r

CHEMICAL KINETICS AND

CATALYSIS

Richard I: Masel
_ m _ ^ )i

University of Illinois at" Urbana-Champaign

iWILEY-
INTERSCIENCE
A JOHN WILEY & SONS, INC., PUBLICATION
New York • Chichester • Weinheim • Brisbane • Singapore • Toronto
 CONTENTS

Preface xi

1 Introduction 1
1.1 Introduction / 1
1.2 Outline of the Presentation / 2
1.3 A Guide for Students / 4

2 Review of Some Elementary Concepts

2.1 Definitions / 5
2.2 Variation in Rate with Conditions / 9
2.3 Empirical Rate Laws / 9
2.4 The Experimental Situation / 13
2.5 Temperature Effects / 17
2.6 Catalysts / 27
2.7 Catalytic Kinetics / 30
2.8 Multiple Steady States, Oscillations, and Other Complexities / 37
2.9 Summary / 39
2.10 Solved Examples / 39
2.11 Problems / 48

3 Analysis of Rate Data 59

3.1 Introduction / 59
3.2 Background / 60
3.3 Brief Overview of the Experimental Techniques / 62
3.4 Direct and Indirect Methods / 66
3.5 Examples of Direct and Indirect Methods / 70
3.6 Examples of Indirect Measurements / 71
3.7 Fitting Data to Empirical Rate Laws: Single Reactants / 71
3.8 Analysis of Data from a Differential Reactor / 72
3.9 Analysis of Rate Data from an Integral Reactor / 74
3.10 Qualitative Behavior / 82
3.11 Fitting Rate Data to Ideal Behavior / 83
3.12 The Half Life Method / 89
3.13 Fitting Data to Empirical Rate Laws: Multiple Reactants / 89
VI CONTENTS

3.14 Sequential Reactions / 92

3.15 Summary / 100
3.16 Supplemental Material: Measuring Rate Data from Volume and
Pressure Changes / 100
3.17 Solved Examples / 103
3.18 Suggestions for Further Reading / 137
3.19 Problems / 138

4 Relationship between Rates and Mechanisms 157

4.1 Introduction / 157
4.2 Historical Overview / 158
4.3 Kinetics of Elementary Reactions / 163
4.4 The Relationship between Kinetics and Equilibrium (Microscopic
Reversibility) / 165
4.5 Rates of Overall Reactions / 167
4.6 Generalization to Other Reactions / 170
4.7 The Pseudo-Steady-State Approximation / 170
4.8 Applications of the Pseudo-Steady-State Approximation to
Determine the Kinetics of a Reaction / 173
4.9 Rate-Determining Steps / 179
4.10 Testing the Accuracy of the Pseudo-Steady-State
Approximation / 182
4.11 Failure of the Pseudo-Steady-State Approximation / 184
4.12 Using the Pseudo-Steady-State Approximation to Infer
Mechanisms / 189
4.13 Summary / 196
4.14 Solved Examples and Supplemental Material / 197
4.15 Suggestion for Further Reading / 220
4.16 Problems / 221

5 Prediction of the Mechanisms of Reactions 235 I

5.1 Introduction / 235
5.2 Why Do Reactions Follow Complex Mechanisms? / 236
5.3 Prediction of Mechanisms of Reactions of Gas-Phase
Species / 237
5.4 Prediction of the Mechanism of Initiation-Propagation I
Mechanisms / 239 |
5.5 Gas-Phase Reactions that Do Not Follow Initiation-Propagation 1
Mechanisms / 260 I
5.6 Summary of Initiation-Propagation Mechanisms / 265 f
5.7 Reactions of Ions / 265 j
5.8 Prediction of the Mechanism of Ionic Reactions / 274 f
- 5.9 Reactions in Polar Solution / 275 |
5.10 Reactions on Metal Surfaces / 277 I
5.11 General Concepts about Adsorption and Reaction on J
Surfaces / 280 |
5.12 Prediction of the Mechanisms of Surface Reactions / 282 I
 CONTENTS vii

5.13 Generic Types of Surface Reactions / 287

5.14 Reactions on Acid Surfaces / 290
5.15 Summary / 291
5.16 Solved Examples / 292
5.17 Suggestions for Further Reading / 299
5.18 Problems / 300

6 Review of Some Thermodynamics and Statistical Mechanics 311

6.1 Group Contribution Methods / 311
6.2 Applications to Metal Surfaces / 316
6.3 Extension to Semiconductors and Insulators / 317
6.4 Calculation of Thermodynamic Properties from Statistical
Mechanics / 318
6.5 Supplemental Material: Molecular Dynamics / 333
6.6 Solved Examples / 334
6.7 Suggestions for Further Reading / 351
6.8 Problems / 352 *

7 Introduction to Reaction Rate Theory 359

7.1 Introduction / 359
7.2 Collision Theory / 361
7.3 The Marcellin-Wigner-Polanyi Model / 369
7.4 Transition State Theory / 372
7.5 Rice-Ramsperger-Kassel-Marcus (RRKM) Theory / 379
7.6 Summary and Plan for the Next Two Chapters / 383
7.7 Solved Examples / 383
7.8 Suggestions for Further Reading / 402
7.9 Problems / 403

8 Reactions as Collisions 413

8.1 Historical Introduction / 413
8.2 Collision Theory / 414
8.3 An Improved Collision Theory / 416
8.4 Molecular Dynamics as a Way to Compute Reaction
Probabilities / 421
8.5 Potential Energy Surfaces for Reactions / 428
8.6 Reaction as Motion on Potential Energy Surfaces / 432
8.7 Qualitative Features of the Collisions: Exchange Reactions / 435
8.8 Summary of Linear Collisions / 446
8.9 The Nonlinear Case / 447
8.10 More Complex Reactions / 450
8.11 Complexities: Unimolecular Reactions / 452
8.12 Bimolecular Recombination Reactions / 454
8.13 Energy Transfer Barrier to Reactions / 454
8.14 Electron Transfer Reactions / 457
8.15 Summary / 458
Viii CONTENTS

