Extractive Metallurgy 1: Basic Thermodynamics and Kinetics

Preface xi

Chapter 1. Metallurgical Thermochemistry 1

1.1. Introduction 1

1.2. Quantities characterizing the state of a system and its evolution 3

1.3. Thermodynamic fundamentals of reactions 16

1.4. Phase diagrams 36

1.5. Bibliography 39

Chapter 2. Oxides, Sulfides, Chlorides and Carbides 41

2.1. Introduction 41

2.2. Metal-oxygen/metal-sulfur systems activities in the intermediate phases 42

2.3. Standard Gibbs free energy: temperature diagrams for oxides – Ellingham-Richardson diagrams 51

2.4. Thermodynamic data for sulfides and chlorides 58

2.5. Metal-carbon phase diagrams and the Ellingham-Richardson diagram for Carbides 63

2.6. Carbon and carbon oxide reactions 67

2.7. Bibliography 71

Chapter 3. Metal Solutions, Slags and Mattes 73

3.1. Introduction 73

3.2. Metal solutions 74

3.3. Mattes 93

3.4. Slags 106

3.5. Bibliography 127

Chapter 4. Aqueous Electrolytic Solutions and Salt Melts 131

4.1. Introduction 131

4.2. Thermodynamics of aqueous electrolyte solutions 131

4.3. Thermodynamics of salt melts (fluxes) 173

4.4. Bibliography 179

Chapter 5. Reaction Kinetics 183

5.1. Introduction 183

5.2. Rate of a chemical reaction 184

5.3. Homogeneous precipitation 189

5.4. Kinetics and mechanism of heterogeneous reactions 194

5.5. Reaction rates for in situ conversion of a solid particle 211

5.6. Heterogeneous precipitation 215

5.7. Bibliography 217

Chapter 6. Transport Kinetics 219

6.1. Introduction 219

6.2. Equations of change and relationships between diffusion fluxes and driving forces 223

6.3. Interphase mass or heat transport (mass and heat transfer) 227

6.4. Mass and heat transfer coefficients 236

6.5. Overall kinetics of extraction processes under mixed control 247

6.6. Bibliography 251

Chapter 7. Particulate Kinetics 253

7.1. Introduction 253

7.2. Gasification/leaching of a particle 254

7.3. Heterogeneous precipitation: growth rate of the particles 263

7.4. In situ conversion of a solid particle 264

7.5. Conversion of a particle undergoing strong exo- or endothermic chemical reactions 270

7.6. Transfer processes between two fluid phases, one phase being dispersed (as drops or bubbles) in the second phase 276

7.7. Bibliography 280

Chapter 8. Electrochemical Reactions 283

8.1. Overview of electrochemical processes 283

8.2. Equilibrium electric potential of an elementary electrochemical reaction 285

8.3. Electrochemical equilibria of metals and metalloids (Pourbaix diagrams)292

8.4. Electrochemical kinetics 306

8.5. Redox electrochemical reactions 314

8.6. Bibliography 322

List of Symbols 325

Index 337

Summaries of Other Volumes 345