Supercritical Water

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.

• Preface ixList of Acronyms and Symbols xiii1 Introduction 11.1 Phase Diagrams of Single Fluids 11.2 The Critical Point 31.3 Supercritical Fluids as Solvents 51.4 Gaseous and Liquid Water 81.5 Near-Critical Water 151.6 Summary 172 Bulk Properties of SCW 222.1 Equations of State(EoS) 222.1.1 PVT Data for SCW 222.1.2 Classical Equations of State of SCW 242.1.3 Scaling Equations of State for SCW 262.1.4 EoS of Supercritical Heavy Water 292.2 Thermophysical Properties of SCW 302.2.1 Heat Capacity 302.2.2 Enthalpy and Entropy 322.2.3 Sound Velocity 342.3 Electrical and Optical Properties 342.3.1 Static Relative Permittivity 342.3.2 Electrical Conductivity 372.3.3 Light Refraction 382.4 Transport Properties 392.4.1 Viscosity 392.4.2 Self-Diffusion 412.4.3 Thermal Conductivity 422.5 Ionic Dissociation of SCW 442.6 Properties Related to the Solvent Power of SCW 472.7 Summary 493 Molecular Properties of SCW 573.1 Diffraction Studies of SCW Structure 603.1.1 X-Ray Diffraction Studies of SCW Structure 613.1.2 Neutron Diffraction Studies of SCW Structure 623.2 Computer Simulations of SCW 663.2.1 Monte Carlo Simulations 673.2.2 Molecular Dynamics Simulations 703.3 Spectroscopic Studies of SCW 743.3.1 Infrared Absorption Spectroscopy 743.3.2 Raman Scattering Spectroscopy 773.3.3 Nuclear Magnetic Resonance 793.3.4 Dielectric Relaxation Spectroscopy 823.4 The Extent of Hydrogen Bonding in SCW 833.5 The Dynamics of Water Molecules in SCW 903.6 Summary 924 SCW as a “Green” Solvent 1004.1 Solutions of Gases in SCW 1014.1.1 Phase Equilibria 1014.1.2 Interactions in the Solutions 1044.2 Solutions of Organic Substances in SCW 1064.2.1 Phase Equilibria 1064.2.2 Interactions in the Solutions 1114.3 Solutions of Salts and Ions in SCW 1154.3.1 Solubilities of Salts and Electrolytes 1154.3.2 Thermodynamic Properties 1214.3.3 Transport Properties 1234.3.4 Ion Association in SCW 1294.3.5 Ion Hydration in SCW 1344.4 Binary Mixtures of Cosolvents with SCW 1384.5 Summary 1415 Applications of SCW 1515.1 Conversion of Organic Substances to Fuel 1525.1.1 Conversion to Hydrogen and Natural Gas 1525.1.2 Conversion to Liquid Fuel 1565.2 Supercritical Water Oxidation 1575.2.1 General Aspects of SCWO Process 1585.2.2 Examples of SCWO Applications 1605.3 Uses of SCW in Organic Synthesis 1625.4 Uses in Powder Technology of Inorganic Substances 1645.5 Geothermal Aspects of SCW 1665.6 Application of SCW in Nuclear Reactors 1695.7 Corrosion Problems with SCW 1715.8 Summary 174Author Index 183Subject Index 199