Dynamic Surface Phenomena

This monograph provides a comprehensive introduction into the fast developing research field of dynamic processes at liquid/gas and liquid/liquid interfaces to postgraduate students, scientists and engineers interested in the fundamentals of non-equilibrium interfacial properties. It also addresses to some extent application fields, such as foams and emulsions. Theory and experiments on dynamic adsorption layers are considered systematically and discussed with respect to processes at interfaces. It is both an introduction for beginners in the present field as well as a systematic preparation of a vast range of the current scientific investigations generalised, together with accumulated knowledge for those already being an insider. It is the first extensive review available on the subject of dynamics of adsorption and gives a general summary of the current state of adsorption kinetics theory and experiments. The book also reviews recent progress in new-designed set-ups and improved and generalised known methods for studying interfacial relaxations. Cover Half Title Title Page Copyright Page Table of Contents Foreword Acknowledgement 1: The Definition of Surface Tension 1.1. The Molecular Definition of the Surface Tension 1.2. The Mechanical Definition of the Surface Tension 1.2.1. The Equation of Kelvin 1.2.2. The Equation of Thomson 1.3. The Thermodynamic Definition of the Surface Tension 2: Surface Thermodynamics 2.1. The Gibbs Equation 2.2. The Position of the Gibbs Dividing Surface 2.3. The Application of the Gibbs Equation 2.4. The Chemical Potential at the Surface 2.5. Adsorption Isotherms 2.6. The Adsorption Derivation for a Surfactant Mixture 2.7. Kinetic Derivation of the Langmuir Isotherm 2.8. Surface Activity Coefficients 2.9. Traube’s Rule, the Hydrophobic Effect and Inter-Chain Penetration 2.10. The Principle of Le Chatelier - Braun 3: Diffusion 3.1. Diffusion Equations 3.2. The Diffusion Penetration Depth 3.3. The Boundary Condition for the Diffusion Equation 4: Methods for Measuring the Dynamic Surface Tension 4.1. Different Experimental Methods 4.2. Classification of Experimental Methods 4.3. Introduction to Hydrodynamics 4.3.1. The Continuity Equation 4.3.2. The Stokes Equation 4.3.3. The Navier-Stokes Equation 4.3.4. Boundary Conditions 4.4. Stress Relaxation Methods 4.4.1. The Vibration or Oscillating Jet Method 4.4.2. The Inclined Plate Method 4.4.3. The Pulsed Drop Technique 4.4.4. Axisymmetric Drop Shape Analysis 4.4.5. The Drop Volume Method 4.4.6. Stepwise Surface Deformation in a Langmuir Trough 4.5. Dilation or θ Methods 4.5.1. The Experiments of Van Voorst Vader and Van Den Tempel 4.5.2. The Stripe Method 4.5.3. The Dynamic Capillary Method 4.6. Methods with Constant Surface Deformation 4.6.1. Experiments in a Langmuir Trough 4.6.2. Epansion of a Drop 4.6.2.1. Expansion of a Drop with Initially Clean Surface 4.6.2.2. The Maximum Bubble Pressure Method 4.6.2.3. The Drop Method of Mac Leod and Radke 4.7. Small Amplitude Periodic Surface Deformation 5: Diffusion Controlled Adsorption Kinetics 5.1. The Equation of Ward and Tordai 5.2. The Sutherland Equation 5.3. The Short and Long Time Approximation of the Ward and Tordai Equation 5.4. The Approximation Making Use of the Diffusion Penetration Depth 5.5. The Rate of Adsorption for Diffusion Controlled Kinetics 5.6. The Ward and Tordai Equation for a Surfactant Mixture 5.7. The Rate of