Ruckenstein / Shulgin Thermodynamics of Solutions

From Gases to Pharmaceutics to Proteins
1. Auflage 2009
ISBN: 978-1-4419-0440-9
Verlag: Springer
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, 346 Seiten

This book consists of a number of papers regarding the thermodynamics and structure of multicomponent systems that we have published during the last decade. Even though they involve different topics and different systems, they have something in common which can be considered as the 'signature' of the present book. First, these papers are concerned with 'difficult' or very nonideal systems, i. e. systems with very strong interactions (e. g. , hyd- gen bonding) between components or systems with large differences in the partial molar v- umes of the components (e. g. , the aqueous solutions of proteins), or systems that are far from 'normal' conditions (e. g. , critical or near-critical mixtures). Second, the conventional th- modynamic methods are not sufficient for the accurate treatment of these mixtures. Last but not least, these systems are of interest for the pharmaceutical, biomedical, and related ind- tries. In order to meet the thermodynamic challenges involved in these complex mixtures, we employed a variety of traditional methods but also new methods, such as the fluctuation t- ory of Kirkwood and Buff and ab initio quantum mechanical techniques. The Kirkwood-Buff (KB) theory is a rigorous formalism which is free of any of the - proximations usually used in the thermodynamic treatment of multicomponent systems. This theory appears to be very fruitful when applied to the above mentioned 'difficult' systems.

Eli Ruckenstein  has won many notable awards, including the Foundes Award from the American Institue of Chemical Engineers, the National Academy of Engineering Founders Award, and the National Medal of Science. His interests include transport phenomena, catalysis, colloids and interfces, phase transformations, thermodynamics, and materials.

Autoren/Hrsg.

Ruckenstein, Eli

Shulgin, Ivan L.

