Cover
Title Page
About the Author
Preface
1 Fundamentals of Chemical Reaction Kinetics
1. 1.1 Concepts of Stoichiometry
2. 1.2 Reacting Systems
3. 1.3 Concepts of Chemical Kinetics
4. 1.4 Description of Ideal Reactors
2 Irreversible Reactions of One Component
1. 2.1 Integral Method
2. 2.2 Differential Method
3. 2.3 Method of Total Pressure
4. 2.4 Method of the Half‐Life Time
3 Irreversible Reactions with Two or Three Components
1. 3.1 Irreversible Reactions with Two Components
2. 3.2 Irreversible Reactions between Three Components
4 Reversible Reactions
1. 4.1 Reversible Reactions of First Order
2. 4.2 Reversible Reactions of Second Order
3. 4.3 Reversible Reactions with Combined Orders
5 Complex Reactions
1. 5.1 Yield and Selectivity
2. 5.2 Simultaneous or Parallel Irreversible Reactions
3. 5.3 Consecutive or In‐Series Irreversible Reactions
6 Special Topics in Kinetic Modelling
1. 6.1 Data Reconciliation
2. 6.2 Methodology for Sensitivity Analysis of Parameters
3. 6.3 Methods for Determining Rate Coefficients in Enzymatic Catalysed Reactions
4. 6.4 A Simple Method for Estimating Gasoline, Gas and Coke Yields in FCC Processes
5. 6.5 Estimation of Activation Energies during Hydrodesulphurization of Middle Distillates
Problems
1. Irreversible Reactions of One Component
2. Irreversible Reactions with Two or Three Components
3. Reversible Reactions
4. Complex Reactions
Nomenclature
1. Greek Letters
2. Subindex
References
Index
End User License Agreement

List of Tables

Chapter 01
1. Table 1.1 Chemical reactions with different molecularity.
2. Table 1.2 Data and results of Example 1.4.
3. Table 1.3 Data and results of Example 1.6.
4. Table 1.4 Data and results of Example 1.7.
5. Table 1.5 Data and results of Example 1.8.
6. Table 1.6 Chemical reactions with differents orders.
7. Table 1.7 Data and results of Example 1.11.
8. Table 1.8 Experimental data of thermal cracking of ethane.
9. Table 1.9 Experimental data of the hydrogenation of ethylene.
10. Table 1.10 Results of the non‐linear regression of Example 1.12.
Chapter 02
1. Table 2.1 Examples of irreversible reactions with one component.
2. Table 2.2 Data and results of Example 2.1.
3. Table 2.3 Data of Example 1.7 and results of Example 2.2.
4. Table 2.4 Procedure to calculate ΔC_A/Δt.
5. Table 2.5 Method of finite differences for five experimental points.
6. Table 2.6 Data of Example 2.3 and results with the method of approaching the derivative −dC_A/dt to ΔC_A/Δt.
7. Table 2.7 Results with the method of polynomium of n^th order for Example 2.3.
8. Table 2.8 Calculation of dC_A/dt with a third‐order polynomial for Example 2.3.
9. Table 2.9 Calculation of dC_A/dt with the method of area compensation for Example 2.3.
10. Table 2.10 Summary of results of Example 2.3.
11. Table 2.11 Data and results of Example 2.4.
12. Table 2.12 Data and results of Example 2.6.
13. Table 2.13 Data and results of Example 2.8.
Chapter 03
1. Table 3.1 Examples of irreversible reactions between two components.
2. Table 3.2 Integral method for irreversible reactions with two components with stoichiometric feed composition.
3. Table 3.3 Data and results of Example 3.1.
4. Table 3.4 Integral method for reactions between two components with non‐stoichiometry feed composition.
5. Table 3.5 Data and results of Example 3.2.
6. Table 3.6 Data and results of Example 3.3.
7. Table 3.7 Data and results of Example 3.4.
8. Table 3.8 Information required for solving Eqs. (3.39)–(3.41) of Example 3.4.
9. Table 3.9 Data and results of Example 3.5.
10. Table 3.10 Data and results of Example 3.6.
Chapter 04
1. Table 4.1 Data and results of Example 4.1.
2. Table 4.2 Integrated equations for reversible reactions of second order.
3. Table 4.3 Data and results of Example 4.2.
4. Table 4.4 Integrated equations for reversible reactions with combined orders.
5. Table 4.5 Integrated equations for reversible reactions of second order with non‐stoichiometric feed composition.
6. Table 4.6 Data and results of Example 4.3.
Chapter 05
1. Table 5.1 Data and results of Example 5.1.
2. Table 5.2 Data and results of Example 5.2.
3. Table 5.3 Data and results of Example 5.3.
4. Table 5.4 Data and results of Example 5.4.
Chapter 06
1. Table 6.1 Experimental data of liquid feed and product.
2. Table 6.2 Required information to determine outliers.
3. Table 6.3 Comparison of traditional methods with data reconciliation.
4. Table 6.4 Example of different linear equations obtained from a same model.
5. Table 6.5 Example of parameter estimation with linear and non‐linear regression analyses.
6. Table 6.6 Summary of results of benzothiophene HDS kinetics (taken from Kilanowski and Gates, 1980).
7. Table 6.7 Comparison of reported and calculated kinetic parameters.
8. Table 6.8 SSE determined with reported, calculated and optimized kinetic parameters.
9. Table 6.9 Experimental data reported in the literature for enzymatic reactions (taken from different sources).
10. Table 6.10 Results of the estimation kinetic parameters.
11. Table 6.11 Summary of experimental data reported in the literature at 548.9 °C and C/O of 4 (taken from Wang, 1970).
12. Table 6.12 Properties of the feeds.
13. Table 6.13 Comparison of kinetic parameter values determined with the two approaches.

