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Supercritical Water

ISBN: 978-0-470-88947-3
218 pages
June 2012
Supercritical Water (0470889470) cover image

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.

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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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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.

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