Inhaltsverzeichnis

1;Preface;5
2;Contents;7
3;Chapter 1 The Kirkwood–Buff integrals and their applications to binary and ternary solutions;8
3.1;Hydrophobic self-assembling in dilute aqueous solutions of alcohols and hydrocarbons;36
3.1.1;1. Introduction;36
3.1.2;2. Theory and formulas;37
3.1.3;3. Evaluations of the correlation volume in aqueous solutions of alcohols and hydrocarbons;38
3.1.4;4. Hydrophobic interactions and self-assemblingat in!nite dilution;39
3.1.5;5. Discussion;39
3.1.6;References;40
3.2;Effect of a third component on the interactions in a binary mixture determined from the fluctuation theory of solutions;42
3.2.1;1. Introduction;42
3.2.2;2. Theory and formulas;43
3.2.3;3. Excess number of molecules near a central one;44
3.2.4;4. Source of data and calculation procedure;46
3.2.5;5. Conclusion;54
3.3;The Kirkwood-Buff Theory of Solutions and the Local Composition of Liquid Mixtures;59
3.3.1;1. Introduction;59
3.3.2;2. A New Procedure to Calculate the Excess (Or Deficit) Number of Molecules around a Central Molecule;60
3.4;Excess around a central molecule with application to binary mixtures;66
3.4.1;1. Introduction;66
3.4.2;2. A simple criterion for preferential solvation in a binary system;68
3.4.3;4. Various binary mixtures;69
3.4.4;5. Discussion and conclusion;72
3.4.5;References;74
3.5;An Improved Local Composition Expression and Its Implication for Phase Equilibrium Models;77
3.5.1;1. Introduction;77
3.5.2;2. The Local Composition in an Ideal Mixture;77
3.5.3;3. A Modification of the NRTL Equation;78
3.5.4;4. Comments on Other Expressions for the Local Concentrations;78
3.5.5;5. A Vapor-Liquid Equilibrium Correlation with Equations 10 and 11;79
3.5.6;6. Conclusion;80
3.5.7;Literature Cited;80
4;Chapter 2 Supercritical mixtures;81
4.1;On Density Microheterogeneities in Dilute Supercritical Solutions;82
4.1.1;Introduction;82
4.1.2;Conclusion;86
4.2;Why density augmentation occurs in dilute supercritical solutions;88
4.2.1;1. Introduction;88
4.2.2;2. Fluctuations in SCR mixtures;89
4.2.3;3. Experimental determination of the local density microheterogeneities in pure SCF;89
4.2.4;4. Local density augmentation in SCR mixtures;89
4.2.5;5. Solute±solute interactions;91
4.2.6;6. Conclusion;93
4.2.7;Appendix A;93
4.2.8;References;93
4.3;Fluctuations in dilute binary supercritical mixtures;95
4.4;Entrainer effect in supercritical mixtures;117
4.4.1;1. Introduction;117
4.4.2;2. Theory and formulas;119
4.4.3;3. Calculations;123
4.4.4;4. Conclusion;125
4.4.5;Appendix A;126
4.4.6;Appendix B;126
4.4.7;Appendix C;128
4.4.8;Appendix D;129
4.4.9;Appendix E;130
4.4.10;References;130
4.5;The solubility of solids in mixtures composed of a supercritical fluid and an entrainer;132
4.5.1;1. Introduction;132
4.5.2;2. Theory;133
4.5.3;3. Calculations;139
4.5.4;4. Discussion and conclusion;143
4.5.5;Appendix A;145
4.5.6;References;145
4.6;A Simple Equation for the Solubility of a Solid in a Supercritical Fluid Cosolvent with a Gas or Another Supercritical Fluid;147
4.6.1;1. Introduction;147
4.6.2;2. Theory;147
4.6.3;3. Calculations;149
4.6.4;4. Results;149
4.6.5;6. Conclusion;151
4.7;Cubic Equation of State and Local Composition Mixing Rules: Correlations and Predictions. Application to the Solubility of Solids in Supercritical Solvents;152
4.7.1;Introduction;152
4.7.2;Theory and Formulas;153
4.7.3;Correlation of Solubility Data;154
4.7.4;Prediction of the Solubility of Solid Substances in SCF;155
4.7.5;Conclusion;156
5;Chapter 3 Solubility of gases in mixed solvents;158
5.1;Henry’s Constant in Mixed Solvents from Binary Data;159
5.1.1;1. Introduction;159
5.1.2;2. Theory;159
5.1.3;3. Calculations and Comparison with Experimental Data;162
5.1.4;Conclusion;163
