Title Details

ANNE E. MARTEEL-PARRISH, PhD, is Chair of the Chemistry Department at Washington College, in Maryland, and the inaugural holder of the college's Frank J. Creegan Chair in Green Chemistry. Among her honors, Dr. Marteel-Parrish is the recipient of the American Chemical Society's Committee on Environmental Improvement Award for Incorporating Sustainability into Chemistry Education.

MARTIN A. ABRAHAM, PhD, is Professor of Chemical Engineering and Founding Dean of the College of Science, Technology, Engineering, and Mathematics at Youngstown State University. A Fellow of the American Chemical Society and the American Institute of Chemical Engineers, Dr. Abraham maintains an active research program in reaction engineering and catalysis. He also serves as Editor for the AIChE's quarterly journal Environmental Progress and Sustainable Energy.

Preface xiii

1 UNDERSTANDING THE ISSUES 1

1.1 A Brief History of Chemistry 1

1.1.1 Fermentation: An Ancient Chemical Process 2

1.1.2 The Advent of Modern Chemistry 2

1.1.3 Chemistry in the 20th Century: The Growth of Modern Processes 2

1.1.4 Risks of Chemicals in the Environment 6

1.1.5 Regulations: Controlling Chemical Processes 11

1.2 Twenty-first Century Chemistry, aka Green Chemistry 13

1.2.1 Green chemistry and Pollution Prevention 13

1.2.2 Sustainability 14

1.3 Layout of the Book 18

References 19

2 PRINCIPLES OF GREEN CHEMISTRY AND GREEN ENGINEERING 21

2.1 Introduction 21

2.2 Green Chemistry 23

2.2.1 Definition 23

2.2.2 Principles of Green Chemistry and Examples 24

2.2.3 Presidential Green Chemistry Challenge Awards 31

2.3 Green Engineering 34

2.3.1 Definition 34

2.3.2 Principles of Green Engineering 35

2.4 Sustainability 38

References 41

3 CHEMISTRY AS AN UNDERLYING FORCE IN ECOSYSTEM INTERACTIONS 43

3.1 Nature and the Environment 44

3.1.1 Air and the Atmosphere (Outdoor and Indoor Pollution) 44

3.1.2 Water (Water Pollutants, Issues Associated with Nonpotable Drinking Water) 52

3.1.3 Chemistry of the Land 53

3.1.4 Energy 56

3.2 Pollution Prevention (P2) 61

3.3 Ecotoxicology 62

3.4 Environmental Assessment Analysis 64

3.5 What Can You Do to Make a Difference? 68

References 70

4 MATTER: THE HEART OF GREEN CHEMISTRY 73

4.1 Matter: Definition, Classification, and the Periodic Table 73

4.1.1 Aluminum (Al) 75

4.1.2 Mercury (Hg) 76

4.1.3 Lead (Pb) 77

4.2 Atomic Structure 77

4.3 Three States of Matter 79

4.4 Molecular and Ionic Compounds 81

4.4.1 Molecular Compounds 82

4.4.2 Ionic Compounds 94

4.5 Chemical Reactions 100

4.6 Mixtures, Acids, and Bases 102

References 107

5 CHEMICAL REACTIONS 109

5.1 Definition of Chemical Reactions and Balancing of Chemical Equations 109

5.2 Chemical Reactions and Quantities of Reactants and Products 112

5.3 Patterns of Chemical Reactions 115

5.3.1 Combination, Synthesis, or Addition Reactions 115

5.3.2 Decomposition Reactions 117

5.3.3 Elimination Reactions 117

5.3.4 Displacement Reactions 118

5.3.5 Exchange or Substitution Reactions 124

5.4 Effectiveness and Efficiency of Chemical Reactions: Yield Versus Atom Economy 135

Reference 138

6 KINETICS, CATALYSIS, AND REACTION ENGINEERING 139

6.1 Basic Concept of Rate 139

6.1.1 Definition of Reaction Rate 139

6.1.2 Parallel Reactions 142

6.1.3 Consecutive Reactions 146

6.1.4 Chemical Equilibrium 150

6.1.5 Effect of Concentration on Reaction Rate 153

6.1.6 Effect of Temperature on Reaction Rate 159

6.2 Role of Industrial and Biological Catalysts 162

6.2.1 Definition of Catalysts 162

6.2.2 Catalytic Kinetics 166

