Experimental Electrochemistry

Preface to the Second Edition ix Preface to the First Edition xi Foreword to the Second Edition xv Symbols and Acronyms xvii 1 Introduction: An Overview of Practical Electrochemistry 1 Practical Hints 2 Electrodes 3 Measuring Instruments 6 Electrochemical Cells 7 Data Recording 9 2 Electrochemistry in Equilibrium 11 Experiment 2.1: The Electrochemical Series 11 Experiment 2.2: Standard Electrode Potentials and the Mean Activity Coefficient 15 Experiment 2.3: pH Measurements and Potentiometrically Indicated Titrations 20 Experiment 2.4: Redox Titrations (Cerimetry) 25 Experiment 2.5: Differential Potentiometric Titration 27 Experiment 2.6: Potentiometric Measurement of the Kinetics of the Oxidation of Oxalic Acid 30 Experiment 2.7: Polarization and Decomposition Voltage 34 Experiment 2.8: A Simple Relative Hydrogen Electrode 39 3 Electrochemistry with Flowing Current 43 Experiment 3.1: Ion Movement in an Electric Field 44 Experiment 3.2: Paper Electrophoresis 46 Experiment 3.3: Charge Transport in Electrolyte Solution 47 Experiment 3.4: Conductance Titration 51 Experiment 3.5: Chemical Constitution and Electrolytic Conductance 54 Experiment 3.6: Faraday’s Law 56 Experiment 3.7: Kinetics of Ester Saponification 58 Experiment 3.8: Movement of Ions and Hittorf Transport Number 62 Experiment 3.9: Polarographic Investigation of the Electroreduction of Formaldehyde 68 Experiment 3.10: Galvanostatic Measurement of Stationary Current–Potential Curves 72 Experiment 3.11: Cyclic Voltammetry 75 Experiment 3.12: Slow Scan Cyclic Voltammetry 82 Experiment 3.13: Kinetic Investigations with Cyclic Voltammetry 86 Experiment 3.14: Numerical Simulation of Cyclic Voltammograms 90 Experiment 3.15: Cyclic Voltammetry with Microelectrodes 92 Experiment 3.16: Cyclic Voltammetry of Organic Molecules 96 Experiment 3.17: Cyclic Voltammetry in Nonaqueous Solutions 102 Experiment 3.18: Cyclic Voltammetry with Sequential Electrode Processes 104 Experiment 3.19: Cyclic Voltammetry of Aromatic Hydrocarbons 107 Experiment 3.20: Cyclic Voltammetry of Aniline and Polyaniline 110 Experiment 3.21: Galvanostatic Step Measurements 115 Experiment 3.22: Cyclic Voltammetry of a Supercapacitor Electrode 118 Experiment 3.23: Chronoamperometry 121 Experiment 3.24: Chronocoulometry 122 Experiment 3.25: Rotating Disk Electrode 124 Experiment 3.26: Rotating Ring-Disk Electrode 130 Experiment 3.27: Measurement of Electrode Impedances 133 Experiment 3.28: Corrosion Cells 136 Experiment 3.29: Aeration Cell 138 Experiment 3.30: Concentration Cell 139 Experiment 3.31: Salt Water Drop Experiment According to Evans 141 Experiment 3.32: Passivation and Activation of an Iron Surface 142 Experiment 3.33: Cyclic Voltammetry with Corroding Electrodes 143 Experiment 3.34: Tafel Plot of a Corroding Electrode 145 Experiment 3.35: Impedance of a Corroding Electrode 148 Experiment 3.36: Linear Polarization Resistance of a Corroding Electrode 150 Experiment 3.37: Oscillating Reactions 152 4 Analytical Electrochemistry 155 Experiment 4.1: Ion-Sensitive Electrode 156 Experiment 4.2: Potentiometrically Indicated Titrations 158 Experiment 4.3: Bipotentiometrically Indicated Titration 163 Experiment 4.4: Conductometrically Indicated Titration 165 Experiment 4.5: Electrogravimetry 167 Experiment 4.6: Coulometric Titration 170 Experiment 4.7: Amperometry 172 Experiment 4.8: Polarography (Fundamentals) 178 Experiment 4.9: Polarography (Advanced Methods) 182 Experiment 4.10: Anodic Stripping Voltammetry 183 Experiment 4.11: Abrasive Stripping Voltammetry 186 Experiment 4.12: Polarographic Analysis of Anions 189 Experiment 4.13: Tensammetry 191 5 Nontraditional Electrochemistry 197 Experiment 5.1: UV-Vis Spectroscopy 197 Experiment 5.2: Surface-Enhanced Raman Spectroscopy 200 Experiment 5.3: Surface-Enhanced Raman Spectroscopy of a Self-Assembled Monolayer 203 Experiment 5.4: Infrared Spectroelectrochemistry 205 Experiment 5.5: Electrochromism 207 Experiment 5.6: Raman Spectroscopic Monitoring of Charge/Discharge of an Intrinsically Conducting Polyaniline Supercapacitor Electrode Material 209 6 Electrochemical Energy Conversion and Storage 211 Experiment 6.1: Lead–Acid Accumulator 211 Experiment 6.2: Discharge Behavior of Nickel–Cadmium Accumulators 216 Experiment 6.3: Performance Data of a Fuel Cell 218 Experiment 6.4: Charging Supercapacitors 221 Experiment 6.5: Discharging Supercapacitors 224 Experiment 6.6: Zinc–Air Cell 227 Experiment 6.7: Lithium-Ion Battery 228 Experiment 6.8: Low-Temperature Discharge Behavior of Nickel–Cadmium Accumulators 230 Experiment 6.9: Discharge Behavior of Nickel–Cadmium Accumulators at Constant Load 233 Experiment 6.10: Impedance of a Button Cell 234 Experiment 6.11: Potentiostatic Polarization Curves 236 Experiment 6.12: Galvanostatic Polarization Curves 237 7 Electrochemical Production 241 Experiment 7.1: Cementation Reaction 241 Experiment 7.2: Galvanic Copper Deposition 242 Experiment 7.3: Electrochemical Oxidation of Aluminum 244 Experiment 7.4: Kolbe Electrolysis of Acetic Acid 245 Experiment 7.5: Electrolysis of Acetyl Acetone 247 Experiment 7.6: Anodic Oxidation of Malonic Acid Diethylester 250 Experiment 7.7: Indirect Anodic Dimerization of Acetoacetic Ester (3-Oxo-Butyric Acid Ethyl Ester) 251 Experiment 7.8: Electrochemical Bromination of Acetone 253 Experiment 7.9: Electrochemical Iodination of Ethanol 255 Experiment 7.10: Electrochemical Production of Potassium Peroxodisulfate 257 Experiment 7.11: Yield of Chlor-Alkali Electrolysis According to the Diaphragm Process 258 Appendix 261 Index 263