Solubilization in Surfactant Aggregates

Cover......Page 1
Half Title......Page 2
Series Page......Page 3
Title Page......Page 6
Copyright Page......Page 7
Dedication......Page 8
Preface......Page 10
Table of Contents......Page 12
Contributors......Page 16
Part I: Overview......Page 20
  Synopsis......Page 22
  I. Introduction......Page 23
  II. Historical Background......Page 24
  III. Typical Behavior of Ionic Micelle/Solubilizate Systems......Page 26
  IV. Representation of Solubilization Results......Page 28
  V. The Solubilization Isotherm......Page 31
  VI. Activity Coefficient Isotherms......Page 36
  VIII. Outline of Book......Page 39
  References......Page 40
Part II: Solubilization in Micelles......Page 52
  Synopsis......Page 54
  II. Early Studies......Page 55
  III. Solubilization of Gases and Low Molecular Weight Vapors......Page 57
  IV. Solubilization of High Molecular Weight Vapors......Page 72
  References......Page 76
 3. Thermodynamics of Solubilization of Polar Additives in Micellar Solutions......Page 78
  I. Introduction......Page 79
  II. Thermodynamic Approach......Page 81
   A. Micellization......Page 86
   B. Additive Distribution......Page 87
   C. Micellization Shift Contribution......Page 89
   D. Fits of Experimental Data......Page 91
  III. Equations......Page 93
   A. Volume......Page 94
   B. Enthalpy......Page 95
   C. Heat Capacity......Page 98
   D. Compressibility......Page 99
  IV. Peculiarities in the Thermodynamic Properties......Page 101
   A. Additive Alkyl Chain Length......Page 109
   B. Surfactant Alkyl Chain Length......Page 111
   C. Polar Head of the Surfactant......Page 113
   D. Polar Head of the Additive......Page 114
  VI. Standard Free Energy, Enthalpy, and Entropy of Transfer from the Aqueous to the Micellar Phases......Page 115
   A. Primary Alcohols......Page 117
   B. Secondary Alcohols......Page 120
   C. Fluorinated Alcohols......Page 122
   E. Benzene and Phenol......Page 123
  VII. Postmicellar Transitions......Page 124
   Symbols......Page 126
   References......Page 130
  Synopsis......Page 134
  I. Introduction......Page 135
  II. The Ionic Micelle......Page 137
  III. Thermodynamics of Micellization......Page 139
   A. The Hydrophobic Effect......Page 140
   B. Chain Conformation Free Energy......Page 141
   C. Interactions Between Ionic Headgroups and Surrounding Water Molecules......Page 143
   D. The Interfacial Energy......Page 145
   E. Electrostatic Interactions......Page 148
  IV. Properties of Ionic Amphiphile-Water Systems Calculated from the PBCM Model......Page 149
  V. Solubilization Properties Calculated by the PBCM Model......Page 151
   A. Solubilization of Pentanol in SDS Micelles......Page 152
   B. The Two-Region Model......Page 155
  VI. Present Studies......Page 156
  References......Page 158
  Synopsis......Page 162
  I. Introduction......Page 163
  II. Microscopic Investigation for the State of Solubilizates in Mixed Micelles......Page 164
  III. Thermodynamic Studies of the Micelle-Water Distribution Equilibria of Solubilizates in Mixed Micellar Systems......Page 165
   A. Review of Relevant Studies......Page 167
   B. Thermodynamic Equations Expressing Synergistic Solubilization Effects in Mixed Micelles......Page 173
  Symbols......Page 203
  References......Page 204
 6. Solubilization in Amphiphilic Copolymer Solutions......Page 210
  I. Introduction......Page 211
   A. PEO-PPO Block Copolymers......Page 212
   B. PS-PEO Block Copolymers......Page 216
   C. Ionic Block Copolymers......Page 217
  III. A Survey of Solubilization Studies in Copolymer Solutions......Page 219
  IV. Effect of Polymer Type and Structure on Solubilization......Page 220
  V. Solute Effects on Solubilization......Page 225
