《The Foundations of Chemical Kinetics》求取 ⇩

PART Ⅰ.THE PHENCMENOLOGICAL DESCRIPTION OF CHEMICAL RATE PROCESSES1

Chapter Ⅰ.Description of Reacting Systems3

1.Description of Equilibrium Systems3

2.Description of Kinetic Systems4

3.Phenomenological Approach5

4.Molecular Approach5

5.Macroscopic Variables of a Chemically Reacting System6

5A.Temperature6

5B.Pressure and Volume6

5C.Chemical Composition;Concentration of Reactants6

5D.Chemical Composition;Concentration of Inert Substances7

5E.Chemical Composition;Catalysis7

5F.Effect of Surfaces;Heterogeneous Reactions8

6.Plotting a Course8

Chapter Ⅱ.Mathematical Characterization of Simple Kinetic Systems11

1.Reaction Order11

2.Nomenclature12

3.Zero-order Reactions13

4.First-order Reactions14

5.Second-order Reactions:Type Ⅰ17

6.Second-order Reactions:Type Ⅱ18

7.A Complication of Type Ⅱ Second-order Reactions20

8.Third-order Reactions21

9.Fractional-and Higher-order Reactions25

Chapter Ⅲ.Mathematical Characterization of Complex Kinetic Systems26

1.Classification of Complex Kinetic Systems26

2.Opposing Reactions;First Order27

3.Opposing Reactions;Higher Orders29

4.Concurrent Reactions31

5.Consecutive Reactions;First Order33

6.Infinite Sequence of First-order Reactions36

6A.First-order Reactions;General Treatment39

7.Consecutive Reactions;Higher Order42

7A.Elimination of Time as an Independent Variable43

7B.Reduction of Second-order to First-order Equation46

8.Classification of Consecutive Reaction Systems49

9.The Stationary-state Hypothesis;Chain Reactions50

10.The Induction Period53

11.Higher-order Reactions54

12.Rate-determining Step55

Chapter Ⅳ.Experimental Characterization of Simple Kinetic Systems58

1.Experimental Methods;Composition58

1A.Total Pressure59

1B.Method of Sampling60

1C.Flow Methods61

1D.Optical Methods of Analysis63

1E.Electrical Methods of Analysis64

1F.Miscellaneous Methods of Analysis64

1G.Errors Due to Heterogeneity65

2.Temperature Dependence of Rate Constants;Activation Energies66

3.Thermodynamic Interpretation of the Rate Equation68

3A.Activation Energies and Heats of Reaction71

4.Entropy of Activation72

4A.Relation between Reaction Rates and Free Energies;Rate Close to Equilibrium73

5.Experimental Determination of Reaction Order;Simple Systems75

5A.Method of Integration75

5B.Method of Half-lives77

5C.Method of Isolation;Pseudo-order Reactions81

5D.Differential Method82

5E.Tracer Methods84

6.Precision of Rate Measurements for Simple Systems86

6A.Precision of Specific Rate Constants86

6B.Weighting of Data89

6C.Precision in Measurements of Activation Energies91

6D.Influence of Temperature on Precision92

6E.Summary93

Chapter Ⅴ.Experimental Characterization of Complex Kinetic Systems95

1.Characteristics of Complex Systems95

2.Equilibrium Systems96

3.Concurrent Reactions98

4.Chain Reactions;Detection of Intermediates99

4A.Mirror Techniques100

4B.Spectroscopic Techniques102

4C.Mass Spectroscopy103

4D.Chemical Methods104

4E.Paramagnetic Properties106

4F.Isotopic Exchange108

4G.Photochemical Methods;Quantum Yield109

4H.Photosensitization109

4I.Chemical Sensitization110

4J.The Induction Period111

4K.Inhibition111

4L.Intermittent Activation112

4M.Thermal Methods for Detection of Free Radicals114

5.Resumé115

6.The Molecular Approach116

PART Ⅱ.STATISTICAL METHODS FOR TREATING SYSTEMS OF LARGE NUMBERS OF PARTICLES AT OR NEAR EQUILIBRIUM119

Chapter Ⅵ.Representation of Equilibrium Properties121

1.Description of a System of Discrete Particles121

2.Distribution Functions122

3.Some Simple Distribution Functions123

4.Distributions in More Than One Variable124

5.Moments of a Distribution Function125

6.Some Important Theorems for Distribution Functions127

7.Illustration:Random Walk in One Dimension128

8.The Normal Law of Error130

9.Note:Stirling’s Approximation133

Chapter Ⅶ.The Kinetic Theory of Gases135

1.Molecular Models135

1A.Ideal Gas Model135

1B.Hard Sphere Model135

