Surfactants and Interfacial Phenomena

• Main Authors: Rosen, Milton J, Kunjappu, Joy T
• Format: eBook Book
• Language: English
• Published: Hoboken, N.J Wiley 2012; John Wiley & Sons; John Wiley & Sons, Incorporated; Wiley-Blackwell
• Edition: 4. Aufl.
• Subjects: Chemistry & Chemical Engineering; General References; Surface active agents; Surface chemistry; Technik; Wissen Chemie

Now in its fourth edition, Surfactants and Interfacial Phenomenaexplains why and how surfactants operate in interfacial processes (such as foaming, wetting, emulsion formation and detergency), and shows the correlations between a surfactant's chemical structure and its action.Updated and revise...

Table of Contents:

• Title Page Preface Table of Contents 1. Characteristic Features of Surfactants 2. Adsorption of Surface-Active Agents at Interfaces: The Electrical Double Layer 3. Micelle Formation by Surfactants 4. Solubilization by Solutions of Surfactants: Micellar Catalysis 5. Reduction of Surface and Interfacial Tension by Surfactants 6. Wetting and its Modification by Surfactants 7. Foaming and Antifoaming by Aqueous Solutions of Surfactants 8. Emulsification by Surfactants 9. Dispersion and Aggregation of Solids in Liquid Media by Surfactants 10. Detergency and its Modification by Surfactants 11. Molecular Interactions and Synergism in Mixtures of Two Surfactants 12. Gemini Surfactants 13. Surfactants in Biology 14. Surfactants in Nanotechnology 15. Surfactants and Molecular Modeling Answers to Selected Problems Index
• B. Interfacial Parameter and Chemical Structural Effects -- III. LIQUID-LIQUID INTERFACIAL TENSION REDUCTION -- IV. DYNAMIC SURFACE TENSION REDUCTION -- A. Dynamic Regions -- B. Apparent Diffusion Coefficients of Surfactants -- REFERENCES -- PROBLEMS -- 6: Wetting and Its Modificationby Surfactants -- I. WETTING EQUILIBRIA -- A. Spreading Wetting -- 1. The Contact Angle -- 2. Measurement of the Contact Angle -- B. Adhesional Wetting -- C. Immersional Wetting -- D. Adsorption and Wetting -- II. MODIFICATION OF WETTING BY SURFACTANTS -- A. General Considerations -- B. Hard Surface (Equilibrium) Wetting -- C. Textile (Nonequilibrium) Wetting -- D. Effect of Additives -- III. SYNERGY IN WETTING BY MIXTURES OF SURFACTANTS -- IV. SUPERSPREADING (SUPERWETTING) -- REFERENCES -- PROBLEMS -- 7: Foaming and Antifoaming by Aqueous Solutions of Surfactants -- I. THEORIES OF FILM ELASTICITY -- II. FACTORS DETERMINING FOAM PERSISTENCE -- A. Drainage of Liquid in the Lamellae -- B. Diffusion of Gas through the Lamellae -- C. Surface Viscosity -- D. The Existence and Thickness of the Electrical Double Layer -- III. THE RELATION OF SURFACTANT CHEMICAL STRUCTURE TO FOAMING IN AQUEOUS SOLUTION -- A. Efficiency as a Foaming Agent -- B. Effectiveness as a Foaming Agent -- C. Low-Foaming Surfactants -- IV. FOAM-STABILIZING ORGANIC ADDITIVES -- V. ANTIFOAMING -- VI. FOAMING OF AQUEOUS DISPERSIONS OF FINELY DIVIDED SOLIDS -- VII. FOAMING AND ANTIFOAMING IN ORGANIC MEDIA -- REFERENCES -- PROBLEMS -- 8: Emulsification by Surfactants -- I. MACROEMULSIONS -- A. Formation -- B. Factors Determining Stability -- 1. Physical Nature of the Interfacial Film -- 2. Existence of an Electrical or Steric Barrier to Coalescence on the Dispersed Droplets -- 3. Viscosity of the Continuous Phase -- 4. Size Distribution of Droplets -- 5. Phase Volume Ratio -- 6. Temperature -- C. Inversion
