Thermodynamics of Silicates

ISBN-13: 9783642693229 / Angielski / Miękka / 2011 / 459 str.

V. I. Babushkin; G. M. Matveyev; O. P. McHedlov-Petrossyan

Opis

The intensification of the production of silicate materials and products makes a de tailed theoretical study of the processes underlying their manufacture and service more and more urgent. The thermodynamic method is of great importance for studying chemical reac tions of silicate technology. Together with a study of the rate and mechanism of sub stance transfer, it permits obtaining necessary data for the efficient operation of technological processes. The progress of science in recent years has solved numerous problems in the field of the physical chemistry of silicates. The great progress in deciphering silicate structures, and working out methods of the synthesis of minerals and studying their properties must be mentioned. New methods of determining thermic constants have appeared. In future these methods should be more widely used for determining the heats of the silicate forma tion and related compounds in crystalline and vitreous state. This concerns in par ticular the system - CaO - Ab03 - Fe203 - Si0 - H 0 -which is of great impor 2 2 tance for the technology of cement and concrete, ceramics, refractories and glass."

Spis treści

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.