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Rate Constant Calculation for Thermal Reactions : Methods and Applications.
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 applicati...
| Clasificación: | Libro Electrónico |
|---|---|
| Autor principal: | |
| Otros Autores: | |
| Formato: | Electrónico eBook |
| Idioma: | Inglés |
| Publicado: |
Hoboken :
John Wiley & Sons,
2011.
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| Temas: | |
| Acceso en línea: | Texto completo |
Tabla de Contenidos:
- Part 1, Methods: Overview of thermochemistry and its application to reaction kinetics / Elke Goos and Alexander Burcat
- Calculation of kinetic data using computational methods / Fernando Cossío
- Quantum instanton evaluation of the kinetic isotope effects and of the temperature dependence of the rate constant / Jiri Vanicek
- Activation energies in computational chemistry : a case study / Michael Busch, Elisabet Ahlberg, and Itai Panas
- No barrier theory : a new approach to calculating rate constants in solution / Peter Guthrie
- Part 2, Minireviews and applications: Quantum chemical and rate constant calculations of thermal isomerizations, decompositions, and ring expansions of organic ring compounds / Faina Dubnikova and Assa Lifshitz
- Challenges in the computation of rate constants for lignin model compounds / Ariana Beste and A.C. Buchanan, III
- Quantum chemistry study on the pyrolysis mechanisms of coal-related model compounds / Baojun Wang, Riguang Zhang and Lixia Ling
- Ab initio kinetic modeling of free-radical polymerization / Michelle L. Coote
- Intermolecular electron transfer reactivity for organic compounds studied using Marcus Cross-rate theory / Stephen F. Nelson and Jack R. Pladziewicz.
- 8.3.1. The Pyrolysis Mechanisms of Oxygen-Containing Model Compounds
- 8.3.1.1. Phenol and Furan
- 8.3.1.2. Benzoic Acid and Benzaldehyde
- 8.3.1.3. Anisole
- 8.3.2. The Pyrolysis Mechanisms of Nitrogen-Containing Model Compounds
- 8.3.2.1. Pyrrole and Indole
- 8.3.2.2. Pyridine
- 8.3.2.3. 2-Picoline
- 8.3.2.4. Quinoline and Isoquinoline
- 8.3.3. The Pyrolysis Mechanisms of Sulfur-Containing Model Compounds
- 8.3.3.1. Thiophene
- 8.3.3.2. Benzenethiol
- 8.4. Conclusion
- References
- 9. Ab Initio Kinetic Modeling of Free-Radical Polymerization
- 9.1. Introduction
- 9.1.1. Free-Radical Polymerization Kinetics
- 9.1.2. Scope of this Chapter
- 9.2. Ab Initio Kinetic Modeling
- 9.2.1. Conventional Kinetic Modeling
- 9.2.2. Ab Initio Kinetic Modeling
- 9.3. Quantum Chemical Methodology
- 9.3.1. Model Systems
- 9.3.2. Theoretical Procedures
- 9.4. Case Study: RAFT Polymerization
- 9.5. Outlook
- References
- 10. Intermolecular Electron Transfer Reactivity for Organic Compounds Studied Using Marcus Cross-Rate Theory
- 10.1. Introduction
- 10.2. Determination of DG! i (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?G! i (fit) with?G! i (self) Values
- 10.7. Estimation of Hab from Experimental Exchange Rate Constants and DFT-Computed?
- 10.8. Comparison with Gas-Phase Reactions
- 10.9. Conclusions
- References
- INDEX.
- Rate Constant Calculation for Thermal Reactions: Methods and Applications
- CONTENTS
- PREFACE
- CONTRIBUTORS
- PART I: METHODS
- 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
- 1.4.1. Measurement of Thermochemical Values
- 1.4.2. Calculation of Thermochemical Values
- 1.4.2.1. Quantum Chemical Calculations of Molecular Properties
- 1.4.2.2. Calculation of Thermodynamic Functions from Molecular Properties
- 1.5. Accuracy of Thermochemical Values
- 1.5.1. Standard Enthalpies of Formation
- 1.5.2. Active Thermochemical Tables
- 1.6. Representation of Thermochemical Data for Use in Engineering Applications
- 1.6.1. Representation in Tables
- 1.6.2. Representation with Group Additivity Values
- 1.6.3. Representation as Polynomials
- 1.6.3.1. How to Change?f H298K Without Recalculating NASA Polynomials
- 1.7. Thermochemical Databases
- 1.8. Conclusion
- References
- 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
- 2.3.1. Hartree-Fock and Post-Hartree-Fock Methods
- 2.3.2. Methods Based on Density Functional Theory
- 2.3.3. Computational Treatment of 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
- 2.6.1. Relative Reactivities of Phosphines in Aza-Wittig Reactions
- 2.6.2. Origins of the Stereocontrol in the Staudinger Reaction Between Ketenes and Imines to Form?-Lactams.
- 7. Challenges in the Computation of Rate Constants for Lignin Model Compounds
- 7.1. Lignin: A Renewable Source of Fuels and Chemicals
- 7.1.1. Origin and Chemical Structure
- 7.1.2. Processing Techniques and Challenges
- 7.2. Mechanistic Study of Lignin Model Compounds
- 7.2.1. Experimental Work
- 7.2.2. Computational Work
- 7.3. Computational Investigation of the Pyrolysis of?-O-4 Model Compounds
- 7.3.1. Methodology
- 7.3.1.1. Overview
- 7.3.1.2. Transition State Theory
- 7.3.1.3. Anharmonic Corrections
- 7.3.2. Analytical Kinetic Models
- 7.3.2.1. Parallel Reactions
- 7.3.2.2. Series of First-Order Reactions
- 7.3.2.3. Product Selectivity for the Pyrolysis of PPE
- 7.3.3. Numerical Integration
- 7.4. Case Studies: Substituent Effects on Reactions of Phenethyl Phenyl Ethers
- 7.4.1. Computational Details
- 7.4.2. Initiation: Homolytic Cleavage
- 7.4.3. Hydrogen Abstraction Reactions and?/?-Selectivities
- 7.4.3.1. PPE and PPE Derivatives with Substituents on Phenethyl Group
- 7.4.3.2. PPE and PPE Derivatives with Substituents on Phenyl Group Adjacent to Ether Oxygen
- 7.4.4. Phenyl Rearrangement
- 7.5. Conclusions and Outlook
- Acknowledgments
- Appendix: Summary of Kinetic Parameters
- References
- 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
- 8.2.1. The Proposal of Local Microstructure Model of Coal
- 8.2.2. Coal-Related Model Compounds Describing the Properties of Coal Pyrolysis
- 8.2.3. The Pyrolysis of Model Compounds Reflecting the Pyrolysis Phenomenon of Coal
- 8.2.4. The Calculation Methods
- 8.3. The Pyrolysis Mechanisms of Coal-Related Model Compounds.