• III. MICELLAR AGGREGATION NUMBERS -- IV. FACTORS AFFECTING THE VALUE OF THE CMC IN AQUEOUS MEDIA -- A. Structure of the Surfactant -- 1. The Hydrophobic Group -- 2. The Hydrophilic Group -- 3. The Counterion in Ionic Surfactants -- Degree of Binding to the Micelle -- 4. Empirical Equations -- B. Electrolyte -- C. Organic Additives -- 1. Class I Materials -- 2. Class II Materials -- D. The Presence of a Second Liquid Phase -- E. Temperature -- V. MICELLIZATION IN AQUEOUS SOLUTION AND ADSORPTION AT THE AQUEOUS SOLUTION-AIR OR AQUEOUS SOLUTION-HYDROCARBON INTERFACE -- A. The CMC/C20 Ratio -- VI. CMCS IN NONAQUEOUS MEDIA -- VII. EQUATIONS FOR THE CMC BASED ON THEORETICAL CONSIDERATIONS -- VIII. THERMODYNAMIC PARAMETERS OF MICELLIZATION -- IX. MIXED MICELLE FORMATION IN MIXTURES OF TWO SURFACTANTS -- REFERENCES -- PROBLEMS -- 4: Solubilization by Solutions of Surfactants: Micellar Catalysis -- I. SOLUBILIZATION IN AQUEOUS MEDIA -- A. Locus of Solubilization -- B. Factors Determining the Extent of Solubilization -- 1. Structure of the Surfactant -- 2. Structure of the Solubilizate -- 3. Effect of Electrolyte -- 4. Effect of Monomeric Organic Additives -- 5. Effect of Polymeric Organic Additives -- 6. Mixed Anionic-Nonionic Micelles -- 7. Effect of Temperature -- 8. Hydrotropy -- C. Rate of Solubilization -- II. SOLUBILIZATION IN NONAQUEOUS SOLVENTS -- A. Secondary Solubilization -- III. SOME EFFECTS OF SOLUBILIZATION -- A. Effect of Solubilization on Micellar Structure -- B. Change in the CPs of Aqueous Solutions of Nonionic Surfactants -- C. Reduction of the CMC -- D. Miscellaneous Effects of Solubilization -- IV. MICELLAR CATALYSIS -- REFERENCES -- PROBLEMS -- 5: Reduction of Surface and Interfacial Tension by Surfactants -- I. EFFICIENCY IN SURFACE TENSION REDUCTION -- II. EFFECTIVENESS IN SURFACE TENSION REDUCTION -- A. The Krafft Point
• A. Effect of Soil and Substrate
• D. Multiple Emulsions -- E. Theories of Emulsion Type -- 1. Qualitative Theories -- 2. Kinetic Theory of Macroemulsion Type -- II. MICROEMULSIONS -- III. NANOEMULSIONS -- IV. SELECTION OF SURFACTANTS AS EMULSIFYING AGENTS -- A. The Hydrophile-Lipophile Balance (HLB) Method -- B. The PIT Method -- C. The Hydrophilic Lipophilic Deviation (HLD) Method -- V. DEMULSIFICATION -- REFERENCES -- PROBLEMS -- 9: Dispersion and Aggregation of Solids in Liquid Media by Surfactants -- I. INTERPARTICLE FORCES -- A. Soft (Electrostatic) and van der Waals Forces: Derjaguin and Landau and Verwey and Overbeek (DLVO) Theory -- 1. Limitations of the DLVO Theory -- B. Steric Forces -- II. ROLE OF THE SURFACTANT IN THE DISPERSION PROCESS -- A. Wetting of the Powder -- B. Deaggregation of Fragmentation of Particle Clusters -- C. Prevention of Reaggregation -- III. COAGULATION OR FLOCCULATION OF DISPERSED SOLIDS BY SURFACTANTS -- A. Neutralization or Reduction of the Potential at the Stern Layer of the Dispersed Particles -- B. Bridging -- C. Reversible Flocculation -- IV. THE RELATION OF SURFACTANT CHEMICAL STRUCTURE TO DISPERSING PROPERTIES -- A. Aqueous Dispersions -- B. Nonaqueous Dispersions -- C. Design of New Dispersants -- REFERENCES -- PROBLEMS -- 10: Detergency and Its Modification by Surfactants -- I. MECHANISMS OF THE CLEANING PROCESS -- A. Removal of Soil from Substrate -- 1. Removal of Liquid Soil -- 2. Removal of Solid Soil -- B. Suspension of the Soil in the Bath and Prevention of Redeposition -- 1. Solid Particulate Soil: Formation of Electrical and Steric Barriers -- Soil Release Agents -- 2. Liquid Oily Soil -- C. Skin Irritation (see Chapter 1, Section IIIB) -- D. Dry Cleaning -- II. EFFECT OF WATER HARDNESS -- A. Builders -- B. LSDAs -- III. FABRIC SOFTENERS -- IV. THE RELATION OF THE CHEMICAL STRUCTURE OF THE SURFACTANT TO ITS DETERGENCY