Adsorption for Diffusion to a Drop Surface 6: Diffusion Controlled Adsorption Kinetics to a Continuously Deformed Surface 6.1. Diffusion to an Expanding Surface 6.1.1. Surface Expansion with Constant Rate dΩ/dt 6.1.2. Expansion with Constant Dilation Rate 6.1.3. Expanding Drop with a Constant Volume Flow Rate 6.1.4. The Drop Volume Technique 6.1.5. The Diffusion Penetration Depth 6.1.6. Expansion at Constant Surface Tension 6.1.7. The Long Time Approximation 6.1.8. Integration of the Convective Diffusion Equation 6.1.8.1. Stress Relaxation Experiments 6.1.8.2. Continuously Expanding Surface 6.1.8.3. Continuously Compressed Surface 6.2. Diffusion to a Compressed Surface 6.2.1. Sutherland Equation for Surface Compression 6.2.2. Compression with a Constant Speed dΩ/dt 6.2.3. Compression with a Constant Dilation Rate θ 6.2.4. The Diffusion Penetration Depth 6.2.5. Compressed Surface at a Constant Surface Pressure 7: The Interfacial Tension During Mass Transfer Across an Interface 7.1. The Transfer of an Alkanol Between Two Immiscible Phases 7.2. The Transfer of a Fatty Acid Between Two Immiscible Phases 7.3. Mass Transfer in Partly Miscible Systems Appendix 8: Periodic Surface Deformation 8.1. Periodic Deformation on a Flat Surface 8.2. Surface Disturbances for Other Geometries 8.2.1. Thin Layers (Foam Films) 8.2.2. Elasticity of a Drop 8.2.2.1. Diffusion Outside the Drop 8.2.2.2. Diffusion Inside the Drop 8.2.3. Elasticity of a Liquid Cylinder 8.2.3.1. Diffusion Outside the Cylinder 8.2.3.2. Diffusion Inside the Cylinder 8.3. The Elasticity for a Surfactant Mixture 8.4. Relation Between Complex Elasticity and Dynamic Surface Tensions 9: Transfer Controlled Adsorption Kinetics 9.1. Departure in Electrode Kinetics 9.2. The Kinetic Equation 9.3. Experimental Confirmation 9.4. Small Amplitude Periodic Deformation 9.5. Experiments with Constant Dilations 10: Micellar Solutions 10.1. Local Equilibrium Between the Monomers and Micelles 10.2. Periodic Small Amplitude Oscillations 10.3. Approximate Solutions for Micellar Systems 10.4. The Diffusion Penetration Depth for Micellar Systems 10.5. Use of the Diffusion-micellisation Penetration Depth to Describe the Dynamic Surface Tension for Micellar Solutions 11: Reorientation at the Surface 11.1. Surface Reorientation with Diffusion Equilibrium 11.2. Surface Reorientation in an Insoluble Monolayer 11.3. Surface Reaction with Diffusion 11.4. Surface Expansion with a Constant Dilation Rate for Diffusion Equilibrium Between the Bulk and the Subsurface 11.5. Small Amplitude Periodic Area Deformations 11.6. Small Amplitude Surface Deformation with Diffusional Exchange 11.7. Unsolved Problems 11.8. The Dynamic Interfacial Tension During the Mass Transfer of Decanoic Acid from Hexane to Water Containing 0.1 NaOH List of Used PhD Theses Symbol Index Subject Index 1. The Definition Of Surface Tension -- 2. Surface Thermodynamics -- 3. Diffusion -- 4. Methods For Measuring The Dynamic Surface Tension -- 5. Diffusion Controlled Adsorption Kinetics -- 6. Diffusion Controlled Adsorption Kinetics To A Continuously Deformed Surface -- 7. The Interfacial Tension During Mass Transfer Across An Interface -- 8. Periodic Surface Deformation -- 9. Transfer Controlled Adsorption Kinetics -- 10. Micellar Solutions -- 11. Reorientation At The Surface -- List Of Used Ph.d. Theses. Paul Joos ; Editors, Valentin B. Fainerman ... [et Al.]. Includes Bibliographical References And Index.