Surface and Colloid Science

By: Egon Matijevic (Editor)

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Hardcover | 31 May 2001

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428 Pages

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The three sections of this volume deal with topics of broad interest.
The first deals with cetyl alcohol and is a most comprehensive study of this essential ingredient in the cosmetic and pharmaceutical industry, with an explanation of its functionality. The second is a most comprehensive, up-to-date review of acid/base interactions of a variety of materials, including small molecules, proteins and polyelectrolytes. The third section describes the combined radiochemical and electrochemical methods in the evaluation of the properties of solids in contact with solutions.

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Published: 25th October 2012

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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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Surface and Colloid Science

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