Reaction Heats and Bond Strengths (eBook)

Front Cover 1
Reaction Heats and Bond Strengths 4
Copyright Page 5
Table of Contents 10
Acknowledgements 6
Preface 8
CHAPTER 1. THE THERMOCHEMICAL APPROACH 14
Introduction 14
Energy Changes in Heats of Reaction 15
Definitions of Bond Strength 17
Heats of Reaction 24
Experimental Methods 28
CHAPTER 2. STRAIN ENERGIES IN SATURATED AND UNSATURATED ORGANIC COMPOUNDS 39
Saturated Cyclic Compounds 39
Unsaturated Compounds 49
Polycyclo-alkanes and Alkenes 55
Exo-endo Isomerism in Olefins 59
Conclusion 62
CHAPTER 3. STABILIZATION ENERGIES IN NON-AROMATIC COMPOUNDS 63
Introduction 63
Conjugation and Hyperconjugation 63
Polar Effects 69
Hybridization 73
Conclusion 76
CHAPTER 4. STRAIN AND RESONANCE ENERGIES IN AROMATIC COMPOUNDS 78
Introduction 78
Experimental Determination of Resonance Energies 80
Five- and Seven-membered Ring Systems 83
Four- and Eight-membered Ring Systems 86
Cata-condensed Hydrocarbons 88
Polycyclic Hydrocarbons 89
Hetero-aromatics 93
Conclusion 97
CHAPTER 5. POLYMERIZATION ENERGIES 99
Heats of Self-polymerization Reactions 99
Free Energies and Entropies 103
Co-polymerization 106
Polymerization of Cyclic Compounds 110
CHAPTER 6. MOLECULAR ADDITION COMPOUNDS 119
Introduction 119
Steric and Inductive Effects 121
Acceptor Molecules: p-Bonding 124
Donor Molecules: Donor Strength and Reorganization Energy 130
Addition Compounds: p-Bonding 133
Conclusion 136
CHAPTER 7. BOND DISSOCIATION ENERGIES AND HEATS OF FORMATION OF FREE RADICALS 138
Introduction 138
Heats of Formation of Free Radicals 139
Stepwise Dissociation Energies 157
CHAPTER 8. METAL-CARBON AND METAL-HALOGEN BONDS 159
Introduction 159
Mean Bond Dissociation Energies 159
Stepwise Dissociation Energies 168
Summary 177
CHAPTER 9. IONIZATION ENERGIES IN AQUEOUS SOLUTION 178
Introduction 178
Heats of Neutralization of Strong Acids and Strong Bases 179
Aliphatic Acids 180
Methyl-substituted Compounds 181
Halogen-Substituted Acetic Acids 192
Dibasic Organic Acids 194
Conclusion 195
CHAPTER 10. BOND STRENGTHS IN SILICON, PHOSPHORUS AND SULPHUR COMPOUNDS 196
Introduction 196
dp—pp-Bonding in Simple Molecules 197
dp—pp-Bonding in Cyclic Systems 204
REFERENCES 215
AUTHOR INDEX 227
SUBJECT INDEX 233