Approaches. Solvent Extraction: Classical and Novel. Vladimir S. Kislik. Campus Givat Ram, Jerusalem 91904, Israel
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1 Solvent Extraction: Classical and Novel Approaches Vladimir S. Kislik Casali Institute of Applied Chemistry The Hebrew University of Jerusalem Campus Givat Ram, Jerusalem 91904, Israel rrr?-rj Amsterdam boston heidelberg London. new york oxford riloiivliik Paris san dieco. san francisco. Singapore. Sydney tokyo
2 f Contents Preface Introduction xi xiii Part I Conventional (Classical) Principles of Solvent Extraction and Practice 1. Modern (Classical) Fundamental Principles of Solvent Extraction 3 1. Introduction 5 2. Solvent Extraction By Solvation 5 3. Solvent Extraction with Chemical Reactions (By Complexation) Driving Forces of Solvent Extraction Influence of Kinetics Factors Selectivity Factors Affecting Extraction Process Module Design Considerations 49 Determination of Distribution Ratios Experimental 10. Summarizing Remarks 58 References Principles of Solvent Extraction of Organic and Mineral Acids Introduction Extraction of Acids by Carbon-Bonded Oxygen-Donor Extractants and Substituted Hydrocarbon Solvents Phosphorus-Bonded Oxygen Donor Extractants Aliphatic Amine Extractants Extraction of Strong (Inorganic) Acids Summarizing Remarks 102 References Chemistry of Metal Solvent Extraction Introduction Metal Extraction by Cation Exchangers (Acidic Extractants) Metal Extraction by Anion Exchangers (Ion Pair Formation) 127
3 GD Contents 4. Extraction Through Formation of H-Bonding and Solvating Complexes Extraction Through Mixed Complex Formation Extractable Complexation of Monovalent Metals Extraction with Aqueous Biphasic Systems 151 References Engineering Development of Solvent Extraction Processes Introduction Extraction Stage Stripping Organic Solutions Extraction Efficiency Equipment Design for Continuous Extraction-Stripping Processes Solvent Losses Economical Considerations Problems with Scale-Up to Industrial Systems 183 References Examples of Application of Solvent Extraction Techniques in Chemical, Radiochemical, Biochemical, Pharmaceutical, Analytical Separations, and Wastewater Treatment Introduction Extraction in Hydrometallurgy (Metals Extraction) Solvent Extraction in Nuclear Chemistry and Technology Solvent Extraction in Analytical Chemistry Application of Solvent Extraction in Biochemical and Pharmaceutical Separations Application of Solvent Extraction in Organic and Biofuels Separation Solvent Extraction in Recovery of Waste and Wastewater Treatment 284 References 297 Part II Novel Competitive Complexation/Solvation Theory (CCST) of Solvent Extraction: Principles and Practice 6. Backgrounds of the Competitive Complexation/ Solvation Theory of Solvent Extraction Introduction 317
4 Contents GD 2. Complexation Through the H-Bonding and Proton Transfer Distribution Isotherm Modified Competitive Preferential Solvation Theory Electronic Acid-Base Theory and Amphoterity Aggregation 328 References Competitive Complexation/Solvation Theory of Solvent Extraction: General Mechanisms and Kinetics Basic Statements Extraction Systems with Low Solute Concentrations in Organic Phase Systems with Medium Concentrations of the Solute Systems with High Solute Concentrations Comparison of Conventional and Presented Theories Description Summarizing Remarks for the CCST 351 References CCST in Engineering Design, Procedures, and Calculations Introduction Engineering Considerations in Experimental Investigation of CCST Experimental Techniques for the Presented Theory Determination of Extraction Constant and its Comparison with CCST Affinity Constant Ratios Analytical Methods Used for the CCST Verification Transferability of the Values of Affinity Constant Ratios 364 References The CCST in Solvent Extraction of Acids by Amine-Based Extractants Introduction Acid-Amine Systems in the CCST Interpretation The Systems with Active Solvent as an Additive Experimental Application of the CCST in Carboxylic Acids Extraction Summarizing Remarks 395 References 397
5 yjii ^) Contents 10. Competitive Complexation/Solvation Theory in Metal Solvent Extraction Introduction CCST Basic Statements Mathematical Supplement for the CCST in Metal Extraction Experimental Verification of the CCST Approach Summarizing Remarks 427 References Final Remarks on the Competitive Complexation/ Solvation Theory of Solvent Extraction and its Application 433 Part III Modern and Future Trends in Fundamentals and Applications of Solvent Extraction 12. Modern and Future Trends in Fundamentals of Solvent Extraction Introduction Novel Molecular Models Theoretical Approach Low Energy Reactions Measurement Expected Advances in Kinetics Studies Supramolecular (SUPRAS) Theoretical Approach 443 References Advances in Development for Liquid-Liquid of Solvents Extraction Introduction Organic Solvents Water as a Solvent Renewable Water-Based Solvents Ionic as Liquids Solvents for Extraction Amphiphilic Compounds (Supramolecules) as Solvents in Solvent Extraction Extraction by Microemulsion Recovery of Reagents Future Trends in the Development of New Solvents Concluding Remarks 477 References 478
6 Contents 14. Recent Advances in Solvent Extraction Processes and Techniques Introduction Equipment Design and Scale-Up 3. Supercritical Considerations 485 Fluid Extraction Subcritical Water Extraction Aqueous Two-Phase Systems Extraction Processes with Ionic Liquids Liquid Membrane and Nondispersive, Membrane-Based Solvent Extraction Techniques Supramolecular-Based Extraction Techniques Solid-Liquid Extraction Systems Assisted Solvent Extraction Extraction of Gas in Analytical Applications 514 References 515 Appendix 525 Index 539
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