5.2;Salting-Out or -In by Fluctuation Theory;165
5.2.1;1. Introduction;165
5.2.2;2. The Henry Constant in a Salt Solution;166
5.2.3;3. One-Parameter Gas Solubility in Aqueous Salt Mixtures: Comparison with Experiment;168
5.2.4;4. Salting-In or Salting-Out?;169
5.2.5;5. Discussion and Conclusion;170
5.2.6;Literature Cited;171
5.3;The Solubility of Binary Mixed Gases by the Fluctuation Theory;172
5.3.1;1. Introduction;172
5.3.2;2. Theory;172
5.3.3;3. Calculation Procedure;174
5.3.4;4. Results and Discussion;174
5.3.5;Literature Cited;175
5.4;Prediction of gas solubility in binary polymer + solvent mixtures;177
5.4.1;1. Introduction;177
5.4.2;2. Theory;178
5.4.3;3. The solubility of gases in binary polymer 1 solvent mixtures;179
5.4.4;4. Discussion;179
5.4.5;5. Conclusion;182
5.4.6;Appendix A;182
5.4.7;Appendix B;183
5.4.8;References;183
5.5;Ideal Multicomponent Liquid Solution as a Mixed Solvent;184
5.5.1;Introduction;184
5.5.2;Theory and Formulas;185
5.5.3;Applications;187
5.5.4;Conclusion;190
5.5.5;Acknowledgment;190
5.5.6;Literature Cited;191
5.6;Solubility and local structure around a dilute solute molecule in an aqueous solvent: From gases to biomolecules;192
5.6.1;1. Introduction;192
5.6.2;2. The application of the Kirkwood–Buff fluctuation theory of solutions to the activity coefficients in ternary and multicomponent solutions;193
5.6.3;3. Solubility of a protein in aqueous solutions;194
5.6.4;4. Solubility of a gas in aqueous salt solutions;195
5.6.5;5. The use of experimental solubility data to analyze hydration phenomena;196
5.6.6;6. Discussion and conclusion;198
5.6.7;Appendix A;199
5.6.8;References;199
6;Chapter 4 Solubility of pharmaceuticals and environmentally important compounds;201
6.1;Solubility of drugs in aqueous solutions Part 1. Ideal mixed solvent approximation;202
6.1.1;1. Introduction;202
6.1.2;2. Theory;203
6.1.3;3. Results and discussion;207
6.1.4;4. Conclusion;208
6.1.5;Acknowledgements;209
6.1.6;References;209
6.2;Solubility of drugs in aqueous solutions Part 2: Binary nonideal mixed solvent;211
6.2.1;1. Introduction;211
6.2.2;2. Theory and formulas;212
6.2.3;3. Calculations and results;214
6.2.4;4. Discussion;216
6.2.5;5. Conclusion;217
6.2.6;Appendix A;217
6.3;Solubility of drugs in aqueous solutions Part 3: Multicomponent mixed solvent;220
6.3.1;1. Introduction;220
6.3.2;2. Solubility of drugs in a multicomponent mixed solvent;222
6.3.3;3. Comparison with experiment;223
6.3.4;4. Discussion and conclusion;225
6.3.5;Acknowledgements;225
6.3.6;References;225
6.4;Solubility of drugs in aqueous solutions Part 4. Drug solubility by the dilute approximation;227
6.4.1;1. Introduction;227
6.4.2;2. Theory;228
6.4.3;3. Application of Eq. (28) to the solubility of drugs in a binary solvent;232
6.4.4;4. Discussion and conclusion;234
6.4.5;References;235
6.5;Solubility of drugs in aqueous solutions Part 5. Thermodynamic consistency test for the solubility data;236
6.5.1;1. Introduction;236
6.5.2;2. General relations for multicomponent mixtures;237
6.5.3;3. Thermodynamic consistency test regarding the solubility of drugs in binary aqueous mixed solvents;237
6.5.4;4. Numerical estimations;238
6.5.5;5. The use of the solubilities of anthracene in 1-propanol-2-propanol and anthracene in n-hexane–cyclohexane mixtures for the determination of the Dmax value;239
6.6;Solubility of Hydrophobic Organic Pollutants in Binary and Multicomponent Aqueous Solvents;244
6.6.1;Introduction;244
6.6.2;Experimental Data;247
6.6.3;Results of the Calculations;248
6.6.4;Discussion;249
6.6.5;Appendix;251
6.6.6;Literature Cited;254
7;Chapter 5 Aqueous solutions of biomolecules;255
7.1;A protein molecule in an aqueous mixed solvent: Fluctuation theory outlook;256