6.2.3 Types of Catalysts and Impact on Green Chemistry 170

6.2.4 Biocatalysis 175

6.3 Reaction Engineering 181

6.3.1 Batch Reactor 181

6.3.2 Continuous Stirred Tank Reactor 184

6.3.3 Plug Flow Reactor (PFR) 188

6.3.4 Multiphase Reactor Design 191

6.4 Summary 194

References 194

7 THERMODYNAMICS, SEPARATIONS, AND EQUILIBRIUM 197

7.1 Ideal Gases 197

7.2 The First Law of Thermodynamics 201

7.2.1 Closed System 203

7.2.2 Open System 204

7.3 Ideal Gas Calculations 205

7.4 Entropy and the Second Law of Thermodynamics 210

7.5 Real Gas Properties 214

7.6 The Phase Diagram 217

7.7 Equilibrium 221

7.7.1 The Flash Calculation 227

7.8 Solubility of a Gas in a Liquid 229

7.9 Solubility of a Solid in a Liquid 230

7.10 Summary 233

References 233

8 RENEWABLE MATERIALS 235

8.1 Introduction 235

8.2 Renewable Feedstocks 236

8.2.1 Role of Biomass and Components 236

8.2.2 Production of Chemicals from Renewable Resources 242

8.3 Applications of Renewable Materials 251

8.3.1 The Case of Biodegradable Plastics 251

8.3.2 The Case of Compostable Chemicals 254

8.3.3 Production of Ethanol from Biomass 254

8.3.4 The Case of Flex-Fuel Vehicles 256

8.3.5 Production of Biodiesel 258

8.4 Conclusion 261

References 261

9 CURRENT AND FUTURE STATE OF ENERGY PRODUCTION AND CONSUMPTION 263

9.1 Introduction 263

9.2 Basic Thermodynamic Functions and Applications 267

9.3 Other Chemical Processes for Energy Transfer 272

9.3.1 Microwave-Assisted Reactions 272

9.3.2 Sonochemistry 273

9.3.3 Electrochemistry 273

9.3.4 Photochemistry and Photovoltaic Cells 274

9.4 Renewable Sources of Energy in the 21st Century and Beyond 275

9.4.1 Solar Energy 275

9.4.2 Wind Power 279

9.4.3 Geothermal Solution 281

9.4.4 Hydropower 283

9.4.5 The Case of Hydrogen Technology 284

9.4.6 Barriers to Development 285

9.5 Concluding Thoughts About Sources of Energy and their Future 285

References 286

10 THE ECONOMICS OF GREEN AND SUSTAINABLE CHEMISTRY

By David E. Meyer and Michael A. Gonzalez 287

10.1 Introduction 287

10.2 Chemical Manufacturing and Economic Theory 289

10.2.1 Plant (Microscale) Scale Economics 290

10.2.2 Corporate Economics 290

10.2.3 Macroeconomics 292

10.3 Economic Impact of Green Chemistry 293

10.4 Business Strategies Regarding Application of Green Chemistry 306

10.5 Incorporation of Green Chemistry in Process Design for Sustainability 310

10.6 Case Studies Demonstrating the Economic Benefits of Green Chemistry and Design 317

10.7 Summary 321

References 322

11 GREEN CHEMISTRY AND TOXICOLOGY

By Dale E. Johnson and Grace L. Anderson 325

11.1 Introduction 325

11.2 Fundamental Principles of Toxicology 326

11.2.1 Basic Concepts 326

11.2.2 Toxicokinetics 330

11.2.3 Cellular Toxicity 333

11.3 Identifying Chemicals of Concern 335

11.3.1 Mode of Action Approaches 336

11.3.2 Adverse Outcome Pathways 337

11.3.3 Threshold of Toxicological Concern 338

11.3.4 Chemistry-Linked-to-Toxicity: Structural Alerts and Mechanistic Domains 338

11.4 Toxicology Data 339

11.4.1 Authoritative Sources of Information 339

11.4.2 Data Gaps: The Challenge and the Opportunity Arising from New Technologies 340

11.5 Computational Toxicology and Green Chemistry 341

11.5.1 Tools for Predictions and Modeling 341

11.5.2 Interoperability of Models for Decision Making and the Case for Metadata 346

11.6 Applications of Toxicology into Green Chemistry Initiatives 346

11.6.1 REACH 346

11.6.2 State of California Green Chemistry Initiatives 348

11.7 Future Perspectives 349

References 350

Index 355