Supercritical Water
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English

Discover the many new and emerging applications of supercritical water as a green solvent

Drawing from thousands of original research articles, this book reviews and summarizes what is currently known about the properties and uses of supercritical water. In particular, it focuses on new and emerging applications of supercritical water as a green solvent, including the catalytic conversion of biomass into fuels and the oxidation of hazardous materials.

Supercritical Water begins with an introduction that defines supercritical fluids in general. It then defines supercritical water in particular, using the saturation curve to illustrate its relationship to regular water. Following this introduction, the book:

  • Describes the bulk macroscopic properties of supercritical water, using equations of state to explain temperature-pressure-density relationships
  • Examines supercritical water's molecular properties, setting forth the latest experimental data as well as computer simulations that shed new light on structure and dynamics
  • Explores the solubilities of gases, organic substances, salts, and ions in supercritical water in terms of the relevant phase equilibria
  • Sets forth the practical uses of supercritical water at both small scales and full industrial scales

Throughout the book, the author uses tables for at-a-glance reviews of key information. Summaries at the end of each chapter reinforce core principles, and references to original research and reviews serve as a gateway and guide to the extensive literature in the field.

Supercritical Water is written for students and professionals in physical chemistry, chemistry of water, chemical engineering, and organic chemistry, interested in exploring the applications and properties of supercritical water.

English

YIZHAK MARCUS, PHD, is Professor Emeritus of Inorganic and Analytical Chemistry at The Hebrew University of Jerusalem. His research focuses on solution chemistry, including aqueous, non-aqueous, and mixed solvents as well as solutions of electrolytes and non-electrolytes. Dr. Marcus has published six books and more than 300 papers in peer-reviewed journals.

English

Preface ix

List of Acronyms and Symbols xiii

1 Introduction 1

1.1 Phase Diagrams of Single Fluids 1

1.2 The Critical Point 3

1.3 Supercritical Fluids as Solvents 5

1.4 Gaseous and Liquid Water 8

1.5 Near-Critical Water 15

1.6 Summary 17

2 Bulk Properties of SCW 22

2.1 Equations of State(EoS) 22

2.1.1 PVT Data for SCW 22

2.1.2 Classical Equations of State of SCW 24

2.1.3 Scaling Equations of State for SCW 26

2.1.4 EoS of Supercritical Heavy Water 29

2.2 Thermophysical Properties of SCW 30

2.2.1 Heat Capacity 30

2.2.2 Enthalpy and Entropy 32

2.2.3 Sound Velocity 34

2.3 Electrical and Optical Properties 34

2.3.1 Static Relative Permittivity 34

2.3.2 Electrical Conductivity 37

2.3.3 Light Refraction 38

2.4 Transport Properties 39

2.4.1 Viscosity 39

2.4.2 Self-Diffusion 41

2.4.3 Thermal Conductivity 42

2.5 Ionic Dissociation of SCW 44

2.6 Properties Related to the Solvent Power of SCW 47

2.7 Summary 49

3 Molecular Properties of SCW 57

3.1 Diffraction Studies of SCW Structure 60

3.1.1 X-Ray Diffraction Studies of SCW Structure 61

3.1.2 Neutron Diffraction Studies of SCW Structure 62

3.2 Computer Simulations of SCW 66

3.2.1 Monte Carlo Simulations 67

3.2.2 Molecular Dynamics Simulations 70

3.3 Spectroscopic Studies of SCW 74

3.3.1 Infrared Absorption Spectroscopy 74

3.3.2 Raman Scattering Spectroscopy 77

3.3.3 Nuclear Magnetic Resonance 79

3.3.4 Dielectric Relaxation Spectroscopy 82

3.4 The Extent of Hydrogen Bonding in SCW 83

3.5 The Dynamics of Water Molecules in SCW 90

3.6 Summary 92

4 SCW as a “Green” Solvent 100

4.1 Solutions of Gases in SCW 101

4.1.1 Phase Equilibria 101

4.1.2 Interactions in the Solutions 104

4.2 Solutions of Organic Substances in SCW 106

4.2.1 Phase Equilibria 106

4.2.2 Interactions in the Solutions 111

4.3 Solutions of Salts and Ions in SCW 115

4.3.1 Solubilities of Salts and Electrolytes 115

4.3.2 Thermodynamic Properties 121

4.3.3 Transport Properties 123

4.3.4 Ion Association in SCW 129

4.3.5 Ion Hydration in SCW 134

4.4 Binary Mixtures of Cosolvents with SCW 138

4.5 Summary 141

5 Applications of SCW 151

5.1 Conversion of Organic Substances to Fuel 152

5.1.1 Conversion to Hydrogen and Natural Gas 152

5.1.2 Conversion to Liquid Fuel 156

5.2 Supercritical Water Oxidation 157

5.2.1 General Aspects of SCWO Process 158

5.2.2 Examples of SCWO Applications 160

5.3 Uses of SCW in Organic Synthesis 162

5.4 Uses in Powder Technology of Inorganic Substances 164

5.5 Geothermal Aspects of SCW 166

5.6 Application of SCW in Nuclear Reactors 169

5.7 Corrosion Problems with SCW 171

5.8 Summary 174

Author Index 183

Subject Index 199

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