Experimental Electrochemistry

Rudolf Holze is Full Professor of Physical Chemistry and Electrochemistry at the Institute of Chemistry at Chemnitz University of Technology. He finished his studies of chemistry at Bonn University with a diploma thesis on new cathode materials for lithium batteries. His doctoral thesis focused on impedance measurements at porous electrodes for energy conversion systems. As a postdoctoral fellow with E.B. Yeager at Case Western Reserve University, Cleveland, Ohio, USA, he studied transition metal complexes as electrocatalysts for fuel cells. Research interests include spectroelectrochemistry, electrochemical materials science (intrinsically conducting polymers, corrosion, functionalized electrode surfaces) and corrosion. He has published several books and more than 280 research papers and reviews. In editorial boards of various journals and as editor he is actively involved in scientific communication, including the organization of conferences and workshops.

• Preface to the Second Edition ixPreface to the First Edition xiForeword to the Second Edition xvSymbols and Acronyms xvii1 Introduction: An Overview of Practical Electrochemistry 1Practical Hints 2Electrodes 3Measuring Instruments 6Electrochemical Cells 7Data Recording 92 Electrochemistry in Equilibrium 11Experiment 2.1: The Electrochemical Series 11Experiment 2.2: Standard Electrode Potentials and the Mean Activity Coefficient 15Experiment 2.3: pH Measurements and Potentiometrically Indicated Titrations 20Experiment 2.4: Redox Titrations (Cerimetry) 25Experiment 2.5: Differential Potentiometric Titration 27Experiment 2.6: Potentiometric Measurement of the Kinetics of the Oxidation of Oxalic Acid 30Experiment 2.7: Polarization and Decomposition Voltage 34Experiment 2.8: A Simple Relative Hydrogen Electrode 393 Electrochemistry with Flowing Current 43Experiment 3.1: Ion Movement in an Electric Field 44Experiment 3.2: Paper Electrophoresis 46Experiment 3.3: Charge Transport in Electrolyte Solution 47Experiment 3.4: Conductance Titration 51Experiment 3.5: Chemical Constitution and Electrolytic Conductance 54Experiment 3.6: Faraday’s Law 56Experiment 3.7: Kinetics of Ester Saponification 58Experiment 3.8: Movement of Ions and Hittorf Transport Number 62Experiment 3.9: Polarographic Investigation of the Electroreduction of Formaldehyde 68Experiment 3.10: Galvanostatic Measurement of Stationary Current–Potential Curves 72Experiment 3.11: Cyclic Voltammetry 75Experiment 3.12: Slow Scan Cyclic Voltammetry 82Experiment 3.13: Kinetic Investigations with Cyclic Voltammetry 86Experiment 3.14: Numerical Simulation of Cyclic Voltammograms 90Experiment 3.15: Cyclic Voltammetry with Microelectrodes 92Experiment 3.16: Cyclic Voltammetry of Organic Molecules 96Experiment 3.17: Cyclic Voltammetry in Nonaqueous Solutions 102Experiment 3.18: Cyclic Voltammetry with Sequential Electrode Processes 104Experiment 3.19: Cyclic Voltammetry of Aromatic Hydrocarbons 107Experiment 3.20: Cyclic Voltammetry of Aniline and Polyaniline 110Experiment 3.21: Galvanostatic Step Measurements 115Experiment 3.22: Cyclic Voltammetry of a Supercapacitor Electrode 118Experiment 3.23: Chronoamperometry 121Experiment 3.24: Chronocoulometry 122Experiment 3.25: Rotating Disk Electrode 124Experiment 3.26: Rotating Ring-Disk Electrode 130Experiment 3.27: Measurement of Electrode Impedances 133Experiment 3.28: Corrosion Cells 136Experiment 3.29: Aeration Cell 138Experiment 3.30: Concentration Cell 139Experiment 3.31: Salt Water Drop Experiment According to Evans 141Experiment 3.32: Passivation and Activation of an Iron Surface 142Experiment 3.33: Cyclic Voltammetry with Corroding Electrodes 143Experiment 3.34: Tafel Plot of a Corroding Electrode 145Experiment 3.35: Impedance of a Corroding Electrode 148Experiment 3.36: Linear Polarization Resistance of a Corroding Electrode 150Experiment 3.37: Oscillating Reactions 1524 Analytical Electrochemistry 155Experiment 4.1: Ion-Sensitive Electrode 156Experiment 4.2: Potentiometrically Indicated Titrations 158Experiment 4.3: Bipotentiometrically Indicated Titration 163Experiment 4.4: Conductometrically Indicated Titration 165Experiment 4.5: Electrogravimetry 167Experiment 4.6: Coulometric Titration 170Experiment 4.7: Amperometry 172Experiment 4.8: Polarography (Fundamentals) 178Experiment 4.9: Polarography (Advanced Methods) 182Experiment 4.10: Anodic Stripping Voltammetry 183Experiment 4.11: Abrasive Stripping Voltammetry 186Experiment 4.12: Polarographic Analysis of Anions 189Experiment 4.13: Tensammetry 1915 Nontraditional Electrochemistry 197Experiment 5.1: UV-Vis Spectroscopy 197Experiment 5.2: Surface-Enhanced Raman Spectroscopy 200Experiment 5.3: Surface-Enhanced Raman Spectroscopy of aSelf-Assembled Monolayer 203Experiment 5.4: Infrared Spectroelectrochemistry 205Experiment 5.5: Electrochromism 207Experiment 5.6: Raman Spectroscopic Monitoring of Charge/Discharge of an Intrinsically Conducting Polyaniline Supercapacitor Electrode Material 2096 Electrochemical Energy Conversion and Storage 211Experiment 6.1: Lead–Acid Accumulator 211Experiment 6.2: Discharge Behavior of Nickel–Cadmium Accumulators 216Experiment 6.3: Performance Data of a Fuel Cell 218Experiment 6.4: Charging Supercapacitors 221Experiment 6.5: Discharging Supercapacitors 224Experiment 6.6: Zinc–Air Cell 227Experiment 6.7: Lithium-Ion Battery 228Experiment 6.8: Low-Temperature Discharge Behavior of Nickel–Cadmium Accumulators 230Experiment 6.9: Discharge Behavior of Nickel–Cadmium Accumulators at Constant Load 233Experiment 6.10: Impedance of a Button Cell 234Experiment 6.11: Potentiostatic Polarization Curves 236Experiment 6.12: Galvanostatic Polarization Curves 2377 Electrochemical Production 241Experiment 7.1: Cementation Reaction 241Experiment 7.2: Galvanic Copper Deposition 242Experiment 7.3: Electrochemical Oxidation of Aluminum 244Experiment 7.4: Kolbe Electrolysis of Acetic Acid 245Experiment 7.5: Electrolysis of Acetyl Acetone 247Experiment 7.6: Anodic Oxidation of Malonic Acid Diethylester 250Experiment 7.7: Indirect Anodic Dimerization of Acetoacetic Ester (3-Oxo-Butyric Acid Ethyl Ester) 251Experiment 7.8: Electrochemical Bromination of Acetone 253Experiment 7.9: Electrochemical Iodination of Ethanol 255Experiment 7.10: Electrochemical Production of Potassium Peroxodisulfate 257Experiment 7.11: Yield of Chlor-Alkali Electrolysis According to the Diaphragm Process 258Appendix 261Index 263