• Intro -- SURFACTANTS AND INTERFACIAL PHENOMENA -- CONTENTS -- PREFACE -- 1: Characteristic Featuresof Surfactants -- I. CONDITIONS UNDER WHICH INTERFACIAL PHENOMENA AND SURFACTANTS BECOME SIGNIFICANT -- II. GENERAL STRUCTURAL FEATURES AND BEHAVIOR OF SURFACTANTS -- A. General Use of Charge Types -- B. General Effects of the Nature of the Hydrophobic Group -- 1. Length of the Hydrophobic Group -- 2. Branching, Unsaturation -- 3. Aromatic Nucleus -- 4. Polyoxypropylene or Polyoxyethylene (POE) Units -- 5. Perfluoroalkyl or Polysiloxane Group -- III. ENVIRONMENTAL EFFECTS OF SURFACTANTS -- A. Surfactant Biodegradab -- B. Surfactant Toxicity -- Skin Irritation -- IV. CHARACTERISTIC FEATURES AND USES OF COMMERCIALLY AVAILABLE SURFACTANTS -- A. Anionics -- 1. Carboxylic Acid Salts -- 2. Sulfonic Acid Salts -- 3. Sulfuric Acid Ester Salts -- 4. Phosphoric and Polyphosphoric Acid Esters -- 5. Fluorinated Anionics -- B. Cationics -- 1. Long-Chain Amines and Their Salts -- 2. Acylated Diamines and Polyamines and Their Salts -- 3. Quaternary Ammonium Salts -- 4. Polyoxyethylenated Long-Chain Amines -- 5. Quaternized POE Long-Chain Amines -- 6. Amine Oxides -- C. Nonionics -- 1. Polyoxyethylenated Alkylphenols, Alkylphenol "Ethoxylates" -- 2. Polyoxyethylenated Straight-Chain Alcohols -- 3. Polyoxyethylenated Polyoxypropylene Glycols -- 4. Polyoxyethylenated Mercaptans -- 5. Long-Chain Carboxylic Acid Esters -- 6. Alkanolamine "Condensates," Alkanolamides -- 7. Tertiary Acetylenic Glycols and Their "Ethoxylates" -- 8. Polyoxyethylenated Silicones -- 9. N-Alkylpyrrolid(in)ones -- 10. Alkylpolyglycosides -- D. Zwitterionics -- 1. pH-Sensitive Zwitterionics -- 2. pH-Insensitive Zwitterionics -- E. Newer Surfactants Based Upon Renewable Raw Materials -- 1. α-Sulfofatty Acid Methyl Esters (SME) -- 2. Acylated Aminoacids -- 3. Nopol Alkoxylates
• V. SOME USEFUL GENERALIZATIONS -- VI. ELECTRONIC SEARCHING OF THE SURFACTANT LITERATURE -- REFERENCES -- PROBLEMS -- 2: Adsorption of Surface-Active Agents at Interfaces: The Electrical Double Layer -- I. THE ELECTRICAL DOUBLE LAYER -- II. ADSORPTION AT THE SOLID-LIQUID INTERFACE -- A. Mechanisms of Adsorption and Aggregation -- B. Adsorption Isotherms -- 1. The Langmuir Adsorption Isotherm -- C. Adsorption from Aqueous Solution onto Adsorbents with Strongly Charged Sites -- 1. Ionic Surfactants -- 2. Nonionic Surfactants -- 3. pH Change -- 4. Ionic Strength -- 5. Temperature -- D. Adsorption from Aqueous Solution onto Nonpolar, Hydrophobic Adsorbents -- E. Adsorption from Aqueous Solution onto Polar Adsorbents without Strongly Charged Sites -- F. Effects of Adsorption from Aqueous Solution on the Surface Properties of the Solid Adsorbent -- 1. Substrates with Strongly Charged Sites -- 2. Nonpolar Adsorbents -- G. Adsorption from Nonaqueous Solution -- H. Determination of the Specific Surface Areas of Solids -- III. ADSORPTION AT THE LIQUID-GAS (L/G) AND LIQUID-LIQUID (L/L) INTERFACES -- A. The Gibbs Adsorption Equation -- B. Calculation of Surface Concentrations and Area Per Molecule at the Interface by Use of the Gibbs Equation -- C. Effectiveness of Adsorption at the L/G and L/L Interfaces -- D. The Szyszkowski, Langmuir, and Frumkin Equations -- E. Efficiency of Adsorption at the L/G and L/L Interfaces -- F. Calculation of Thermodynamic Parameters of Adsorption at the L/G and L/L Interfaces -- G. Adsorption from Mixtures of Two Surfactants -- REFERENCES -- PROBLEMS -- 3: Micelle Formation by Surfactants -- I. THE CRITICAL MICELLE CONCENTRATION (CMC) -- II. MICELLAR STRUCTURE AND SHAPE -- A. The Packing Parameter -- B. Surfactant Structure and Micellar Shape -- C. Liquid Crystals -- D. Rheology of Surfactant Solutions