| Physical Chemistry of Cetyl Alcohol: Occurrence and Function of Liquid Crystals in O/W Creams | |
| Introduction | p. 1 |
| Cetyl Alcohol | p. 2 |
| Description of Cetyl Alcohol | p. 2 |
| Short History of Cetyl Alcohol | p. 2 |
| Definitions in Official Books | p. 4 |
| Physical Properties of Cetyl Alcohols | p. 7 |
| Polymorphism of Higher Alcohols | p. 7 |
| Crystal Structure of Higher Alcohols | p. 12 |
| Melting Point and Transition Point of Higher Alcohols | p. 12 |
| Transition Point and Infrared Absorption | p. 14 |
| Specific Interaction between 1-Hexadecanol and 1-Octadecanol | p. 20 |
| Composition of Commercially Available Cetyl Alcohol | p. 20 |
| Transition Point of 1-Hexadecanol | p. 20 |
| Interaction between Higher Alcohols and Water | p. 24 |
| Experimental Facts | p. 24 |
| Formation of Hemihydrate | p. 28 |
| Structure of Hydrated Alcohols | p. 31 |
| Phase Diagram of the 1-Hexadecanol/1-Octadecanol/Water Ternary System | p. 33 |
| Studies on Higher Alcohol/Surfactant/Water Systems | p. 35 |
| The 1-Decanol/Sodium Caprylate/Water System | p. 35 |
| The 1-Hexadecanol/OTAC/Water System | p. 35 |
| Rheology of Ternary Systems Containing 1-Hexadecanol or a Homologous Alcohol | p. 35 |
| Influence of the Amount of 1-Hexadecanol | p. 38 |
| Influence of the Nature of Surfactant and of Higher Alcohol | p. 40 |
| Influence of Alkyl Chain Length of Surfactant | p. 41 |
| Conclusion | p. 43 |
| Nature of Ternary Systems Prepared with Hexaoctadecanols | p. 43 |
| Stability and Rheological Properties of Ternary Systems as a Function of Temperature | p. 44 |
| Variations in External Appearance | p. 44 |
| Variations in Viscosity | p. 45 |
| Microscopic Observation | p. 45 |
| X-Ray Diffraction Analysis | p. 46 |
| Low-Angle X-Ray Diffraction Analysis | p. 50 |
| Thermal Property | p. 51 |
| Polymorphism of Hexaoctadecanol (3:2) and Stability of a Ternary Cream | p. 52 |
| Liquid Crystalline Phases in Hexaoctadecanol (3:2)/Surfactant/Water Ternary Systems | p. 54 |
| Phase Diagram | p. 54 |
| D[subscript 2] Region | p. 56 |
| M Region | p. 60 |
| The Location and State of the D[subscript 2] Phase and M Particles in a Ternary Cream | p. 62 |
| Temperature and the Process Yielding the Liquid Crystalline Phase | p. 65 |
| Temperature of the Formation of the Liquid Crystalline Phase | p. 65 |
| Method of Phase Separation Experiments | p. 65 |
| Results of the Phase Separation Experiment | p. 66 |
| G Phase and S Phase | p. 67 |
| Microscopic Observation | p. 67 |
| X-Ray Diffraction | p. 69 |
| Differential Scanning Calorimetry | p. 69 |
| Temperature at which the LC Phase is Formed | p. 69 |
| In situ Formation of G and M Phases | p. 71 |
| The Function of Liquid Crystalline Phases in O/W Creams | p. 74 |
| Studies on O/W Creams | p. 74 |
| The Difference in the Viscosity-Increasing Effects due to the Nature of Higher Alcohols | p. 77 |
| The Difference in the Viscosity-Increasing Effect due to the Nature of Surfactants | p. 78 |
| The Viscosity Change due to the Ratio of Cetostearyl Alcohol to Surfactant | p. 78 |
| The Effect of Mixing 1-Hexadecanol with 1-Octadecanol | p. 81 |
| Crystallization of Cetyl Alcohol in Cosmetic Creams | p. 83 |
| Internal Structure and Stability of O/W C Creams | p. 84 |
| Internal Structure of O/W Creams | p. 84 |
| A Novel Theory for the Stabilization of O/W Creams | p. 86 |
| Additional References on Cetyl and Homologous Alcohols | p. 88 |
| Appendix 2 | p. 94 |
| References | p. 94 |
| Ionization Processes and Proton Binding in Polyprotic Systems: Small Molecules, Proteins, Interfaces, and Polyelectrolytes | |
| Introduction | p. 99 |
| Experimental Techniques | p. 107 |
| Macroscopic Techniques | p. 107 |
| Definition and Measurement of pH | p. 107 |
| Potentiometric Titration Techniques | p. 110 |
| Other Macroscopic Techniques | p. 114 |
| Spectroscopic Methods | p. 116 |
| Nuclear Magnetic Resonance (NMR) Techniques | p. 116 |
| Optical and Other Spectroscopic Methods | p. 127 |
| Modeling of Ionizable Systems | p. 131 |
| General Considerations | p. 131 |
| Computer Simulation Techniques | p. 134 |
| Simple Electrolyte Solutions | p. 135 |
| Poisson-Boltzmann (PB) and Debye-Huckel (DH) Approximations | p. 136 |
| An Illustrative Example | p. 138 |
| Beyond the Poisson-Boltzmann (PB) Approximation | p. 142 |
| Charged Molecules and Macromolecules in Water | p. 144 |
| Debye-Huckel (DH) and Poisson-Boltzmann (PB) Treatment | p. 144 |
| High-Salt versus Low-Salt Regime | p. 145 |
| Toward Detailed Molecular Models | p. 148 |
| Treatment of Ionization Equilibria | p. 152 |
| Single Ionizable Site | p. 152 |
| Localized versus Delocalized Binding | p. 155 |
| Macroscopic Description | p. 155 |
