Micelles: Theoretical and Applied AspectsAlmost thirty years ago the author began his studies in colloid chemistry at the laboratory of Professor Ryohei Matuura of Kyushu University. His graduate thesis was on the elimination of radioactive species from aqueous solution by foam fractionation. He has, except for a few years of absence, been at the university ever since, and many students have contributed to his subsequent work on micelle formation and related phenomena. Nearly sixty papers have been published thus far. Recently, in search of a new orientation, he decided to assemble his findings and publish them in book form for review and critique. In addition, his use of the mass action model of micelle has received much criticism, especially since the introduction of the phase separation model. Many recent reports have postulated a role for Laplace pressure in micellization. Although such a hypothesis would provide an easy explanation for micelle formation, it neglects the fact that an interfacial tension exists between two macroscopic phases. The present book cautions against too ready an acceptance of the phase separation model of micelle formation. Most references cited in this book are studies introduced in small group meetings of colloid chemists, the participants at which included Professors M. Saito, M. Manabe, S. Kaneshina, S. Miyagishi, A. Yamauchi, H. Akisada, H. Matuo, M. Sakai, and Drs. O. Shibata, N. Nishikido, and Y. Murata, to whom the author wishes to express his gratitude for useful discussions. |
Contents
Introduction | 1 |
References | 5 |
SurfaceActive Agents | 7 |
22 HydrophileLipophile Balance | 8 |
23 Purification of Surfactants | 15 |
References | 23 |
Dissolution of Amphiphiles in Water | 25 |
32 Thermodynamic Parameters of Mixing | 26 |
73 Potential Energy Due to Electrical Double Layers | 140 |
74 Potential Energy Due to the van der Waals London Force | 143 |
75 Total Potential Energy and the SchulzeHardy Rule | 145 |
References | 148 |
Adsorption of Surfactants | 149 |
83 Thermodynamics of Adsorption | 156 |
84 Adsorption from Surfactant Solutions | 163 |
References | 164 |
33 Lattice Theory of Solution | 28 |
34 Solubility | 33 |
35 Solubility of Weak Acids and Dissociation Constant | 35 |
References | 40 |
Micelle Formation | 41 |
42 Shape and Structure of Micelles | 44 |
43 Critical Micelle Concentration | 47 |
44 Thermodynamics of Micelle Formation | 56 |
45 Counterion Binding to Micelles | 61 |
46 Size Distribution and Morphologic Alterations | 66 |
47 Kinetics of Micelle Formation | 74 |
48 Temperature and Pressure Effects on Micelles | 83 |
References | 90 |
Application of the Thermodynamics of Small Systems to Micellar Solutions | 97 |
53 Small Systems in Solution | 99 |
54 Size Distribution of Micelles | 103 |
55 Thermodynamic Functions of Micelle Formation | 107 |
56 Micellar Parameters Based on Turbidity Data | 109 |
References | 112 |
Micelle Temperature Range MTR or Krafft Point | 113 |
62 Krafft Point and Related Technical Terms | 114 |
63 The Physicochemical Meaning of the MTR | 115 |
64 MTR Change of Homologous Surfactants | 124 |
65 MTR Change with Additives | 125 |
References | 128 |
Stability of Colloidal Particles | 131 |
72 The Diffuse Double Layer | 136 |
Solubilization | 167 |
92 Phase Rule of Solubilization | 168 |
93 Thermodynamics of Solubilization | 169 |
95 Factors Influencing Solubilization | 177 |
96 Location of Solubilizates in Micelles | 179 |
References | 180 |
Mixed Micelle Formation | 183 |
102 TwoComponent Surfactant Systems | 185 |
103 Partially Miscible Micelles and Demicellization | 189 |
104 Multicomponent Surfactant Systems | 191 |
References | 193 |
Micellar Catalysis | 195 |
112 Characteristics of Enzymatic Reactions | 197 |
113 MicelleCatalyzed Reactions | 200 |
114 Inhibition in Micellar Solutions | 206 |
References | 208 |
Photochemistry in Micellar Systems | 211 |
123 Determination of Micellar Aggregation Number | 213 |
124 Kinetics of Redox Reactions | 222 |
References | 230 |
Interactions between Amphiphiles and Polymers | 233 |
132 Analytic Models for Binding | 234 |
133 Binding of Amphiphiles to Synthetic Polymers | 239 |
134 Binding of Amphiphiles to Proteins | 243 |
246 | |
249 | |
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Common terms and phrases
Academic Press acid activity coefficient adsorption alkyl American Chemical Society amphiphiles anionic association constant average number becomes binding C₁ carbon number charge Chem chemical potential chemical species CMC values Colloid Interface Sci Colloid Polym component counterions curve decrease determined dissociation dm³ dodecanol dodecyl sulfate equilibrium Faraday Soc Figure following equation free energy function Grätzel HLB values hydrocarbon hydrophilic hydrophobic increase interaction interfacial tension ionic surfactants K₁ kinetics Krafft point layer Matuura micellar aggregation number micellar surface micelle formation mixed micelle mol dm-3 mole fraction monomer monomeric Moroi MPTH Mukerjee n₁ nonionic nonionic surfactants obtained parameters permission of Academic phase rule Phys Plenum Press Poisson distribution Polym pressure rate constant reactants reaction Reproduced with permission Shinoda small systems sodium sodium dodecyl sulfate solubility solvent surfactant ions surfactant molecules surfactant solution temperature thermodynamic total surfactant concentration variables
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Page 247 - AL Shapiro, E. Vinuela and JV Maizel, Jr., Biochem. Biophys. Res. Commun., 28, 815 (1967).