The Experimental Determination of Solubilities

* Guidelines are provided on the reliability of various methods, as well as information for selecting the appropriate technique.
* Unique coverage of the whole range of solubility measurements.
* Very useful for investigators interested in embarking upon solubility measurements.In diesem Band werden vielfältige experimentelle Verfahren zur Bestimmung von Löslichkeiten beschrieben.
- Commission on Solubility Data der IUPAC beschloß, die Qualität der Löslichkeitsdaten international anzugleichen und zu verbessern, indem verläßliche Verfahren zur Ermittlung dieser Daten zusammengefaßt veröffentlicht werden
- alle Datentypen wurden hier berücksichtigt
- ausführliche Angaben zur Zuverlässigkeit der einzelnen Verfahren und zur Auswahl der jeweils geeigneten Methode

List of Contributors xi

Series Preface xv

Preface xvii

Acknowledgements xxi

List of Symbols xxiii

Quantities, Units and Conversions 1
John W. Lorimer

1. Quantities and Units Used to Describe Solubility 2

2. Quantities and Units Used to Describe Solubilities of Gases 6

3. References 14

1 Fundamentals of Solubility 17

Chapter 1.1 Thermodynamics of Solubility 19
John W. Lorimer and Roger Cohen-Adad

1. Introduction 19

2. Basic Definitions in Thermodynamics of Solubility 19

3. Thermodynamics of Solubility 22

4. Solubility of Gases in Liquids 26

5. Solubility of Liquids in Liquids 41

6. Solubility of Solids in Liquids 50

7. Concluding Remarks 62

8. References 62

Appendix A: Some Useful Thermodynamic Concepts and Relations 70

Appendix B: Numerical and Statistical Procedures in Constructing Fitting Equations 74

Chapter 1.2 Kinetics and Mechanisms of Crystal Growth and Dissolution 77
Jørgen Christoffersen and Margaret R. Christoffersen

1. Introduction 77

2. Fundamental Concepts 77

3. Mechanisms and Rate Expressions for Dissolution and Growth 81

4. Comparison of Dissolution and Precipitation Kinetics 93

5. Kinetics of Approach to Equilibrium 93

6. Summary of Rate-determining Mechanisms 95

7. Acknowledgement 95

8. References 96

2 Gases 99

Chapter 2.1 Solubility of Gases in Liquids 101
H. Lawrence Clever and Rubin Battino

1. Introduction 101

2. Quantities Used as a Measure of Gas Solubility 102

3. The Solution Components 107

4. Degassing The Solvent 108

5. Experimental Methods 110

6. Related Experiments that Complement Gas Solubility Data 130

7. Treatment of Data 132

8. Standards 137

9. Summary and Recommendations 144

10. References 145

Chapter 2.2 Solubility of Gases in Polymers 151
Y uri Y ampolski and Russell Paterson

1. Introduction 151

2. Manometric Methods 152

3. Gravimetric Methods 156

4. Inverse Gas Chromatography 160

5. Miscellaneous 165

6. Conclusions 167

7. References 168

Chapter 2.3 Solubility of Gases in Molten Salts and Molten Metals 173
Reginald P.T. Tomkins

1. Solubility of Gases in Molten Salts 173

2. Solubility of Gases in Molten Metals 203

3. References 215

Chapter 2.4 Solubility of Gases in Solid Metals 219
Y Sakamoto and F. A. Lewis

1. Sieverts Method 220

2. Equilibrate.Quench.Analyze Method 222

3. Gravimetric Method 224

4. Changes of Lattice Parameters and Electrical Resistivity Due to Dissolved Hydrogen in Metals 225

5. Determination of Changes of Hydrogen Solubilities from Measurements of Electrode Potential Under Conditions of Controlled Electolyte Stirring 228

6. References 232

3 Liquids 235

Chapter 3 Liquid–Liquid Solubilities 237
Glenn T. Hefter

1. Introduction 237

2. The Synthetic Method 238

3. The Analytical Method 244

4. Miscellaneous Methods 249

5. Sample Purity 253

6. Test Systems 253

7. References 254

4 Solids 257

Chapter 4.1 Solubility of Solids in Liquids 259
Roger Cohen-Adad and Marie-Thérèse Cohen Adad

