Rate Constant Calculation for Thermal Reactions (eBook, ePUB)

Methods and Applications
Redaktion: Dacosta, Herbert; Fan, Maohong

• Format: ePub

Produktbeschreibung

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.

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Produktdetails

• Verlag: John Wiley & Sons
• Seitenzahl: 360
• Erscheinungstermin: 28. Dezember 2011
• Englisch
• ISBN-13: 9781118166116
• Artikelnr.: 37484605

Autorenporträt

Herbert DaCosta is currently a principal consultant at Chem-Innovations LLC and an adjunct professor of chemistry at Illinois Central College. His research interests include environmental catalysis and clean energy, nanomaterial design and synthesis, computational chemistry, and kinetics. Maohong Fan is Associate Professor at the University of Wyoming and an adjunct associate professor at the Georgia Institute of Technology. His research interests include nanomaterial synthesis and application, green processes for chemical production, and new approaches to clean energy generation.

Inhaltsangabe

PREFACE xiii Herbert DaCosta and Maohong Fan CONTRIBUTORS xv PART I METHODS
1 1. Overview of Thermochemistry and Its Application to Reaction Kinetics 3
Elke Goos and Alexander Burcat 1.1. History of Thermochemistry 3 1.2.
Thermochemical Properties 5 1.3. Consequences of Thermodynamic Laws to
Chemical Kinetics 8 1.4. How to Get Thermochemical Values? 10 1.4.1.
Measurement of Thermochemical Values 10 1.4.2. Calculation of
Thermochemical Values 10 1.4.2.1. Quantum Chemical Calculations of
Molecular Properties 10 1.4.2.2. Calculation of Thermodynamic Functions
from Molecular Properties 12 1.5. Accuracy of Thermochemical Values 16
1.5.1. Standard Enthalpies of Formation 16 1.5.2. Active Thermochemical
Tables 18 1.6. Representation of Thermochemical Data for Use in Engineering
Applications 21 1.6.1. Representation in Tables 21 1.6.2. Representation
with Group Additivity Values 21 1.6.3. Representation as Polynomials 22
1.6.3.1. How to Change Df H298K Without Recalculating NASA Polynomials 25
1.7. Thermochemical Databases 26 1.8. Conclusion 27 References 27 2.
Calculation of Kinetic Data Using Computational Methods 33 Fernando P.
Cossío 2.1. Introduction 33 2.2. Stationary Points and Potential Energy
Hypersurfaces 34 2.3. Calculation of Reaction and Activation Energies:
Levels of Theory and Solvent Effects 38 2.3.1. Hartree-Fock and
Post-Hartree-Fock Methods 38 2.3.2. Methods Based on Density Functional
Theory 41 2.3.3. Computational Treatment of Solvent Effects 44 2.4.
Estimate of Relative Free Energies: Standard States 47 2.5. Theoretical
Approximate Kinetic Constants and Treatment of Data 50 2.6. Selected
Examples 51 2.6.1. Relative Reactivities of Phosphines in Aza-Wittig
Reactions 52 2.6.2. Origins of the Stereocontrol in the Staudinger Reaction
Between Ketenes and Imines to Form ²-Lactams 54 2.6.3. Origins of the
Stereocontrol in the Reaction Between Imines and Homophthalic Anhydride 58
2.7. Conclusions and Outlook 61 References 62 3. Quantum Instanton
Evaluation of the Kinetic Isotope Effects and of the Temperature Dependence
of the Rate Constant 67 JiYí Vanícek 3.1. Introduction 67 3.2. Arrhenius
Equation, Transition State Theory, and the Wigner Tunneling Correction 68
3.3. Quantum Instanton Approximation for the Rate Constant 69 3.4. Kinetic
Isotope Effects 71 3.4.1. Transition State Theory Framework for KIE 71
3.4.2. Quantum Instanton Approach and the Thermodynamic Integration with
