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Some Problems of Chemical Kinetics and Reactivity - 1st Edition - ISBN: 9781483167473, 9781483194950

Some Problems of Chemical Kinetics and Reactivity

1st Edition

Volume 1

Author: N. N. Semenov
eBook ISBN: 9781483194950
Imprint: Pergamon
Published Date: 1st January 1958
Page Count: 316
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Some Problems of Chemical Kinetics and Reactivity, Volume 1 consists of calculations on radical and radical chain reactions. The subject bond dissociation energies are fully discussed. The concept of uniradical reactivities is comprehensively explained. Isomerizations are a class of radical reactions in which the free valency takes another bond in the same radical. The text provides sample of experiments on the subject. The book contains a section on polar factors in organic reactions. Polymerizations are another concept covered in the book. Subjects such as the reactions of biradicals, the start and end of a chain reaction, and ions of variable valency are explained. A separate chapter of the book focuses on the kinetics of chain reactions. The cracking of hydrocarbons such as the alkane is analyzed in detail. The oxidation of hydrocarbons is another topic explained in the book. The text will provide excellent insight for chemists, students, and researchers in the field of chemistry.

Table of Contents


Part I Radical Reactions (Propagation and Branching of Chain Reactions)

1. Uniradical Reactivities

1. Radical Reactions: Basic Types

2. Experimental Determination of Activation Energies

3. Bond Dissociation Energies

4. The Correlation of Activation Energies with Heats of Reaction

5. Radical and Molecular Activities

6. Empirical Formula for Computing Bond-Energies in Organic Molecules

7. Addition at Multiple Bonds

8. Radical Decomposition and the Energies of π-Bonds

9. Radical Isomerizations

10. Transfer Reactions

11. Polar Factors in Organic Reactions

12. Polar Factors in Polymerization

2. Alternative Univalent Free-Radical Reactions

1. The Occurrence of Alternative Radical Reactions

2. The Influence of Temperature and Pressure on Alternative Radical Reactions

3. Intermediary and Terminal Products in Chain Reactions

3. The Reactions of Biradicals

1. The Transition of Atoms to the Active-Valence State

2. Reactivity in the Molecules O2, S2 and Se2

3. Divalent Carbon

4. Complex Biradicals

5. Production and Reactivity of >Ch2 and —O—

6. The Role of Biradicals in Chain Reactions

Part II Initiation and Termination of Chain Reactions

4. Molecular Dissociation and Radical Combination

1. Homogeneous Initiation of Chains

2. Homogeneous Recombination of Radicals

3. Dependence of Overall Reaction Kinetics on Chain-Termination Mechanism

4. Special Aspects of Radical Generation and Recombination in Liquids

5. The Effects of Inhibitors on the Rates of Chain Reactions

5. Ions of Variable Valency as Chain Initiators

1. Formation of Radicals and Ionic Radicals by Electron Transfer

2. Thermodynamic and Kinetic Aspects of Free Radical Formation

3. Ions of Variable Valency as Chain Initiators

6. Wall Initiation and Retardation of Chain Reactions

1. Generation and Removal of Free Radicals at the Vessel Walls

2. The Method of Differential Calorimetry

3. Free Valencies in the Walls

4. Radical Production at Active Surfaces

5. Heterogeneous Production of Radicals When Gaseous Admixtures are Present

6. Heterogeneous Molecular Reactions Giving Free Radicals

7. Application of the above Concepts to Heterogeneous Catalysis

8. Heterogeneous Catalysis in Biology

Part III Kinetics of Chain Reactions

7. Chain Reactions Competing with Reactions between Saturated Molecules

1. Energy Dependence of Chain Reactions and Molecular Reactions

2. The Relative Rates of Direct Molecular and Chain Reactions

3. Alkyl Bromide Decompositions

4. Alkyl Chloride Decompositions

5. The Cracking of Hydrocarbons

6. Factors Influencing the Chain Length

7. The Elementary Act of Decomposition

8. Free-Radical Production by Reaction Molecules between Stable

9 Particular Examples

Appendix I. The Activated Complex

Appendix II. The Quantum-Mechanical Calculation of Activation Energies

Name Index

Subject Index


No. of pages:
© Pergamon 1958
1st January 1958
eBook ISBN:

About the Author

N. N. Semenov

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