  VI. Temperature Effects on Solubilization......Page 227
  VII. Effect of Solution Ionic Strength and pH on Solubilization......Page 231
  VIII. Modeling of Solubilization in Block Copolymer Micelles......Page 235
   A. Phenomenological Theory of Solubilization in Block Copolymer Micelles......Page 236
   B. Self-Consistent Mean-Field Lattice Theory of Solubilization in Block Copolymer Micelles......Page 239
   C. Lattice Theory for Monomers with Internal Degrees of Freedom......Page 245
   D. Effect of Copolymer Molecular Weight on Solubilization......Page 248
  IX. Conclusions......Page 250
  References......Page 252
  Synopsis......Page 256
  I. Introduction......Page 257
   A. Passive Drop-On-Fiber......Page 259
   A. Insoluble Oil/Aqueous Micellar Surfactant......Page 260
   B. Soluble Oil/Aqueous Micellar Surfactant......Page 271
   C. Solubilization in Mixed Surfactant Systems......Page 273
   D. Solubilization in Binary Surfactant Mixtures......Page 274
   E. Differential Solubilization Effects......Page 282
   F. Interfacial Liquid Crystal Formation......Page 287
  IV. Summary......Page 289
  References......Page 291
Part III: Solubilization in Nonmicellar Surfactant Aggregates......Page 294
  Synopsis......Page 296
   B. Background......Page 297
  II. Studies of Adsolubilization......Page 302
   A. Characterization of Admicelles......Page 303
   B. Separation Processes......Page 307
   C. Thin-Film Formation......Page 310
   D. Studies of Adsolubilization in Admicellar Catalysis......Page 311
  III. Summary and Conclusions......Page 312
  References......Page 313
  Synopsis......Page 316
   A. Brief Outline of Fluorescence Parameters Used in Solubilization Studies......Page 317
   B. Definitions of Partition Coefficients......Page 318
   A. Partition Coefficients for Fluorophores......Page 320
   B. Partition Coefficients for Fluorescence Quenchers......Page 326
   C. Partition Coefficients for Additives that are not Quenchers but Modify a Fluorescence Characteristic......Page 330
   A. Location of the Fluorophore or the Quencher Inside the Aggregates......Page 334
   B. Dependence of the Partition Coefficient on the Solute Concentration......Page 340
   C. Changes in the Properties of the Aggregates Elicited by the Additive......Page 342
  References......Page 346
 10. Solubilization of Organic Compounds by Vesicles......Page 352
  I. Introduction......Page 353
   B. Basic Precautions for Vesicle Preparation......Page 354
   C. Typical Preparation Methods for Vesicles......Page 356
  III. Solubilization of Amphoteric Compounds by Liposomes......Page 360
   B. Incorporation of a Nonionic Surfactant into a Bilayer......Page 361
   C. Surface Charge Density of Liposomes with Nonionic Surfactants......Page 363
  IV. Solubilization of Lipophilic Compounds by Vesicles......Page 365
   A. Incorporation of a Lipophilic Compound into a Bilayer Membrane......Page 366
   B. Solubilization Sites of Lipophilic Compounds in a Bilayer Membrane......Page 368
  V. Solubilization of an Alcoholic Compound by Vesicles......Page 371
   A. Semiequilibrium Dialysis (SED) Method for Vesicle Solubilization......Page 373
   C. Activity Coefficients of the Surfactant and PEA......Page 375
   D. Competition for Sites at the Aggregate Surface......Page 377
  References......Page 380
Part IV: Methods of Measuring Solubilization......Page 384
 11. Solubilization, as Studied by Nuclear Spin Relaxation and NMR-Based Self-Diffusion Techniques......Page 386
  I. Introduction......Page 387
  II. Molecular Dynamics and Order in Micelles, as Derived from Nuclear Spin Relaxation......Page 388
   B. Determining the Location of Solubilizates, from 2D Cross-Relaxation (NOESY) Experiments......Page 389
