List of Figures v
List of Tables ix
List of Symbols x
Acronyms and Abbreviations xiii
Glossary xix
Acknowledgments xxxviii
Dedication xl
Foreword xlii
Preface xliii

1 Introduction 1
1.1 Scope 1
1.2 Overview 2
1.3 Effective Reactive Chemical Management 9
1.4 Summary 11

2 Key Elements of Chemical Reactivity 13
2.1 The Nature of Reactive Chemistry 13
2.2 Energy and Molecular Transformation 17
2.3 Types of Chemistry 20
2.4 Loss of Control of Reaction 21
2.5 Process Risk Assessment 27
2.6 Process Scale-Up and Design 28
2.7 Summary 30

3 Methods for Reactive Hazards Evaluation and Assessment 31
3.1 Qualitative Methods – Benefits and Limitations 32
3.2 Thermochemical Methods 47
3.3 Quantitative Methods – Data Generation and Evaluation 54
3.4 Summary 119

4 Applicability of Reactivity Data to Engineering Design 125
4.1 Batch System Scale-Up 125
4.2 Industrial Design of Batch Reactors 146
4.3 Industrial Design of Continuous and Semi-Batch Reactors 175
4.4 Reactivity Characterization 201
4.5 Secondary Containment/Effluent Handling Systems 213
4.6 Summary 232

5 Hazard Identification and Risk Analysis 233
5.1 Application of the Results in Hazard Identification and Risk Analysis (HIRA) 233
5.2 Use of Reactivity Information in HIRA Processes 237
5.3 Warehousing 278
5.4 Summary 280

6 Implementation of Risk Based Process Safety (RBPS) and the Related Cycle Elements 283
6.1 Introduction 283
6.2 Cycle Element: Inform (Know) 285
6.3 Cycle Element: Implement (Do) 292
6.4 Cycle Element: Communicate (Tell) 319
6.5 Cycle Element: Verify (Check) 343
6.6 Technology Transfer Plan 373
6.7 Roles and Responsibilities 377
6.8 Summary 381

7 Learning from Past Events 383
7.1 Introduction 383
7.2 Contamination 383
7.3 Inadequate Communication to Operations 387
7.4 Failure to Recognize Reactive Potential 392
7.5 Ignoring Warnings in the Literature 405
7.6 Technology Transfer Plan 406
7.7 Extended Period of Downtime/Lack of Monitoring 407
7.8 Events with Significant External Factors 410
7.9 Summary 412

Appendix A1 Other Tests 415

Appendix A2 Key Macroscopic Properties of Reactive Systems 419
A2.1 Heat-Transfer Limiting Models 419
A2.2 Temperature of No Return 421
A2.3 Self-Accelerating Reaction Temperature (SART) – Semenov 425
A2.4 Steady-State Multiplicity 427
A2.5 SART – Frank-Kamenetskii 436
A2.6 Pressure 437
A2.7 Summary 438

Appendix A3 HIRA Checklist 439

References 447
Additional Reading 481
Index 483