List of Illustrations

Chapter 01
1. Figure 1.1 Reacting system at constant density.
2. Figure 1.2 Reacting system at variable density.
3. Figure 1.3 Graphical representation of the reaction rate.
4. Figure 1.4 Graphical representation of the activation energy.
5. Figure 1.5 Graphical representation of the Arrhenius equation and its linearization by the traditional method.
6. Figure 1.6 Graphical representation of the reparameterized Arrhenius equation.
7. Figure 1.7 Graphical representation of the Arrhenius equation with the method of reduction of orders of magnitude.
8. Figure 1.8 Results of Example 1.11. () TM, () RM.
9. Figure 1.9 Results of Case 1 for Example 1.12.
10. Figure 1.10 Results of Case 2 for Example 1.12.
11. Figure 1.11 Results of Case 3 for Example 1.12.
12. Figure 1.12 Residuals analysis for Case 2 for Example 1.12.
13. Figure 1.13 Typical experimental setup of a batch reactor.
14. Figure 1.14 Typical pressure (‐‐‐) and temperature (–) profiles in a batch reactor operated isothermally.
15. Figure 1.15 Typical pressure (‐‐‐) and temperature (–) profiles in a batch reactor operated by temperature scanning.
16. Figure 1.16 Schematic of a batch reactor.
17. Figure 1.17 Schematic of a plug flow reactor.
18. Figure 1.18 Schematic of a continuous stirred tank reactor.
19. Figure 1.19 Examples of a laboratory batch reactor, PFR and CSTR.
Chapter 02
1. Figure 2.1 Graphical integral method for irreversible reactions of one component of zero order.
2. Figure 2.2 Graphical integral method for irreversible reactions of one component of the first order.
3. Figure 2.3 Graphical integral method for irreversible reactions of one component of the second order.
4. Figure 2.4 Graphical integral method for irreversible reactions of one component of the n^th order.
5. Figure 2.5 Results of Example 2.1.
6. Figure 2.6 Differential method for analysis of kinetic data with Eq. (2.31).
7. Figure 2.7 Method of numerical differentiation by approaching the derivative (−dC_A/dt) to (ΔC_A/Δt).
8. Figure 2.8 Method of graphic differentiation by area compensation.
9. Figure 2.9 Application of the method of approaching the derivative (−dC_A/dt) to (ΔC_A/Δt) for Example 2.3.
10. Figure 2.10 Method of finite differences.
11. Figure 2.11 Application of the method of a polynomial of the n^th order for Example 2.3.
12. Figure 2.12 Calculation of ΔC_A/Δt at regular intervals of time.
13. Figure 2.13 Application of the method of area compensation for Example 2.3.
14. Figure 2.14 Application of the integral method for n = 1 for Example 2.3.
15. Figure 2.15 Method of total pressure for irreversible reactions of one component.
16. Figure 2.16 Differential method with data of total pressure.
17. Figure 2.17 Application of the differential method with data of total pressure for Example 2.5.
18. Figure 2.18 Data required to use the method of half‐life time.
19. Figure 2.19 Method of half‐life time for irreversible reactions of one component.
20. Figure 2.20 Direct method to calculate n and k with data of half‐life time.
21. Figure 2.21 Application of the direct method with data of half‐life time for Example 2.7.
22. Figure 2.22 Calculation of E_A with data of t_1/2.
23. Figure 2.23 Calculation of E_A for Example 2.8.
Chapter 03
1. Figure 3.1 Profile of concentrations during a reaction with a reactant in excess.
2. Figure 3.2 Experiment 1 for the method of initial reaction rates.
3. Figure 3.3 Experiment 2 for the method of initial reaction rates.
