Thermodynamics of Silicates

I. The Basic Concepts and Laws of Thermodynamics.- 1 Basic Concepts of Thermodynamics.- 2 The First Law of Thermodynamics: Thermochemistry.- 3 The Second Law of Thermodynamics.- 4 Methods of Thermodynamics.- 5 The Third Law of Thermodynamics.- 6 Chemical Equilibrium and the Principles of Calculating It.- 7 Phase Equilibria.- 8 Phase Diagrams.- 9 Methods of Obtaining Initial Thermodynamic Data.- 10 The Calculation of ?G =f(T) of Reactions in Silicate Systems Based on Simple Thermodynamic Data.- 11 The Peculiarities of Applying the Methods of Chemical Thermodynamics to Silicate Systems.- II. Pyrosilicate Reactions.- 1 General Principles.- 1.1 Types of Pyrosilicate Reactions.- 1.2 Polymorphic Transformations of Silicates and Oxides.- 1.2.1 The Case of Enantiotropic Transformations.- 1.2.2 The Case of Monotropic Transformations.- 1.3 Chemical Interaction in Solid Phases.- 1.4 Reactions with Gaseous Substances.- 1.4.1 Carbonate Dissociation.- 1.4.2 Sulphate Dissociation.- 1.4.3 Reactions of Silicate Formation with Gaseous Phase Release.- 1.5 Reactions with Substances in Molten State and Combined Reactions.- 1.5.1 On the Nature of Silicate Melts.- 1.5.2 Thermodynamics of Melts.- 1.5.3 The Application of the Theory of Regular Solutions.- 1.5.4 Binary Systems.- 1.5.4.1 Equations of the Gibbs Free Energy and of Activity Coefficients.- 1.5.4.2 System FeO-SiO2.- 1.5.4.3 System PbO-SiO2.- 1.5.4.4 Systems CaO-SiO2 and MgO-SiO2.- 1.5.5 Ternary Systems.- 1.5.5.1 System FeO-CaO-SiO2.- 1.5.5.2 System CaO-Al2O3-SiO2.- 2 The Thermodynamic Analysis of the Silicate Formation Reactions in Binary and Ternary Systems.- 2.1 System BeO-SiO2.- 2.2 System MgCO3-MgSO4-MgO-SiO2.- 2.2.1 System MgO-SiO2.- 2.2.2 System MgCO3-MgO-SiO2.- 2.2.3 System MgSO4-MgO-SiO2.- 2.3 System CaCO3-CaSO4-CaO-SiO2.- 2.3.1 System CaCO3-CaO-SiO2.- 2.3.2 System CaSO4-SiO2.- 2.4 System SrCO3-SrSO4-SrO-SiO2.- 2.4.1 System SrCO3-SrO-SiO2.- 2.4.2 System SrSO4-SrO-SiO2.- 2.5 System BaCO3-BaSO4-BaO-SiO2.- 2.5.1 System BaCO3-BaO-SiO2.- 2.5.2 System BaSO4-SiO2.- 2.6 General Regularities of the Reactions of Silicate Formation in the Systems Under Consideration.- 2.6.1 The Interaction of Quartz with Oxides of Alkali-Earth Metals.- 2.6.2 The Interaction of Quartz with Carbonates of Alkali-Earth Metals.- 2.6.3 The Interaction of Quartz with Sulphates of Alkali-Earth Metals.- 2.7 System Iron Oxides-Silica.- 2.8 System Manganese Oxides-Silica.- 2.9 System MgO-SrO-SiO2.- 2.10 System Na2O-CaO-SiO2.- 2.11 System CaO-Al2O3-SiO2.- 3 Reactions in the Firing of Ceramics and Refractories.- 3.1 Stability of Oxides.- 3.2 System Al2O3-SiO2.- 3.3 System ZrO2-SiO2.- 3.4 Kaolinite Dissociation at Heating.- 4 Reactions of Glass Formation and Devitrification.- 4.1 General.- 4.2 Silicate Formation in Glass Production.- 4.2.1 System Na2CO3-Na2SO4-SiO2.- 4.2.2 System K2CO3-K2SO4-SiO2.- 4.2.3 System Li2CO3-Li2SO4-Li2O-SiO2.- 4.2.4 System Rb2CO3-Rb2SO4-SiO2.- 4.2.5 System Cs2CO3-Cs2SO4-SiO2.- 4.2.6 System PbO-SiO2.- 4.3 Peculiarities of Some Vitreous Systems.- 4.4 Devitrification of Glasses.- 4.5 The Calculation of the Heat Consumption of Glass Melting.- 5 Reactions Proceeding During Firing Binders.- 6 Instances of Using Thermodynamic Calculations for Solving Other Problems of the Study of Materials.- 6.1 Composite Materials.- 6.2 The Interaction of Ceramics with Metals.- 6.3 Binding Oxides for Enamels.- 6.4 Water Resistance of Silicates.- III. Hydration Reactions.- 1 General.- 2 The Basic Properties and Thermodynamic Stability of Water.- 3 Gypsum Hemihydrate Hydration and Hydrolysis Reactions.- 4 Reactions in the System CaO-H2O.- 5 Reactions in the System SiO2-H2O.- 6 Reactions in the Systems CaO-SiO2-H2O, ?-2 CaO SiO2-H2O and 3CaO SiO2-H2O.- 6.1 General.- 6.2 The Calculation of Thermochemical Values of Calcium Hydrosilicates.- 6.3 Thermodynamic Calculations of the Main and Secondary Reactions in the System Ca(OH)2-SiO2-H2O at Normal and Hydrothermal Conditions.- 6.4 The Energetics of the Processes of the C2S and C3S Hydration.- 7 Reactions of Hydration of Calcium Aluminates and of Iron-Containing Phases of Portland Cement Clinker.- 7.1 General.- 7.2 Reactions of Calcium Aluminates with Water.- 7.3 Hydration of Calcium Aluminates in the Presence of Gypsum.- 7.4 Dicalcium Ferrite Hydration.- 7.5 Reactions of the Tetracalcium Alumoferrite Hydration.- 7.6 Hydration of Iron-Containing Phases with Gypsum.- 8 Reactions in the System MgO-SiO2-HaO.- 9 Thermochemistry and the Energy Principles of the Cement Hydration Processes.- 10 A Calculation of Colloid-Chemical Equilibria in the Systems Binder-Water.- IV. Corrosion Reactions.- 1 Reactions of the Interaction of the Constituents of Cement Stone and Concrete with Acid Gases.- 2 Reactions of the Interaction of the Constituents of Cement Stone and Concrete with Hydrogen Ions.- 3 Corrosion Resistance of Aluminium and Iron-Containing Phases of Cement Stone in Sulphate Media.- 4 Reactions in the Acid-Sulphate Corrosion of Concrete.- V. Thermodynamics of Irreversible Processes.- 1 Local Macrocharacteristics of a System, Conservation Laws and Balance Equations.- 2 The Second Law of Thermodynamics, Local Equilibrium and the Entropy Balance Equation.- 3 The Linear Thermodynamics of Irreversible Processes.- 4 The Application of the Thermodynamics of Irreversible Processes to the Study of Silicate Systems.- References.- Appendix 1. Standard Enthalpies, Gibbs Free Energies and Heat Capacity Equations of Some Elements, Simple Substances and Compounds.- Appendix 2. Thermodynamic Properties of Ions and Molecules in Aqueous Solutions.- References to Appendices 1 and 2.- Appendix 3. The Heats of Polymorphic Transitions and Melting.- References to Appendix 3.- Author Index.