Reaction Heats and Bond Strengths

1. The Thermochemical Approach

Introduction

Energy changes in Heats of Reaction

Definitions of Bond Strength


1. Bond Energies


2. Bond Dissociation Energies

Heats of Reaction

Experimental Methods


2. Strain Energies in Saturated and Unsaturated Organic Compounds

Saturated Cyclic Compounds


1. Cyclo-alkanes


2. Heterocyclic Compounds


3. Decalins


4. Perhydroanthracenes


5. Dimethylcyclohexanes


6. Dimethylcyclopentanes


7. Hydrindanes

Unsaturated Compounds


1. Cyclic Olefins


2. Cyclic or^o-Substituted Benzene Derivatives


3. Acyclic Olefins

Polycyclo-alkanes and Alkenes

Exo-Endo Isomerism in Olefins

Conclusion


3. Stabilization Energiesm in Non-Aromatic Compounds

Introduction

Conjugation and Hyper conjugation


1. Olefins


2. Acetylenes

Polar Effects

Hybridization

Conclusion


4. Strain and Resonance Energies in Aromatic Compounds

Introduction

Experimental Determination of Resonance Energies


1. Bond Compressional Energy


2. Hybridization Changes


3. Charge Separation


4. Steric Effects

Five- and Seven-membered Ring Systems

Four- and Eight-membered Ring Systems

Cat a-Condensed Hydrocarbons

Polycyclic Hydrocarbons


1. Stabilization Energies


2. Strain Energies

Hetero-aromatics

Conclusion


5. Polymerization Energies

Heats of Self-Polymerization Reactions

Free Energies and Entropies

Co-polymerization

Polymerization of Cyclic Compounds


1. Cyclo-alkanes


2. Heterocyclic Compounds


6. Molecular Addition Compounds

Introduction

Steric and Inductive Effects

Acceptor Molecules: n-Bonding

Donor Molecules: Donor Strength and Reorganization Energy

Addition compounds: ^-Bonding


1. Acceptor Atoms with Available d-Orbitals


2. Acceptor Atoms with pseudo pπ-Orbitals

Conclusion


7. Bond Dissociation Energies and Heats of Formation of Free Radicals

Introduction

Heats of Formation of Free Radicals


1. Alkyl Radicals


2. Vinyl Radical


3. Benzyl Radical


4. Phenyl Radical


5. Cyanide Radical


6. Halogen-substituted Alkyl Radicals


7. Alkoxy Radicals


8. Thioalkoxy Radicals


9. Alkyl Amino Radicals


10. Radicals RCOO

Stepwise Dissociation Energies


8. Metal-Carbon and Metal-Halogen Bonds

Introduction

Mean Bond Dissociation Energies


1. Representative and 6-Group Elements


2. Transition Metals, Carbonyls


3. Cyclopentadienyl and Benzene Compounds

Stepwise Dissociation Energies


1. b-Group Metal Alkyls


2. Transition Metal Halides

Summary


9. Ionization Energies in Aqueous Solution

Introduction

Heats of Neutralization of Strong Acids and Strong Bases

Aliphatic Acids

Methyl-substituted Compounds


1. Picolines


2. Cresols


3. Chlorophenols


4. Nitrophenols


5. Toluidines


6. Methyl-Benzoic Acids


7. Lutidines and Xylenols


8. Summary of Data for Methyl-substituted Compounds

Halogen Substituted Acetic Acids

Dibasic Organic Acids

Conclusion


10. Bond Strengths in Silicon, Phosphorus and Sulfur Compounds

Introduction

dπ-pπ-Bonding in Simple Molecules


1. Silicon


2. Phosphorus


3. Sulfur

dπ-pπ-Bonding in Cyclic Systems


1. Cyclic Phosphazenes


2. Sulphanuric and Thiazyl Compounds

References

Author Index

Subject Index