| Microscopic Description | p. 157 |
| Adding Internal Degrees of Freedom | p. 162 |
| Small Molecules | p. 163 |
| Monoprotic Acids and Bases | p. 163 |
| Equilibrium Constants | p. 163 |
| Titration Behavior | p. 165 |
| Experimental Data | p. 167 |
| Diprotic Acids and Bases | p. 169 |
| Macroscopic Description | p. 169 |
| Microscopic Description | p. 170 |
| Conformational Degrees of Freedom | p. 176 |
| Equivalent Sites | p. 177 |
| Oligoprotic Acids and Bases | p. 178 |
| Macroscopic Description | p. 178 |
| Microscopic Description for Triprotic Acids and Bases | p. 180 |
| Equivalent Sites | p. 184 |
| Linear Molecules | p. 185 |
| Noninteracting Sites | p. 195 |
| Microscopic versus Macroscopic Picture | p. 195 |
| Affinity Distributions | p. 199 |
| Interpretation and Prediction of Ionization Constants | p. 203 |
| Empirical Methods | p. 203 |
| Methods Based on First Principles | p. 206 |
| Proteins | p. 212 |
| The Null Model | p. 213 |
| The Smeared-Out Charge Model | p. 217 |
| The Tanford-Kirkwood Model | p. 222 |
| Solution Techniques of the Ionization Problem | p. 224 |
| Shifts in Ionization Constants | p. 225 |
| Recent Developments in Dielectric Continuum Models | p. 227 |
| General Methodology | p. 227 |
| Case Studies | p. 229 |
| Side Chain Flexibility | p. 237 |
| Beyond Dielectric Continuum Models | p. 238 |
| Protein Folding | p. 245 |
| Polyelectrolytes | p. 246 |
| Mean-Field Models | p. 247 |
| Nearest-Neighbor Chain Interaction Models | p. 249 |
| Discrete Charge Model | p. 252 |
| Mean-Field and Smearing-Out Approximations | p. 255 |
| Chain Flexibility | p. 257 |
| Polyamines | p. 260 |
| Linear Polyamines | p. 260 |
| Branched Polyamines | p. 263 |
| Polycarboxylates | p. 268 |
| Weakly Charged Linear Polycarboxylates | p. 268 |
| Highly Charged Linear Polycarboxylates | p. 272 |
| Humic Acids | p. 274 |
| Ionizable Interfaces | p. 276 |
| Diffuse Layer Model and Its Generalization | p. 276 |
| Nernstian Surface | p. 281 |
| Basic Stern Model | p. 282 |
| Specific Counterion Binding | p. 283 |
| Discrete Charge Model | p. 284 |
| Smearing-Out Approximation | p. 287 |
| 1-pK versus 2-pK Models | p. 288 |
| pK Shifts | p. 290 |
| Latex Particles | p. 291 |
| Ionizable Monolayers | p. 295 |
| Metal Oxide and Metal Hydroxide Particles | p. 297 |
| Experimental Aspects | p. 297 |
| Data Interpretation | p. 299 |
| Goethite | p. 302 |
| Hematite | p. 305 |
| Rutile and Anatase | p. 306 |
| Gibbsite | p. 307 |
| Silica | p. 308 |
| Discussion | p. 309 |
| Electrostatics of Point Charges | p. 312 |
| Planar Interface | p. 313 |
| Sphere | p. 315 |
| Cylinder | p. 318 |
| Further Tools in the Ising Model Analysis | p. 319 |
| Cluster Expansion | p. 319 |
| Other Choices of State Variables | p. 321 |
| Mean-Field Cluster Expansions | p. 322 |
| Mean-Field Treatment of Nonequivalent Sites | p. 323 |
| Square Lattice with Nearest-Neighbor Interactions | p. 324 |
| Affinity Distribution Approach | p. 325 |
| Derivation from Simple Models | p. 326 |
| Experimental Data Inversion | p. 327 |
| References | p. 330 |
| Combined Application of Radiochemical and Electrochemical Methods for the Investigation of Solid/Liquid Interfaces | |
| Introduction | p. 341 |
| On the Significance of Radiotracer Methods in Sorption Studies | p. 341 |
| General Problems of Radioactive Contamination Studies | p. 344 |
| An Overview of Radiotracer Methods | p. 346 |
| Methods Used for the Investigation of Interfacial Phenomena | p. 346 |
| Experimental Techniques: A Historical Survey | p. 347 |
| Recent Progress | p. 353 |
| Methods Used for the Investigation of Radioactive Contamination-Decontamination of Constructional Materials | p. 360 |
| Selected Results | p. 362 |
| Adsorption of Anions and Cations on Polycrystalline Gold | p. 362 |
| Comparative Study of Specific Adsorption of Cl[superscript -], HSO[superscript - subscript 4]/SO[superscript 2- subscript 4] and HSO[superscript - subscript 3]/SO[superscript 2- subscript 3] Ions | p. 362 |
| Electrosorption of Ag and Co Species | p. 373 |
| Accumulation of [superscript 110m]Ag on an Austenitic Stainless Steel | p. 381 |
| Sorption Behavior of Duplex Stainless Steels in HCl and H[subscript 2]SO[subscript 4] Solutions | p. 385 |
| Time and Concentration Dependence of Cl[superscript -] and HSO[superscript - subscript 4]/SO[superscript 2- subscript 4] Accumulations | p. 385 |
| Potential Dependence of Cl[superscript -] and HSO[superscript - subscript 4]/SO[superscript 2- subscript 4] Accumulations | p. 387 |
| Conclusions | p. 390 |
| References | p. 390 |
| Author Index | p. 395 |
| Subject Index | p. 405 |
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