1C.Hard Sphere Model with Central Attractive Forces136

1D.Symmetrical Molecule with Central Forces136

1E.Rectangular Well Model136

2.Velocity Distribution of an Ideal Gas;Cartesian Coordinates137

3.Velocity Distribution in Spherical Coordinates139

4.Velocity Groups142

5.Translational Energy Distributions143

6.Pressure Exerted by an Ideal Gas;Collisions with a Wall144

7.Absolute Temperature:Relation to Thermedynamics147

8.Molecular Collisions148

8A.Mechanics of a Collision149

8B.Collision Frequency of a Single Molecule Moving through a Station-ary Gas150

8C.Collision Frequency of a Molecule Moving through a Homogeneous Gas151

8D.Collision Frequency of a Molecule in a Maxwellian Gas152

8E.Collision Frequency between Maxwellian Molecules153

8F.Bimolecular Collision Frequencies154

8G.Duration of a Collision155

8H.Termolecular Collisions;Collision Complexes156

9.Distribution of Free Paths157

10.Molecular Effusion;Isotope Separation158

11.Energy Transfer in Collisions161

11A.Translational Exchange161

11B.Inelastic Collisions162

11C.Vibrational Exchange163

Chapter Ⅷ.Transport Properties of Gases168

1.Mechanism of Transport168

1A.Transport of Momentum168

1B.Transport of Energy169

1C.Transport of Matter169

2.Viscosity of a Fluid169

3.Viscosity of a Dilute Gas170

4.Comparison with Experiment174

5.Viscosity at Low Densities176

6.Thermal Conductivity177

7.Thermal Conductivity at Low Pressures179

8.Mass Diffusion181

9.Experimental Results for Diffusion184

10.Generalized Diffusion;Thermal Diffusion186

11.Criticism of the Nonequilibrium Kinetic Theory188

Chapter Ⅸ.Statistical Treatment of Interacting Systems190

1.The Canonical Distribution190

2.The Phase Integral191

3.Application to Gases193

4.Molecular Distribution Functions:Ideal Gas in a Force Field195

5.Virial Theorem197

6.Quantum Statistics201

7.Partition Functions201

8.Translational Partition Function202

9.Vibrational Partition Function203

10.Rotational Partition Function204

11.Equilibrium Constant205

12.An Example:The Dissociation of Iodine206

13.Application to Rate Processes207

PART Ⅲ.THE KINETICS OF HOMOGENEOUS REACTION IN GASES209

Chapter Ⅹ.Spontaneous Decomposition of Excited Molecules211

1.Chemical Stability and Temperature211

2.Mechanical Stability of Molecules212

3.Spontaneous Decomposition of an Energized Molecule;Potential Energy214

4.Rate of Spontaneous Decomposition216

5.Quantitative Theories of Spontaneous Decomposition218

6.Detailed Theory of Spontaneous Decomposition219

7.Distribution Function for Energized Molecules222

Chapter Ⅺ.Unimolecular Reactions225

1.Detailed Scheme for a Unimolecular Reaction:Isomerization225

2.Pressure Dependence of Unimolecular Reactions;High-pressure Limit228

3.Pressure Dependence of Unimolecular Reactions;Moderate Pressures230

4.Pressure Dependence of Unimolecular Reaction;Low-pressure Limit234

5.Detailed Scheme for Unimolecular Decompositions239

6.Quantum Effects in Unimotecular Reactions242

7.Equilibrium Theory of Reaction Rates;The Transition-state Method247

8.Summary of the Various Theories of Unimolecular Reactions250

9.Some Unimolecular Isomerizations252

10.Some Unimolecular Fission Reactions;Decomposition into Stable Molecules257

11.Some Unimolecular Fissions;Production of Free Radicals261

12.Unimolecular Reactions;Resumé264

Chapter Ⅻ.Bimolecular and Termolecular Reactions267

1.Association Reactions267

2.Exchange Reactions268

3.Collision Model for Bimolecular Reactions271

4.Transition-state Model274

5.Comparison of Different Theories of Bimolecular Rate Constants;Experi-mental Activation Energies275

6.The Preexponential Factors of Bimolecular Reactions276

7.A Priori Calculation of Preexponential Factors of Bimolecular Reactions281

8.The Reaction H+H2？H2+H(Exchange)282

9.The Reaction H2+I2→2HI285

10.Reactions of CH3 Radicals and H Atoms286

11.Estimations of Preexponential Factors from Calculated Equilibrium Con-stants and Experimental Rate Constants288