7.1.1;INTRODUCTION;256
7.1.2;THE KIRKWOOD-BUFF INTEGRALS IN TERNARY MIXTURES;257
7.1.3;THE EXCESS AND DEFICIT NUMBERS OF MOLECULES OF WATER AND COSOLVENT AROUND A PROTEIN MOLECULE;258
7.1.4;NUMERICAL ESTIMATIONS FOR VARIOUS SYSTEMS;258
7.1.5;RESULTS AND DISCUSSION;259
7.1.6;CONCLUSION;262
7.2;Relationship between preferential interaction of a protein in an aqueous mixed solvent and its solubility;265
7.2.1;1. Introduction;265
7.2.2;2. Theoretical part;266
7.2.3;3. Calculations;268
7.2.4;4. Discussion;269
7.2.5;5. Conclusion;270
7.2.6;References;270
7.3;A Protein Molecule in a Mixed Solvent: The Preferential Binding Parameter via the Kirkwood-Buff Theory;272
7.3.1;INTRODUCTION;272
7.3.2;IDEAL TERNARY MIXTURE;273
7.3.3;DISCUSSION;273
7.3.4;REFERENCES;274
7.4;Preferential hydration and solubility of proteins in aqueous solutions of polyethylene glycol;276
7.4.1;1. Introduction;276
7.4.2;2. Theoretical part;278
7.4.3;3. Numerical estimations for various water/protein/PEG systems;280
7.4.4;References;286
7.5;Effect of salts and organic additives on the solubility of proteins in aqueous solutions;287
7.5.1;1. Introduction;287
7.5.2;2. The aqueous protein solubility and the osmotic second virial coefficient;288
7.5.3;3. The aqueous protein solubility and the preferential binding parameter;289
7.5.4;4. Discussion;291
7.5.5;References;292
7.6;Local Composition in the Vicinity of a Protein Molecule in an Aqueous Mixed Solvent;294
7.6.1;1. Introduction;294
7.6.2;2. Theory;295
7.6.3;3. Calculation of ¢n12 (¢n32) and Their Dependence on Various Factors;296
7.6.4;4. Calculation of J21 (J23) and the Excesses (or Deficits) ¢n12 (¢n32) Using Various Theories;298
7.6.5;5. Discussion and Conclusion;300
7.7;Local Composition in Solvent + Polymer or Biopolymer Systems;303
7.7.1;1. Introduction;303
7.7.2;2. Theoretical Background;303
7.7.3;3. Excesses (or Deficits) in Various Solvent-Polymer (Protein) Mixtures;305
7.7.4;4. Discussion and Conclusion;308
7.7.5;References and Notes;312
7.8;Various Contributions to the Osmotic Second Virial Coefficient in Protein-Water-Cosolvent Solutions;313
7.8.1;1. Introduction;313
7.8.2;2. Theory;314
7.8.3;3. Numerical Estimations for Various Systems;315
7.8.4;4. Results;317
7.8.5;5. Discussion and Conclusion;317
7.8.6;References and Notes;318
8;Chapter 6 Water and dilute aqueous solutions;320
8.1;Simple Computer Experiments with Ordinary Ice;321
8.1.1;1. Introduction;321
8.1.2;2. Methodology and Program Code;321
8.1.3;3. Calculations;322
8.1.4;4. Results of Computations;323
8.1.5;5. Discussion of Results and Comparison with Available Models and Experimental Information;324
8.1.6;6. Conclusion;324
8.2;Cooperativity in Ordinary Ice and Breaking of Hydrogen Bonds;326
8.2.1;1. Introduction;326
8.2.2;2. H-Bond Energy Between Two Water Molecules with Various Numbers of Additionally Bound Water Molecules;327
8.2.3;3. Algorithm, Code, and Calculations;329
8.2.4;4. Results and Discussion;330
8.2.5;5. Conclusion;331
8.2.6;Appendix A;332
8.2.7;References and Notes;332
8.3;The Structure of Dilute Clusters of Methane and Water by ab Initio Quantum Mechanical Calculations;334
8.3.1;1. Introduction;334
8.3.2;2. Methodology of Calculations;336
8.3.3;3. Results of the ab Initio Computations;336
8.3.4;4. Discussion;338
8.3.5;5. Conclusion;339
8.3.6;References and Notes;339
8.4;Treatment of Dilute Clusters of Methanol and Water by ab Initio Quantum Mechanical Calculations;341
8.4.1;1. Introduction;341
8.4.2;2. Nanometer Features of Water and Methanol and their Mixture;342
8.4.3;3. Methodology of Calculations;344
8.4.4;4. Results of the ab Initio Computations;344
8.4.5;5. Discussion;346
8.4.6;6. Conclusions;348
8.4.7;References and Notes;348