Chapter 04
1. Figure 4.1 Graphical representation of Eqs. (4.5) and (4.6).
2. Figure 4.2 Graphic representation of Eqs. (4.17) and (4.19).
Chapter 05
1. Figure 5.1 Profiles of product yield and conversion for a reaction in series with different values of K.
2. Figure 5.2 Typical profile of concentration for simultaneous or parallel irreversible reactions.
3. Figure 5.3 Calculation of k₀ for simultaneous irreversible reactions.
4. Figure 5.4 Calculation of R₂₁ and R_n1 for simultaneous irreversible reactions.
5. Figure 5.5 Calculation of R₂₁ and R₃₁.
6. Figure 5.6 Calculation of k₂ for simultaneous reactions with combined orders.
7. Figure 5.7 Calculation of k₂/k₁ for consecutive reactions with combined orders with the differential method.
8. Figure 5.8 Profiles of concentration for consecutive irreversible reactions.
Chapter 06
1. Figure 6.1 Bench‐scale plant flow sheet.
2. Figure 6.2 Bench‐scale global mass balances. Liquid (), gas ().
3. Figure 6.3 Boxplots of outliers data for run 2.
4. Figure 6.4 Reconciled mass balances, Case 1. Liquid (), gas ().
5. Figure 6.5 Reconciled mass balances, Case 2. Liquid (), gas ().
6. Figure 6.6 Proposed methodology for parameter estimation.
7. Figure 6.7 Results of Monte Carlo simulation at 252.5 °C. (a) 1 < k < 100, (b) 0.01 < k < 10, (c) 0.001 < k < 0.00001.
8. Figure 6.8 Iterative process for minimization of the objective function at 252.5 °C.
9. Figure 6.9 Sensitivity analysis of calculated parameters for the model at 252.5 °C. (◆) k, (∆) K_BT , () K _H2S.
10. Figure 6.10 Sensitivity analysis of calculated parameters for the model at 302 °C. (◆) k, (∆) K_BT , (x) K _H2, () K _H2S.
11. Figure 6.11 Sensitivity analysis of calculated parameters for the model at 332.5 °C. (◆) k, (∆) K_BT , (x) K _H2, () K _H2S.
12. Figure 6.12 Sensitivity analysis of parameter K _H2S with ±10% perturbation for the model at 252.5 °C.
13. Figure 6.13 New sensitivity analysis of optimized parameters for the model at 252.5 °C. (◆) k, (∆) K_BT , (x) K _H2, () K _H2S.
14. Figure 6.14 Residual analysis for the model at () 252.5 °C, () 302 °C, (∆) 332.5 °C.
15. Figure 6.15 Model for the behaviour of an enzymatic reaction.
16. Figure 6.16 Graphical representation of the Michaelis–Menten equation.
17. Figure 6.17 Optimal values of parameters of the Michaelis–Menten equation.
18. Figure 6.18 Global minimum and local minima in a non‐lineal regression.
19. Figure 6.19 Application of the lineal regression method for example 1.
20. Figure 6.20 Representation of the graphical method (Case 1) and integral method.
21. Figure 6.21 Comparison of R ² for the four methods of lineal regression.
22. Figure 6.22 Three‐lump kinetic model.
23. Figure 6.23 Four‐lump kinetic model.
24. Figure 6.24 Comparison between SOP (•) and FOP (ο) for conversion prediction.
25. Figure 6.25 Experimental (symbols) and predicted (lines) gasoline, gas and coke yields using data reported in the literature.
26. Figure 6.26 Effect of reaction temperature and time on (a) sulphur content in the product, (b) specific gravity of the product. () QS, () LCO, () LSRGO, (■) HSRGO.
27. Figure 6.27 Sum of squared errors of the differences between experimental and calculated sulphur contents. () QS, () LCO, () LSRGO, (■) HSRGO.
28. Figure 6.28 Linear representation of (a) power law model, (b) Arrhenius equation. () QS, () LCO, () LSRGO, (■) HSRGO.
29. Figure 6.29 Relationship between reaction order () and activation energy () with sulphur content in the feed.