12.Bimolecular Exchange Reactions between Molecules290

13.Bimolecular Exchange Reactions That Involve Free Radicals or Atoms292

14.Bimolecular Association Reactions299

15.Termolecular Reactions:Mechanism305

16.Some Third-order Reactions308

17.Rates of Activation313

18.Activation Energies for Simple Kinetic Processes316

Chapter ⅩⅢ.Some Complex Gas-phase Reactions319

1.Complexity of Gas-phase Reactions319

2.The Reaction System H2+Br2？2HBr320

3.Some Omitted Reactions in the H2+Br2 System322

4.The System H2+Br2;Photolysis and Wall Effects325

5.Summary of the Chain Reaction H2+Br2→2HBr329

6.Two-center Chain Reaction:Chain Lengths and Induction Periods331

7.Reactions of H2 witn the Halogens337

8.Reactions of CH4 with the Halogens343

9.The Pyrolysis of Hydrocarbons;The Rice-Herzfeld Mechanisms;Decom-position of Butanes343

10.Pyrolysis of Ethane349

11.Pyrolysis of Ethane:Some Further Steps in the Chain359

12.Pyrolysis of Di-tertiary Butyl Peroxide;A Thermal Source of Methyl Radicals363

13.Photolysis of Acetone:A Photochemical Source of Methyl Radicals370

14.Pyrolysis of Acetaldehyde379

15.Pyrolysis of Dimethyl Ether386

16.Hot Radical Reactions:The Transfer of Energy392

17.Hot Radical Reactions:Photolysis of Iodides396

18.Decomposition of Ozone400

19.Oxides of Nitrogen:Decomposition of N2O6408

20.Pyrolysis of Nitrites and Nitrates419

Chapter ⅩⅣ.The Kinetic Behavior of Non-stationary-state Systems425

1.The Approach to the Stationary State in a Reacting System425

2.Temperature Gradients in Reacting Systems427

3.Thermal Explosions431

4.Chemically Sensitized Explosions;Branching Chains438

5.The Branching Ghain Explosion;Upper and Lower Limits440

6.Concentration Gradients in Chemical Reactions446

7.The Reaction of Hydrogen with Oxygen452

8.The Reaction of CO with O2459

9.Ignition and Combustion461

10.Stationary Flames464

11.Shock Waves and Detonations471

12.The Combustion of Hydrocarbons479

PART Ⅳ.REACTIONS IN CONDENSED PHASES491

Chapter ⅩⅤ.Physical Models for Solution Reactions493

1.A Model for Chemical Reactions in Solution493

2.Collisions in a Solution494

3.Transition-state Model for Solution Reactions502

4.The Effect of Solvent504

5.Changes in External Variables;Pressure Effects510

6.Interactions between Charged Particles in a Solution518

7.Activity Coefficients in Ionic Solutions521

8.The Effect of Ionic Strength on Reactions between Ions525

9.Association of Ions523

10.Effect of Solvent on Reactions of Ions531

11.Reactions of Ions with Polar Molecules534

12.Entropy Changes in Ionic Reactions537

13.Cage Effects in Liquid Reactions541

Chapter ⅩⅥ.Further Kinetic As pects of Solution Reactions548

1.Displacement Reactions548

2.Acid-Base Catalysis558

3.The Br？nsted Relation:Linear Free Energy Relations564

4.Some Acid-Base-catalyzed Reactions of the Carbonyl Group569

5.Reactions in Concentrated Solutions;The Acidity Function575

6.Lewis Acids:Addition to MultipleBonds581

7.Electron-transfer Reactions:Oxidation and Reduction587

8.Intermediate Valence States in Oxidation-Reduction Reactions592

9.Ion-Radical Reactions;Decomposition of Peroxide596

10.Free Radical Polymerization599

11.Absolute Rate Constants inPolymerization605

12.Structure andReactivity611

Chapter ⅩⅦ.Heterogeneous Reactions616

1.Catalysis bySolids616

2.Initiation of Chains at Solid Surfaces618

3.Chemisorption at Solid Surfaces621

4.The Mechanisms of Reactions at Solid Surfaces627

5.Inhibition and Competitionin Surface Reactions630

6.Some Catalytic Reactions Involving H2 and Metals634

7.Oxidation of Metals;Rates of Chemisorption639

8.Electrode Reactions642

9.Phase Formation648

10.Enzyme-catalyzed Reactions652

Appendix A.Some Atomic Constants659

B.Some Useful Mathematical Relations660

C.Some Thermodynamic Data for Atoms,Molecules,and Free Rad-icals in the Gas Phase662

D.The Estimation of Thermodynamic Properties for Simple Molecules in the Ideal Gas State665

E.ApproximateBond Dissociation Energies of Organic Compounds670

Selected Problems673

Author Index681

Subject Index691