THE CHEMISTRY OF ELECTRODE PROCESSES
Part I Experimental Determination of Interfacial Stress Changes in Electrochemical Systems 1 Introduction and Basic Concepts 3 11 Issues Related to Electrified Interfaces and Electrocapillarity: Some Introductory Remarks 3 12 Selected Concepts and Definitions in Electrochemistry and Surface Science 4 121 What Is an “Electrode” and What Is a “Solid Electrode”? 5 122 Surface, Interface, and Interphase 7 123 Elastic and Plastic Surface Strains 8 124 “Surface Stress” or “Interfacial Stress”? 10 References 11 2 Elements of the Thermodynamic Theory of Electrified Interfaces 13 21 Introduction 13 22 Basic Concepts and Notions 13 23 Gibbs and Guggenheim Model of the Interface 14 24 Adsorption 17 25 The Electrocapillary Equation and the Lippmann Equation 25 251 Example for the Application of the Electrocapillary Equation 28 252 The Ideally Polarizable Electrode when There Is no Complete Equilibrium Established Between the Bulk of a Solid and the Interface 30 253 Additional Remarks 31 References 32 3 Some Problems Related to the Surface Thermodynamics of “Solid Electrodes” 33 31 The “Generalized Lippmann Equation” 33 311 On the Derivation of the Generalized Lippmann Equation 34 312 On the Derivation of the Shuttleworth Equation 37 References 38 4 Experimental Methods for the Measurement of Surface Stress Changes 41 41 Introduction 41 42 The Piezoelectric Method 43 43 The Extensometer Method and Related Techniques 46 44 Contact Angle Measurements 55 45 Bending Plate and Bending Beam Methods 58 References 70 5 Optical Detection of the Deformation 75 51 Direct Optical Position Sensing 75 511 Experimental Arrangements 75 512 Basic Principles 77 513 Effect of Refraction 80 514 Effects of Nonnormal Incidence 84 515 Other Possible Sources of Errors 91 52 Interferometric Detection 96 521 Principles of Interferometry 96 522 The K€osters Laser Interferometer 98 523 Electrochemical Application 99 524 Adjustment of the Interferometer 101 525 Design of the Electrochemical Cell 102 526 Calibration 104 527 Detection of the Light Intensity 107 528 Fast K€osters Interferometry 107 529 Measurement of (Surface) Mass Changes 108 5210 Holographic Interferometry 110 References 111 6 Detection of the Cantilever Deflection by Microscopy 115 61 Scanning Tunneling Microscopy 115 62 Atomic Force Microscopy 117 References 118 7 Applications: Selected Experimental Results 121 71 Introduction 121 72 Platinum and Gold in Contact with Electrolyte Solutions 121 73 Stress Changes in Thin Films and Layers on Metals 128 731 Anodic Films and Passive Layers 128 732 Monitoring of the Electrochemical Degradation of Polymer Films 129 733 Insertion of Species into Materials, Absorption, and Intercalation 133 References 134 8 Mathematical Methods in Interfacial Thermodynamics 137 81 Important Mathematical Concepts 137 811 Homogeneous Functions 137 812 Legendre Transformation 151 References 155 Part II Probe Beam Deflection (PBD) 9 Introduction to Probe Beam Deflection Techniques 159 91 Introduction 159 92 Importance of the Field 159 93 History 160 References 162 10 Basic Principles of Probe Beam Deflection Techniques 167 101 Optical Principles 167 102 Theoretical Framework of Probe Beam Deflection 169 103 Probe Beam Deflection Techniques 171 1031 Potential Step Chronodeflectometry 171 1032 Pulse Voltadeflectometry (PVD) 180 1033 Current Step Chronodeflectometry 183 1034 Alternating Current Deflectometry (ACD) 185 1035 Cyclic Voltadeflectometry 185 1036 Water Concentration Effects 194 1037 Thermal Effects 194 104 Experimental Probe Beam Deflection Setup 194 105 Values of the Variation of Refractive Index with Concentration 196 References 196 11 Application of Probe Beam Deflection Techniques to the Study of Surface-Confined Electrochemical Systems 199 111 Introduction 199 112 Noble Metal Electrode Surfaces 199 113 Carbon Materials 201 114 Underpotential Deposition 201 115 Anion Adsorption on Metals 202 116 Electroactive Thin Films 204 1161 Electrochromic Oxides 205 1162 Inorganic Complex Films 209 1163 Electroactive Polymer Films 209 1164 Other Electroactive Polymers 219 117 Nanostructured Systems 220 1171 Determination of the Potential of Zero Charge of Porous Carbon 220 1172 Determination of pzc of Nanostructured Pt 222 1173 Double Layer Charging of Monolithic Nanoporous Carbon 224 1174 Hierarchical Porous Carbon Structures 224 1175 CO Oxidation on Nanostructured Pt Electrodes 225 1176 Layer-by-Layer Self-Assembled Monolayers 229 References 230 12 Application of Probe Beam Deflection to Solution Electrochemical Systems 237 121 Introduction 237 122 Ferricyanide FeðCNÞ 6 3 Reduction 237 123 Ferric Ion (Fe3+) Reduction 238 124 Oxygen Reduction 239 125 Oxidation of Small Organic Molecules 240 126 Metal Deposition and Corrosion 240 127 Silicon Corrosion 240 128 Thiophene Polymerization 241 References 241 13 In Situ Electrochemical Photothermal Deflection Techniques 243 131 Basic Principles 243 132 Photothermal Deflection Techniques 245 1321 Continuous Excitation 245 1322 Pulsed Excitation 245 1323 Sinusoidal Periodic Perturbation 247 133 Probe Beam Deflection Spectroscopy 248 1331 General Principles 248 1332 Square Wave Periodic Perturbation 249 134 Photothermal Monitoring of Concentration Gradients 251 135 Experimental Setup 251 136 Photothermal Deflection: Experimental Results 253 1361 In Situ PDS of Soluble Species 254 1362 In Situ PDS of Surface Films 254 1363 Voltammetric Absorptiometry 256 137 Conclusions 259 References 260 14 Comparison of Probe Beam Deflection Techniques with Other Methods to Monitor Fluxes of Mobile Species 263 141 Introduction 263 142 Electrochemical Techniques 263 1421 Ring-Disk Voltammetry 264 1422 Scanning Electrochemical Microscopy 265 143 Electrochemical Quartz Crystal Microbalance 266 144 Spectroelectrochemistry 268 1441 UV–Visible Spectroscopy with Indicator Dyes 268 1442 In Situ FTIR Spectroscopy 269 1443 In Situ Raman Spectroscopy 270 145 Radiotracer Detection 270 146 Surface Plasmon Resonance 270 147 Interferometry 271 148 Conclusions 272 References 272