8.16 Supplemental Material / 459

8.17 Solved Examples / 467
8.18 Suggestions for Further Reading / 484
8.19 Problems / 484

9 Transition State Theory, the RRKM Model, and Related Results 497
9.1 Arrhenius' Model and Tolman's Equation / 497
9.2 Conventional Transition State Theory / 505
9.3 Successes of Conventional Transition State Theory / 510
9.4 The Role of the Transmission Coefficient / 519
9.5 Tunneling / 520
9.6 Variational Transition State Theory / 527
9.7 Multi Conflgurational Transition State Theory / 528
9.8 Unimolecular Reactions / 530
9.9 Laser Photolysis / 531
9.10 The RRKM Model / 534
9.11 Barrierless Reactions / 540
9.12 Collision Theory for Barrierless Reactions / 541
9.13 Thermal Unimolecular Reactions / 543
9.14 Summary / 548
9.15 Solved Examples / 549
9.16 Suggestions for Further Reading / 564
9.17 Problems / 565

10 Why Do Reactions Have Activation Barriers? 571

10.1 Introduction / 571
10.2 Barriers Associated with Bond Extensions / 573
10.3 Derivation of the Polanyi Relationship / 574
10.4 The Polanyi Relationship / 577
10.5 The Marcus Equation / 583
10.6 Pauli Repulsions / 592
10.7 A Model for the Role of Pauli Repulsions on the Barriers to
Reaction / 599
10.8 Limitations of the Models: Quantum Effects / 606
10.9 The Configuration Mixing Model / 606
10.10 Symmetry-Forbidden Reactions / 613
10.11 Qualitative Results / 616
10.12 Conservation of Orbital Symmetry / 621
10.13 Examples of Symmetry-Allowed and Symmetry-Forbidden
Reactions / 623
10.14 Summary / 623
10.15 Solved Examples / 624
10.16 Suggestions for Further Reading / 625
10.17 Problems / 625

11 More about Activation Energies 633

11.1 Introduction / 633
 CONTENTS ix

11.2 Empirical Correlations for Reaction Rates: The Polanyi

Relationship and Br0nsted Catalysis Law / 634
11.3 Linear Free-Energy Relationships / 640
11.4 The Polanyi Relationship / 648
11.5 Quantum-Mechanical Methods / 652
11.6 Summary / 668
11.7 Solved Examples / 668
11.8 Suggestions for Further Reading / 680
11.9 Problems / 681

12 Introduction to Catalysis 689

12.1 Introduction / 689
12.2 Overview of Homogeneous Catalysts / 692
12.3 Introduction to Heterogeneous Catalyst / 698
12.4 General Overview of Catalytic Action / 707
12.5 Catalysts Can Be Designed to Initiate Reactions / 709
12.6 Catalysts Can Be Designed to Stabilize Intermediates / 711
12.7 Derivation of Sabatier's Principle / 719
12.8 Catalysts Can Be Designed to Hold the Reactants in Close
Proximity / 725
12.9 Catalysts Can Be Designed to Hold the Reactants in the Correct
Configuration to React / 726
12.10 Catalysts Stretch Bonds and Otherwise Make Bonds Easier to
Break / 727
12.11 Stabilization of Transition States / 729
12.12 Catalysts Can Be Designed to Block Side Reactions / 734
12.13 Catalysts Can Be Designed to Donate and Accept
Electrons / 736
12.14 Catalysts Can Act as an Efficient Means for Energy
Transfer / 738
12.15 Mass Transfer Effects Are More Important When a Catalyst Is
Present / 738
12.16 Summary of Potential Catalyst Functions / 742
12.17 Kinetics of Catalytic Reactions / 743
12.18 Summary / 758
12.19 Supplemental Material / 759
12.20 Solved Examples / 763
12.21 Suggestions for Further Reading / 775
12.22 Problems / 776

13 Solvents as Catalysts 795

13.1 Introduction / 795
13.2 Examples of the Role of Solvents in Changing Rates of
Reactions / 797
13.3 Why Do Solvents Change Rates? / 800
133
13.4 Solvents Stabilize Transition States and Thereby Modify the
Intrinsic Barriers to Reactions / 803
 CONTENTS

13.5 Introduction to Solvation / 806

13.6 Qualitative Predictions of the Effects of Solvents on Rates / 810
13.7 Semiquantitative Predictions / 813
13.8 Dynamic Corrections / 821
13.9 Summary / 826
13.10 Supplemental Material: Derivation of Equation (13.52) / 827
13.11 Suggestions for Further Reading / 832
13.12 Problems / 832

14 Catalysis by Metals 837

14.1 Introduction / 837
14.2 Elementary Reactions on Metals / 848
14.3 Overall Mechanisms of Metal-Catalyzed Reactions / 854
14.4 Principles of Catalytic Action / 862
14.5 Trends over the Periodic Table / 874
14.6 Models for Trends over the Periodic Table / 879
14.7 Metal Catalysts for Specific Organic Transformations / 881
14.8 The Blowers-Masel Equation as a Quantitative Tool for Catalyst
Selection / 884
14.9 Kinetics of Reactions on Metals / 886
14.10 Summary / 887
14.11 Solved Examples / 887
14.12 Suggestions for Further Reading / 893
14.13 Problems / 893

References 901

Index 915