   C. "Micellar Viscosity" from Spin Relaxation of a Solubilized Probe......Page 390
   B. Partition Equilibria, as Studied by Self-Diffusion Measurements......Page 391
   C. NMR Self-Diffusion Measurements through the Pulsed Gradientspin-Echo Experiment......Page 393
   D. Studies of Solubilization Equilibria by FT-PGSE NMR Self-Diffusion Measurements......Page 395
   E. Final Comments......Page 398
  References......Page 399
 12. The Partitioning of Neutral Solutes Between Micelles and Water as Deduced from Critical Micelle Concentration Determinations......Page 402
  I. Introduction......Page 403
  II. Calculations of Partition Coefficients According to Various Chemical Models......Page 404
   A. Experimental Techniques......Page 417
   B. Comparison of Partition Coefficients as Deduced from Various Experimental Techniques......Page 419
   A. Computed literature CMC-Based Partition Coefficients......Page 426
   B. Tentative Group-Contribution Approach to Micellar Solubilization......Page 431
  V. Solutes as Cosolvents in Aqueous Surfactant Solutions......Page 435
  VI. Conclusions......Page 437
  Appendix A......Page 439
  References......Page 443
  Synopsis......Page 448
  I. Solute Vapor Pressure Apparatus......Page 449
  II. Vapor Pressure Data Treatment......Page 452
  III. Solubilization of Volatile Aromatics and Halocarbons......Page 455
  IV. Solubilization of Cyclohexane and Hexane......Page 461
  V. Solubilization in Mixed Micelles......Page 464
  VI. Thermodynamics of Solubilization......Page 467
  VII. Conclusion......Page 471
  References......Page 472
 14. Comparison of Experimental Methods for the Determination of the Partition Coefficients of n-Alcohols in SDS and DTAB Micelles......Page 474
   A. General Background and Overview......Page 475
   B. The Mass Action and Pseudophase Models of Micelle Formation: Interpretation of Solubilization......Page 476
   C. The Gibbs Energy of Transfer of Solubilizates from Water to Micellar Phases......Page 478
   D. Solubilization and Mixed Micelle Formation......Page 479
  II. NMR Spectroscopy of Micellar and Mixed Micellar Solutions: The NMR Paramagnetic Relaxation Enhancement Method for Determining p-Values......Page 481
   A. Overview......Page 485
   B. Total Solubility Method......Page 486
   C. Krafft Point Method......Page 487
   E. Electron Spin-Echo Modulation Method......Page 488
  IV. Comparison of K[x] Values......Page 489
  V. Discussion of the NMR Paramagnetic Relaxation Enhancement Method......Page 497
  VI. Conclusions......Page 502
  Symbols......Page 504
  References......Page 506
Part V: Applications of Solubilization......Page 510
  Synopsis......Page 512
  I. The Challenge of the Detergent Industry......Page 513
   A. Roll-Up......Page 514
   B. Solubilization......Page 515
   A. General Phase Behavior of Ethoxylated Fatty Alcohols......Page 516
   B. Systems Based on Anionic Surfactants......Page 530
  IV. Solubilization in Nonaqueous Media......Page 531
   A. Hansen's Solubility Parameters......Page 532
   B. Solvent Molar Volume......Page 533
  References......Page 534
 16. Solubilization in Micellar Separations......Page 536
  II. Structure and Properties of Micelles......Page 537
   A. Normal Micelles......Page 539
  III. Solubilization in Micellar Liquid Chromatography......Page 540
   A. Partitioning Theory......Page 542
   B. Electrostatic and Hydrophobic Interactions......Page 543
   D. Micellar Selectivity in MLC......Page 544
   E. Selectivity Due to Other Parameters......Page 545
   G. Applications Using Micellar Chromatography......Page 546
  IV. Electrokinetic Chromatography Based on Micellar Solubilization......Page 549
   A. Theory of Separation......Page 550
   C. Applications of MEKC......Page 553
  References......Page 555
Index......Page 560