Rate Constant Calculation for Thermal Reactions E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 566

Veröffentlichungsjahr: 2011

Beschreibung

Providing an overview of the latest computational approaches to estimate rate constants for thermal reactions, this book addresses the theories behind various first-principle and approximation methods that have emerged in the last twenty years with validation examples. It presents in-depth applications of those theories to a wide range of basic and applied research areas. When doing modeling and simulation of chemical reactions (as in many other cases), one often has to compromise between higher-accuracy/higher-precision approaches (which are usually time-consuming) and approximate/lower-precision approaches (which often has the advantage of speed in providing results). This book covers both approaches. It is augmented by a wide-range of applications of the above methods to fuel combustion, unimolecular and bimolecular reactions, isomerization, polymerization, and to emission control of nitrogen oxides. An excellent resource for academics and industry members in physical chemistry, chemical engineering, and related fields.

Leseprobe

Contents

Cover

Title Page

Copyright

Preface

Contributors

Part I: Methods

Chapter 1: Overview of Thermochemistry and Its Application to Reaction Kinetics

1.1 History of Thermochemistry

1.2 Thermochemical Properties

1.3 Consequences of Thermodynamic Laws to Chemical Kinetics

1.4 How to Get Thermochemical Values?

1.5 Accuracy of Thermochemical Values

1.6 Representation of Thermochemical Data for Use in Engineering Applications

1.7 Thermochemical Databases

1.8 Conclusion

References

Chapter 2: Calculation of Kinetic Data Using Computational Methods

2.1 Introduction

2.2 Stationary Points and Potential Energy Hypersurfaces

2.3 Calculation of Reaction and Activation Energies: Levels of Theory and Solvent Effects

2.4 Estimate of Relative Free Energies: Standard States

2.5 Theoretical Approximate Kinetic Constants and Treatment of Data

2.6 Selected Examples

2.7 Conclusions and Outlook

References

Chapter 3: Quantum Instanton Evaluation of the Kinetic Isotope Effects and of the Temperature Dependence of the Rate Constant

3.1 Introduction

3.2 Arrhenius Equation, Transition State Theory, and the Wigner Tunneling Correction

3.3 Quantum Instanton Approximation for the Rate Constant

3.4 Kinetic Isotope Effects

3.5 Temperature Dependence of the Rate Constant

3.6 Path Integral Representation of Relevant Quantities

3.7 Examples

3.8 Summary

Appendix: Reactions

Acknowledgments

References

Chapter 4: Activation Energies in Computational Chemistry—A Case Study

4.1 Introduction

4.2 Context and Theoretical Background

4.3 Computational Details

4.4 Recent Advances and New Results

4.5 Concluding Remarks

Acknowledgments

References

Chapter 5: No Barrier Theory—A New Approach to Calculating Rate Constants in Solution

5.1 Introduction

5.2 The Idea Behind No Barrier Theory

5.3 How to Define the Surface and Find the Transition State

5.4 What is Needed for a Calculation?

5.5 Applications to Date

5.6 Future Prospects for NBT

5.7 Summary

References

Part II: Minireviews and Applications

Chapter 6: Quantum Chemical and Rate Constant Calculations of Thermal Isomerizations, Decompositions, and Ring Expansions of Organic Ring Compounds, Its Significance to Cohbusion Kinetics

6.1 Prologue

6.2 Small Organic Ring Compounds

6.3 Pyrrole and Indole

6.4 Dihydrofurans and Dihydrobenzofurans

6.5 Naphthyl Acetylene–Naphthyl Ethylene

6.6 Ring Expansion Processes

6.7 Benzoxazole–Benzisoxazoles

6.8 Conclusion

Acknowledgment

References

Chapter 7: Challenges in the Computation of Rate Constants for Lignin Model Compounds

7.1 Lignin: A Renewable Source of Fuels and Chemicals

7.2 Mechanistic Study of Lignin Model Compounds

7.3 Computational Investigation of the Pyrolysis of β-O-4 Model Compounds

7.4 Case Studies: Substituent Effects on Reactions of Phenethyl Phenyl Ethers

7.5 Conclusions and Outlook

Acknowledgments

Appendix Summary of Kinetic Parameters

References

Chapter 8: Quantum Chemistry Study on the Pyrolysis Mechanisms of Coal-Related Model Compounds

8.1 Introduction to the Application of Quantum Chemistry Calculation to Investigation on Models of Coal Structure

8.2 The Model for Coal Structure and Calculation Methods

8.3 The Pyrolysis Mechanisms of Coal-Related Model Compounds

8.4 Conclusion

References

Chapter 9: Ab Initio Kinetic Modeling of Free-Radical Polymerization

9.1 Introduction

9.2 Ab Initio Kinetic Modeling

9.3 Quantum Chemical Methodology

9.4 Case Study: RAFT Polymerization

9.5 Outlook

References

Chapter 10: Intermolecular Electron Transfer Reactivity for Organic Compounds Studied Using Marcus Cross-Rate Theory

10.1 Introduction

10.2 Determination of ΔG‡ii (fit) Values

10.3 Why is the Success of Cross-Rate Theory Surprising?

10.4 Major Factors Determining Intrinsic Reactivities of Hydrazine Couples

10.5 Nonhydrazine Couples

10.6 Comparison of ΔG‡ii (fit) with ΔG‡ii (self) Values

10.7 Estimation of Hab from Experimental Exchange Rate Constants and DFT-Computed λ

10.8 Comparison with Gas-Phase Reactions

10.9 Conclusions

References

Index

Copyright © 2012 by John Wiley & Sons, Inc. All rights reserved

Published by John Wiley & Sons, Inc., Hoboken, New JerseyPublished simultaneously in Canada

No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, [phone], fax [phone], or on the web at www.copyright.com. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, [phone], fax [phone], or online at http://www.wiley.com/go/permission.

Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives or written sales materials. The advice and strategies contained herein may not be suitable for your situation. You should consult with a professional where appropriate. Neither the publisher nor author shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages.

For general information on our other products and services or for technical support, please contact our Customer Care Department within the United States at [phone], outside the United States at [phone] or fax [phone].

Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic formats. For more information about Wiley products, visit our web site at www.wiley.com.

Library of Congress Cataloging-in-Publication Data:

Rate constant estimation for thermal reactions: methods and applications / edited by Herbert DaCosta, Maohong Fan.

p. cm.

Includes bibliographical references and index.

ISBN 978-0-470-58230-5

1. Thermochemistry–Mathematics. 2. Chemical kinetics–Effect of temperature on–Mathematics. 3. Numerical calculations. I. DaCosta, Herbert. II. Fan, Maohong.

QD504.R38 2012

541′.36–dc23

2011041445

Preface

In the past 30 years, the computational chemistry field has experienced an exponential growth. This growth has been enabled by tremendous improvements in computer hardware, theoretical methods, and numerical methods to integrate the theoretical methods into computer software. Applications of computational chemistry are now abundant in diversified areas, including nanotechnology, drug design, materials design, molecular design, tribology, lubricants, coal chemistry, petroleum chemistry, biomass chemistry, combustion, and catalysis.

The recent developments in computational chemistry have also enabled a large qualitative leap in the field of computational kinetics, thus yielding significant contributions to the chemical and engineering literatures. Despite all these progresses, to our knowledge, a book describing the modern methods used by scientists and engineers in order to predict rate constants has not as yet been published. This book addresses this need, as it was designed to serve as a major reference for prediction of rate constants of thermal reactions. Some successful examples along with the highlights of certain computational methods currently used in the literature are presented in this book. Therefore, it will be a useful tool for academic and industrial chemists and engineers working in the areas of chemical kinetics and reaction engineering.

The first five chapters (Part I) present an overview of some methods that have been used in the recent literature to calculate rate constants and the associated case studies. The main topics covered in this part include thermochemistry and kinetics, computational chemistry and kinetics, quantum instanton, kinetic calculations in liquid solutions, and new applications of density functional theory in kinetic calculations. The remaining five chapters (Part II) are focused on applications even though methodologies are discussed. The topics in the second part include the kinetics of molecules relevant to combustion processes, intermolecular electron transfer reactivity of organic compounds, lignin model compounds, and coal model compounds in addition to free radical polymerization.

This book is also part of Wiley's special celebration activities in marking the International Year of Chemistry in 2011.

We would like to thank the whole Wiley team, in particular our Senior Acquisitions Editor, Mrs. Anita Lekhwani, for her vision, persistence, and support throughout the whole editing process, as well as Ms. Becky Amos and Ms. Catherine Odal, for their many helps.

We would also like to thank the outstanding body of researchers who contributed their time, knowledge, and expertise to the publication of this book.

Happy International Year of Chemistry!

Herbert DaCostaMaohong Fan

Contributors

Elisabet Ahlberg, Department of Chemistry, Electrochemistry, University of Gothenburg, Gothenburg, Sweden

Ariana Beste, Computer Science and Mathematics Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA

A.C. Buchanan, III, Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA

Alexander Burcat, Faculty of Aerospace Engineering, Technion: Israel Institute of Technology, Haifa, Israel

Michael Busch, Department of Chemistry, Electrochemistry, University of Gothenburg, Gothenburg, Sweden

Michelle L. Coote, ARC Centre of Excellence in Free-Radical Chemistry and Biotechnology, Research School of Chemistry, Australian National University, Canberra, Australia

Fernando P. Cossío, Departamento de Química Orgánica I, Universidad del País Vasco-Euskal Herriko Unibertsitatea, San Sebastián-Donostia, Spain

Faina Dubnikova, Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem, Israel

Elke Goos, Institute of Combustion Technology, German Aerospace Center (DLR), Stuttgart, Germany

J. Peter Guthrie, Department of Chemistry, University of Western Ontario, London, Ontario, Canada

Assa Lifshitz, Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem, Israel

Lixia Ling, Research Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan, China

Stephen F. Nelsen, Department of Chemistry, University of Wisconsin, Madison, WI, USA

Itai Panas, Department of Chemistry and Biotechnology, Energy and Materials, Chalmers University of Technology, Gothenburg, Sweden

Jack R. Pladziewicz, Department of Chemistry, University of Wisconsin, Eau Claire, WI, USA

Jií Vaníek, Laboratory of Theoretical Physical Chemistry, Institut des Sciences et Ingénierie Chimiques, École Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland

Baojun Wang, Key Laboratory of Coal Science and Technology, Taiyuan University of Technology, Ministry of Education and Shanxi Province, Taiyuan, China

Riguang Zhang, Key Laboratory of Coal Science and Technology, Taiyuan University of Technology, Ministry of Education and Shanxi Province, Taiyuan, China

Part I

Methods