1. General Review of Methods 259

2. Analytical Methods 264

3. Synthetic Methods 277

4. Combinatorial. Methods 306

5. Summary of Experimental Difficulties 309

6. References 311

Chapter 4.2 Solubility of Sparingly Soluble Ionic Solids in Liquids 315
Heinz Gamsjger and Erich Königsberger

1. Introduction 315

2. Fundamentals and Applications of Solubility Measurements 316

3. The Experimental Determination of Solubilities of Sparingly Soluble Compounds 331

4. Summary, Conclusions and Recommendations 351

5. References 353

Chapter 4.3 Solubility of Salt–Water Systems at High Temperatures and Pressures 359
Vladimir M. Valyashko and B.R. Churagulov

1. Introduction 359

2. Phase Diagram Construction (Theory) 361

3. Methods and Equipment for Studying Phase Equilibria in Aqueous Systems at High Pressures and Temperatures 387

4. References 427

Chapter 4.4 Solubility of Metals and Non-metallic Substances in Liquid Metals 437
Cezary Guminski and Hans U. Borgstedt

1. Methods Based on Phase Separation 437

2. Methods Without Separation of the Solute from the Saturated Solution 448

3. Indirect Methods 465

4. Solubility Determinations of Metals and Non-metals in Solid Metals 469

5. References 469

Chapter 4.5 Solubility of Solids in Solids 477
James Sangster

1. Introduction 477

2. The Equilibrium Phase Diagram 477

3. Thermal Analysis 479

4. Quenching Followed by Analysis 485

5. X-Ray Examination 486

6. Ionic Conductivity 486

7. Interdiffusion 487

8. Other Methods 487

9. References 489

5 Special Systems 491

Chapter 5.1 Solubility of Solids and Liquids in Supercritical Fluids 493
Karel Aim and Maurizio Fermeglia

1. Introduction 493

2. Basic Equations and Nomenclature 496

3. Experimental Determination of Solubilities in Dense Gases 498

4. Static Methods 504

5. Recirculation Methods 515

6. Flow Methods 522

7. Saturation (Transpiration) Methods 528

8. Dew- and Bubble-point Methods 534

9. Supercritical Fluid Chromatography 538

10. References 541

Chapter 5.2 Solubility of Solids and Liquids in Cryogenic Liquids 557
Elzbieta Szczepaniec-Cieciak

1. Introduction 557

2. Experimental Techniques for the Determination of Solid.Liquid (S.L) and Solid.Liquid.Vapor (S.L.V) Equilibria in Cryogenic Systems 565

3. Concluding Remarks 584

4. References 586

Chapter 5.3 Solubility of Polymers in Liquids 595
Sonja Krause

1. Sample Problems 596

2. Kinetic Problems 600

3. Phase Diagrams 601

4. Methods 605

5. References 615

Index 617

"...a must for any serious library...the value of this volume and this series extends far beyond chemistry..." (Applied Organometallic Chemistry, Vol 19 (10), October 2005)

G. T. Hefter and R. P. T. Tomkins are the authors of The Experimental Determination of Solubilities, published by Wiley.

This book covers the most useful experimental methods for all types of solubility measurements. The importance of solubility phenomena has been long recognized throughout science. For example, in medicine, the solubility of gases in liquids forms the basis of life itself; in the environment, solubility phenomena influence the weathering of rocks, the creation of soils, the composition of natural water bodies and the behaviour and fate of many chemicals. However, until now, no systematic critical presentation of the methods for obtaining solubilities has been given.

The book is divided into five sections: the first addresses the fundamental thermodynamic and kinetic background necessary for a full understanding of solubility phenomena. The next three sections cover the major types of solubility determinations according to the physical state of the solute: gases, liquids and solids; whilst the final section deals with those technologically important areas whose traditions are sufficiently different to justify their separate presentation.

Each chapter aims to be comprehensive but not encyclopaedic, with coverage of the reliable methods in the particular area. Illustrations have been included to enable the novice investigator quickly develop apparatus of their own. Where appropriate, contributors have included sets of data to enable workers to properly assess the quality of their apparatus, technique and data.