This edition first published 2017
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Library of Congress Cataloging‐in‐Publication Data

Names: Ancheyta, Jorge.
Title: Chemical reaction kinetics : concepts, methods and case studies /
Prof. Jorge Ancheyta.
Description: Hoboken, NJ : John Wiley & Sons, Inc., 2017. | Includes
bibliographical references and index.
Identifiers: LCCN 2017004766 (print) | LCCN 2017005385 (ebook) |
ISBN 9781119226642 (cloth) | ISBN 9781119226659 (Adobe PDF) |
ISBN 9781119227007 (ePub)
Subjects: LCSH: Chemical kinetics. | Chemical reactions.
Classification: LCC QD502 .A53 2017 (print) | LCC QD502 (ebook) | DDC
541/.394–dc23
LC record available at https://lccn.loc.gov/2017004766

Cover Design: Wiley
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Preface

Reaction kinetics is mainly focused on studying the rate at which chemical reactions proceed. It is also used to analyse the factors that affect the reaction rates and the mechanisms by means of which they take place.

The study of the chemical kinetics of a reaction is a fundamental tool to perform in the design of chemical reactors, to predict the reactor’s performance and to develop new processes. In fact, the first step for designing a chemical reactor is always the generation of experimental data whereby the reaction rate expressions are determined.

Chemical Reaction Kinetics: Concepts, Methods and Case Studies is devoted to describing the fundamentals of reaction kinetics, with particular emphasis on the mathematical treatment of the experimental data. The book is organized in six chapters, each one having detailed deductions of the kinetic models with examples.

Chapter 1 deals with the definitions of the main concepts of stoichiometry, reacting systems, chemical kinetics and ideal reactors.

Chapter 2 gives details about the mathematical methods to determine the reaction order and the reaction rate coefficient for irreversible reactions with one component. The methods described here include the integral method, differential method, total pressure method and half‐life time method.

Chapter 3 reports the mathematical methods for evaluating the kinetics of irreversible reactions with two or three components by employing the integral method, differential method and initial reaction rate method. All of the mathematical treatments are performed according to the type of feed composition: stoichiometric, non‐stoichiometric and with a reactant in excess.

Chapter 4 describes the reversible reactions of first order, second order and combined orders.

Chapter 5 presents the mathematical treatment of complex reactions, that is, simultaneous or parallel irreversible reactions and consecutive or in‐series irreversible reactions, with the same order or with combined orders.

Chapter 6 is devoted to special topics in kinetic modelling, which include reconciliation of data generated during experiments to minimize the inconsistencies of mass balances due to experimental errors, a method for sensitivity analysis to assure that kinetic parameters are properly estimated and the convergence of the objective function to the global minimum is achieved, estimation of kinetic parameters of enzymatic reactions by means of different approaches, estimation of kinetic parameters of catalytic cracking reaction using a lumping approach and estimation of kinetic parameters of hydrodesulphurization of petroleum distillates.

Each chapter illustrates the application of the different methods with detailed examples by using experimental information reported in the literature. Step‐by‐step solutions are provided so that the methods can be easily followed and applied for other situations. Some exercises are provided at the end to allow the reader to apply all of the methods developed in the previous chapters.

Chemical Reaction Kinetics: Concepts, Methods and Case Studies is oriented to cover the contents of undergraduate and postgraduate courses on reaction kinetics of chemical engineering and similar careers. It is anticipated that Chemical Reaction Kinetics: Concepts, Methods and Case Studies will become an outstanding and distinctive textbook because it emphasizes detailed description of fundamentals, mathematical treatments and examples of chemical reaction kinetics, which are not described with such details in previous textbooks related to the topic. The particular manner in which the kinetic models are developed will help the readers adapt to their own reaction studied and experimental data.

I would like to acknowledge Prof. Miguel A. Valenzuela from the School of Chemical Engineering and Extractive Industries at the National Polytechnic Institute of Mexico, who contributed some ideas during the preparation of the Spanish version of this book, and also to hundreds of students who during more than 20 years of delivering lectures encouraged me to write this book.

Jorge Ancheyta