Respect to the Isotope Mass 72 3.5. Temperature Dependence of the Rate
Constant 73 3.5.1. Transition State Theory Framework for the Temperature
Dependence of k(T) 73 3.5.2. Quantum Instanton Approach and the
Thermodynamic Integration with Respect to the Inverse Temperature 74 3.6.
Path Integral Representation of Relevant Quantities 75 3.6.1. Path Integral
Formalism 75 3.6.2. Estimators 76 3.6.3. Estimators for Er 77 3.6.4.
Estimators for Eii 78 3.6.5. Estimators for the Derivatives of Fr and F z
with Respect to Mass 79 3.6.6. Statistical Errors and Efficiency 79 3.6.7.
Treatment of Potential Energy Surfaces for Many-Dimensional Systems 80 3.7.
Examples 81 3.7.1. Eckart Barrier 81 3.7.2. Full-Dimensional H+H2--> H2 +H
Reaction 84 3.7.3. [1,5]-Sigmatropic Hydrogen Shift in cis-1,3-Pentadiene
86 3.8. Summary 88 Appendix: Reactions 89 Acknowledgments 89 References 89
4. Activation Energies in Computational Chemistry--A Case Study 93 Michael
Busch, Elisabet Ahlberg and Itai Panas 4.1. Introduction 93 4.2. Context
and Theoretical Background 95 4.2.1. Density Functional Theory 95 4.2.2.
Calculating Transition States 96 4.2.3. The Tyrosine/Tyrosyl-Radical
Reference Potential 98 4.3. Computational Details 99 4.4. Recent Advances
and New Results 99 4.4.1. Homogenous OER Catalysts 99 4.4.2. Embedded
Transition Metal Dimers 102 4.5. Concluding Remarks 107 Acknowledgments 108
References 108 5. No Barrier Theory--A New Approach to Calculating Rate
Constants in Solution 113 J. Peter Guthrie 5.1. Introduction 113 5.2. The
Idea Behind No Barrier Theory 114 5.3. How to Define the Surface and Find
the Transition State 118 5.4. What is Needed for a Calculation? 124 5.5.
Applications to Date 125 5.5.1. Proton Transfer Reactions 125 5.5.2.
Addition of Water to Carbonyls 126 5.5.3. Cyanohydrin Formation 130 5.5.4.
The Reaction of Carbocations With Either Water or Azide Ion 131 5.5.5.
Decarboxylation 134 5.5.6. The E2 Elimination Reaction 136 5.5.7. The
Strecker Reaction 138 5.5.8. The Aldol Addition 138 5.6. Future Prospects
for NBT 140 5.7. Summary 141 References 142 PART II MINIREVIEWS AND
APPLICATIONS 147 6. Quantum Chemical and Rate Constant Calculations of
Thermal Isomerizations, Decompositions, and Ring Expansions of Organic Ring
Compounds, Its Significance to Cohbusion Kinetics 149 Faina Dubnikova and
Assa Lifshitz 6.1. Prologue 149 6.1.1. Introduction 149 6.1.2. Quantum
Chemical Calculations 150 6.1.3. Rate Constant Calculations 151 6.1.4.
Experimental Methods 152 6.2. Small Organic Ring Compounds 152 6.2.1.
Cyclopropane 152 6.2.2. Cyclopropane Carbonitrile 153 6.2.3. The Epoxy
Family of Molecules 154 6.3. Pyrrole and Indole 156 6.3.1. Pyrrole 156
6.3.2. Indole 157 6.4. Dihydrofurans and Dihydrobenzofurans 160 6.4.1.
2,3-Dihydrofuran 160 6.4.2. 5-Methyl-2,3-Dihydrofuran 160 6.4.3. Van der
Waals Interactions in H2 Elimination: 2,5-Dihydrofuran 161 6.4.4.
Dihydrobenzofuran and iso-Dihydrobenzofuran 163 6.5. Naphthyl
Acetylene-Naphthyl Ethylene 166 6.6. Ring Expansion Processes 168 6.6.1.
Methylcyclopentadiene 169 6.6.2. Methyl Pyrrole 170 6.6.3. Methylindene and
Methylindole 171 6.7. Benzoxazole-Benzisoxazoles 173 6.7.1. Benzoxazole 174
6.7.2. 1,2-Benzisoxazole 174 6.7.3. 2,1-Benzisoxazole--Intersystem Crossing
176 6.8. Conclusion 181 Acknowledgment 185 References 185 7. Challenges in
the Computation of Rate Constants for Lignin Model Compounds 191 Ariana
Beste and A.C. Buchanan, III 7.1. Lignin: A Renewable Source of Fuels and
