In-situ Thermoelectrochemistry (eBook)

Preface of the Editor 6
Preface of the Author 8
Acknowledgements 10
Contents 12
Chapter 1: Introduction 14
References 15
Chapter 2: Fundamentals 16
2.1 Reasons to Reconsider Thermoelectrochemistry 16
2.2 Isothermal and Non-isothermal Cells 16
2.3 Thermodynamics 18
2.3.1 Voltage and Potential in Non-isothermal Cells 18
2.3.2 Heat and Entropy Flow in Open Non-isothermal Cells 19
2.3.3 Entropy Flow with Charge Transfer: The Electrochemical Peltier Effect 21
2.4 Properties of the Interface Electrode/Solution 22
2.5 Properties of Solvent and of Ions in Solution 28
2.6 Kinetics and Transport Processes 30
References 33
Chapter 3: History of Modern Thermoelectrochemistry 35
3.1 Classical Thermoelectrochemistry in Isothermal Open Cells and Half-Cells 35
3.2 High-Temperature Electrochemistry: Electrochemistry in Subcritical and Supercritical Fluids 44
3.2.1 Open High-Temperature Cells 45
3.2.2 Autoclave Cells 46
3.2.3 Electrochemistry in Supercritical Fluids 49
3.3 Sonoelectrochemistry 51
3.4 Electrochemical Calorimetry 52
3.5 Miscellaneous 55
References 55
Chapter 4: Modern Thermoelectrochemistry 64
4.1 Objectives 64
4.2 Heated Electrodes 65
4.2.1 Techniques of Heating 65
4.2.1.1 Heating of Solution Fractions 66
4.2.1.2 Heating of the Electrode Body 72
Heating by Laser or by Focused Tungsten Light 72
Indirect Electric Heating 76
Direct Electric Heating: ``Hot-Wire Electrochemistry´´ and ``Hot-Layer Electrochemistry´´ 77
Inductive Heating 80
References 80
Chapter 5: Dynamic Processes in Cells with Heated Electrode-Solution Interfaces 84
5.1 Temperature Profile and Concentration Profiles 85
5.2 Thermal Convection and Streaming Phenomena 89
5.3 The Complex Layer Structure at a Heated Thin Cylinder Electrode and Consequences for Voltammetry 94
References 97
Chapter 6: Working with Electrically Heated Electrodes 98
6.1 Heated Wires (Hot-Wire Electrochemistry) 98
6.1.1 Heated Microwires and Their Virtual ``Absurd´´ Characteristics 99
6.1.2 Design of Experiments 100
6.1.2.1 Electrodes and Cells 100
6.1.2.2 Electronics 104
6.1.2.3 Temperature Determination of Heated Wire Electrodes 107
6.2 Heated Macrostructures 110
6.3 New Thermoelectrochemical Methods 110
6.3.1 Methods with Continuous Electrode Heating 110
6.3.2 Methods with Pulsed Heating 112
6.3.2.1 Temperature-Pulse Voltammetry (TPV) 112
6.3.2.2 Temperature-Pulse Potentiometry (TPP) 118
6.3.2.3 Temperature-Pulse Amperometry (TPA) 119
6.4 Application Examples with Permanent Heating 119
6.4.1 Analytical Determinations 119
6.4.1.1 Volatile or Unstable Constituents 120
6.4.1.2 Stripping Analysis 120
6.4.2 Analysis of Bioactive Compounds and Development of Biosensors 121
6.4.2.1 Adsorptive Accumulation 121
6.4.2.2 DNA Determination and Hybridisation Analysis 121
6.4.2.3 Enzyme Sensors 122
6.4.3 Detectors for Flow Stream and Electrophoresis 123
6.4.4 Electrochemiluminescence 123
6.5 Application Examples with Pulsed Heating 125
6.5.1 Switched Passive Layers [75] 126
6.5.2 Heated Modified Electrodes [76] 127
6.5.3 Electropolymerisation [77] 128
References 128
Appendix A: A Calculation Procedure for Temperature Profiles at Heated Wire Electrodes 131
Reference 135
Appendix B: A Home-Built Device for Temperature-Pulse Voltammetry 137
The Analog Part 139
The ``Lower-Level´´ Program 140
The ``Higher-Level´´ Program 142
References 145
About the Author 147
About the Editor 149
Index 150