Supercritical Water

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