Contents. Publisher s Foreword. Glossary of Symbols and Abbreviations

Transcription

1 Publisher s Foreword Glossary of Symbols and Abbreviations v xiii 1 Equilibrium Electrochemistry and the Nernst Equation Cell Thermodynamics The Nernst Equation The Nernst Equation The Nernst Equation Theory of the Nernst Equation The Debye Hückel Limiting Law Cell Reaction and Equilibrium Constant Cell Reaction and Equilibrium Constant Cell Reaction and Solubility Product Cell Reaction and pk a Cell Thermodynamics and Temperature Cell Thermodynamics and Temperature Cell Energetics Cell EMF and ph Cell Reaction and Equilibria Cell Reaction and K w Cell Reaction and Disproportionation Fuel Cell Energetics Fuel Cell Energetics vii

2 viii Understanding Voltammetry: Problems and Solutions 1.20 The Influence of Temperature on the Self-Ionisation of Water Cell Reaction and Complexation Reference Electrodes Formal Potentials Formal Potentials Standard Potentials and ph Standard Potentials and ph Standard Potentials and ph Electrode Kinetics Faraday s Laws of Electrolysis Electrodeposition Tafel Analysis: One-Electron Processes Tafel Analysis: Electrochemically Reversible Processes Tafel Analysis: Mass Transport Correction Tafel Analysis: Two-Electron Processes The Butler Volmer Equation and the Nernst Equation The Hydrogen Evolution Reaction Requirement for Supporting Electrolyte Frumkin Corrections Marcus Theory and Standard Electrochemical Rate Constants Marcus Theory and Butler Volmer Kinetics Marcus Theory and the Role of Solvent Marcus Theory and the Inverted Region Diffusion Fick s Laws of Diffusion Fick s Laws of Diffusion Diffusion Distances The Cottrell Equation Derivation of the Cottrell Equation Diffusion and Root-Mean-Square Displacement Cyclic Voltammetry at Macroelectrodes Cyclic Voltammetry: Electrochemically Reversible Voltammetry Cyclic Voltammetry: Electrochemically Irreversible Voltammetry Reversible vs Irreversible Voltammetry Voltammetric Diagnostics Voltammetry and Scan Rate Effects

3 ix 4.6 Ferrocene Voltammetry Ferrocene Voltammetry Features of Cyclic Voltammograms Derivation of the Randles Ševčík Equation Reversible Two-Electron Transfer The Influence of ph on Cyclic Voltammetry The Scheme of Squares The EE-Comproportionation Mechanism Voltammetry at Microelectrodes Steady-State Concentration Profile in Spherical Space Current Transients at a Spherical Electrode Linear vs Convergent Diffusion Dissolution of Microparticles Steady-State Limiting Current at a Microdisc Microdisc vs Planar Electrode The Shoup Szabo Equation Steady-State Electrolysis Effect of Unequal Diffusion Coefficients Temperature Effects on Steady-State Currents ECE Mechanism at a Microdisc Electrode EC Mechanism at a Microdisc Electrode Size Effects on Half-Wave Potentials Extracting Parameters from Microdisc Chronoamperometry Extracting Parameters from Microdisc Chronoamperometry Voltammetry at Heterogeneous Surfaces Graphitic Electrodes Carbon Nanotubes and Their Reactivity Highly Ordered Pyrolytic Graphite and the Influence of Defects Advantages of Arrays Diffusional Cases Geometry of a Regular Array Analysis of Diffusion to Electrode Arrays Partially Blocked Electrodes Cyclic Voltammetry: Coupled Homogeneous Kinetics and Adsorption EE Mechanism and Comproportionation EE mechanism: The Reduction of [(η 6 -C 6 Me 6 ) 2 Ru][BF 4 ]

4 x Understanding Voltammetry: Problems and Solutions 7.3 EC 2 Mechanism: The Reduction of the 2,6-Diphenyl Pyrylium Cation Analysis of an Unknown Reaction Mechanism EC Mechanism: Diethyl Maleate ECE Mechanism: p-chlorobenzonitrile ECE vs DISP 1: Voltammetry of Fluorescein Reduction of Anthracene in DMF CE Mechanism EC Mechanism EC Mechanism: Cysteine and Ferrocyanide EC Mechanism: Oxygen and Anthraquinone Chronoamperometry of Adsorbed Species Voltammetry of an Ideal Adsorbed Species Non-Ideal Adsorbed Species Irreversible Electron Transfer and Adsorbed Redox Species Voltammetry of Ferrocyanide/Ferricyanide Hydrodynamic Electrodes Channel Electrodes and Limiting Currents Channel Electrodes and Reynolds Number Flow to Rotating Discs and in Channels Channel Electrodes and ECE Processes Channel Electrodes and ECE Processes Channel Electrodes and Entry Length Channel Electrodes and Diffusion Coefficients Channel Electrodes and Current Distribution Wall-Jet Electrodes and Current Distribution Wall-Jet Electrodes and Diffusion Coefficients Wall-Jet Electrode and a DISP 1 Process Wall-Jet Electrode and EC Processes Sono-Voltammetry Rotating Disc Electrodes and Reynolds Number Wall-Jet and Rotating Disc Electrodes Rotating Disc Electrodes and ECE Processes Voltammetry for Electroanalysis Electrochemical Sizing of Gold Surfaces Differential Pulse Voltammetry Square-Wave Voltammetry Square-Wave Voltammetry and Dissolved Oxygen Stripping Voltammetry

5 xi 9.6 Analysis of DNA The Clark Cell Calibration and Limits of Detection Enzyme Electrodes Glucose Biosensors Detection of Vitamin B The Anodic Stripping Voltammetry of Industrial Effluent Adsorptive Stripping Voltammetry at Carbon Nanotube Modified Electrodes Surface Modified Electrodes Electron Transfer Rates at Carbon Electrodes Voltammetry in Weakly Supported Media: Migration and Other Effects Coulomb s Law The Nernst Planck Equation Migration and the Electric Field Transport Numbers and Liquid Junction Potentials Transport Numbers and the Hittorf Method The Gouy Chapman Equation Ohmic Drop The Zero-Field Approximation Self-Supported Reduction of the Cobaltocenium Cation Voltammetry at the Nanoscale Debye Length vs Diffusion Layer Thickness Altered Electrode Kinetics and Reactivity at the Nanoscale Nanoparticles: Case 4 Behaviour Coulomb Staircase Effects Ultrafast Single Molecule Voltammetry Thin-Layer Effects in Nanoscale Voltammetry Voltammetry in a Nanochannel Index 249