Chemicals 191 7.1.1. Origin and Chemical Structure 193 7.1.2. Processing
Techniques and Challenges 195 7.2. Mechanistic Study of Lignin Model
Compounds 196 7.2.1. Experimental Work 197 7.2.2. Computational Work 201
7.3. Computational Investigation of the Pyrolysis of ²-O-4 Model Compounds
201 7.3.1. Methodology 202 7.3.1.1. Overview 202 7.3.1.2. Transition State
Theory 203 7.3.1.3. Anharmonic Corrections 207 7.3.2. Analytical Kinetic
Models 210 7.3.2.1. Parallel Reactions 210 7.3.2.2. Series of First-Order
Reactions 211 7.3.2.3. Product Selectivity for the Pyrolysis of PPE 211
7.3.3. Numerical Integration 213 7.4. Case Studies: Substituent Effects on
Reactions of Phenethyl Phenyl Ethers 214 7.4.1. Computational Details 215
7.4.2. Initiation: Homolytic Cleavage 215 7.4.3. Hydrogen Abstraction
Reactions and a/b-Selectivities 217 7.4.3.1. PPE and PPE Derivatives with
Substituents on Phenethyl Group 217 7.4.3.2. PPE and PPE Derivatives with
Substituents on Phenyl Group Adjacent to Ether Oxygen 221 7.4.4. Phenyl
Rearrangement 229 7.5. Conclusions and Outlook 232 Acknowledgments 234
Appendix Summary of Kinetic Parameters 234 References 235 8. Quantum
Chemistry Study on the Pyrolysis Mechanisms of Coal-Related Model Compounds
239 Baojun Wang, Riguang Zhang and Lixia Ling 8.1. Introduction to the
Application of Quantum Chemistry Calculation to Investigation on Models of
Coal Structure 239 8.2. The Model for Coal Structure and Calculation
Methods 240 8.2.1. The Proposal of Local Microstructure Model of Coal 240
8.2.2. Coal-Related Model Compounds Describing the Properties of Coal
Pyrolysis 241 8.2.3. The Pyrolysis of Model Compounds Reflecting the
Pyrolysis Phenomenon of Coal 242 8.2.4. The Calculation Methods 242 8.3.
The Pyrolysis Mechanisms of Coal-Related Model Compounds 243 8.3.1. The
Pyrolysis Mechanisms of Oxygen-Containing Model Compounds 243 8.3.1.1.
Phenol and Furan 243 8.3.1.2. Benzoic Acid and Benzaldehyde 246 8.3.1.3.
Anisole 251 8.3.2. The Pyrolysis Mechanisms of Nitrogen-Containing Model
Compounds 255 8.3.2.1. Pyrrole and Indole 256 8.3.2.2. Pyridine 258
8.3.2.3. 2-Picoline 260 8.3.2.4. Quinoline and Isoquinoline 263 8.3.3. The
Pyrolysis Mechanisms of Sulfur-Containing Model Compounds 267 8.3.3.1.
Thiophene 268 8.3.3.2. Benzenethiol 270 8.4. Conclusion 276 References 276
9. Ab Initio Kinetic Modeling of Free-Radical Polymerization 283 Michelle
L. Coote 9.1. Introduction 283 9.1.1. Free-Radical Polymerization Kinetics
283 9.1.2. Scope of this Chapter 286 9.2. Ab Initio Kinetic Modeling 287
9.2.1. Conventional Kinetic Modeling 287 9.2.2. Ab Initio Kinetic Modeling
289 9.3. Quantum Chemical Methodology 291 9.3.1. Model Systems 291 9.3.2.
Theoretical Procedures 293 9.4. Case Study: RAFT Polymerization 296 9.5.
Outlook 300 References 301 10. Intermolecular Electron Transfer Reactivity
for Organic Compounds Studied Using Marcus Cross-Rate Theory 305 Stephen F.
Nelsen and Jack R. Pladziewicz 10.1. Introduction 305 10.2. Determination
of deltaGiiii (fit) Values 307 10.3. Why is the Success of Cross-Rate
Theory Surprising? 309 10.4. Major Factors Determining Intrinsic
Reactivities of Hydrazine Couples 310 10.5. Nonhydrazine Couples 315 10.6.
Comparison of DdeltaGiiii (fit) with DdeltaGiiii (self) Values 318 10.7.
Estimation of Hab from Experimental Exchange Rate Constants and
DFT-Computed l 320 10.8. Comparison with Gas-Phase Reactions 333 10.9.
Conclusions 333 References 334 INDEX 337