
Understanding Voltammetry
by Compton, Richard G.; Banks, Craig E.Buy New
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Summary
Table of Contents
Preface | p. vii |
Equilibrium Electrochemistry and the Nernst Equation | p. 1 |
Chemical Equilibrium | p. 1 |
Electrochemical Equilibrium: Introduction | p. 5 |
Electrochemical Equilibrium: Electron Transfer at the Solution-Electrode Interface | p. 9 |
Electrochemical Equilibrium: The Nernst Equation | p. 11 |
Walther Hermann Nernst | p. 17 |
Reference Electrodes and the Measurement of Electrode Potentials | p. 19 |
The Hydrogen Electrode as a Reference Electrode | p. 26 |
Standard Electrode Potentials and Formal Potentials | p. 27 |
Formal Potentials and Experimental Voltammetry | p. 30 |
Electrode Processes: Kinetics vs. Thermodynamics | p. 32 |
Electrode Kinetics | p. 35 |
Currents and Reaction Fluxes | p. 35 |
Studying Electrode Kinetics Requires Three Electrodes | p. 37 |
Butler-Volmer Kinetics | p. 40 |
Standard Electrochemical Rate Constants and Formal Potentials | p. 43 |
The Need for Supporting Electrolyte | p. 45 |
The Tafel Law | p. 46 |
Julius Tafel | p. 47 |
Multistep Electron Transfer Processes | p. 49 |
Tafel Analysis and the Hydrogen Evolution Reaction | p. 52 |
B. Stanley Pons | p. 57 |
Cold Fusion - The Musical! | p. 58 |
Why Are Some Standard Electrochemical Rate Constants Large but Others Slow? The Marcus Theory of Electron Transfer: An Introduction | p. 60 |
Marcus Theory: Taking it Further. Inner and Outer Sphere Electron Transfer | p. 66 |
Marcus Theory: Taking it Further. Adiabatic and Non-Adiabatic Reactions | p. 67 |
Marcus Theory: Taking it Further. Calculating the Gibbs Energy of Activation | p. 70 |
Relationship between Marcus Theory and Butler-Volmer Kinetics | p. 73 |
Marcus Theory and Experiment. Success! | p. 74 |
Diffusion | p. 77 |
Fick's 1st Law of Diffusion | p. 77 |
Fick's 2nd Law of Diffusion | p. 79 |
The Molecular Basis of Fick's Laws | p. 81 |
How Did Fick Discover His Laws? | p. 83 |
The Cottrell Equation: Solving Fick's 2nd Law | p. 88 |
The Cottrell Problem: The Case of Unequal Diffusion Coefficients | p. 92 |
The Nernst Diffusion Layer | p. 94 |
Mass Transfer vs. Electrode Kinetics: Steady-State Current-Voltage Waveshapes | p. 97 |
Mass Transport Corrected Tafel Relationships | p. 100 |
Cyclic Voltammetry at Macroelectrodes | p. 107 |
Cyclic Voltammetry: The Experiment | p. 107 |
Cyclic Voltammetry: Solving the Transport Equations | p. 109 |
Cyclic Voltammetry: Reversible and Irreversible Kinetics | p. 111 |
What Dictates 'Reversible' and 'Irreversible' Behaviour? | p. 119 |
Reversible and Irreversible Behaviour: The Effect of Voltage Scan Rate | p. 120 |
Reversible versus Irreversible Voltammetry: A Summary | p. 126 |
The Measurement of Cyclic Voltammograms: Three Practical Considerations | p. 127 |
The Effect of Unequal Diffusion Coefficients, DA ≠ DB | p. 129 |
Multiple Electron Transfer: Reversible Electrode Kinetics | p. 133 |
Multiple Electron Transfer: Irreversible Electrode Kinetics | p. 142 |
The Influence of pH on Cyclic Voltammetry | p. 147 |
The Scheme of Squares | p. 151 |
Simultaneous Two-Electron Transfer in Electrode Kinetics? | p. 152 |
Voltammetry at Microelectrodes | p. 157 |
The Cottrell Equation for a Spherical or Hemispherical Electrode | p. 157 |
Potential Step Transients at Microdisc Electrodes | p. 162 |
Microelectrodes Have Large Current Densities and Fast Response Times | p. 163 |
Applications of Potential Step Chronoamperometry Using Microdisc Electrodes | p. 165 |
Double Potential Step Microdisc Chronoamperometry Exploring the Diffusion Coefficient of Electrogenerated Species | p. 168 |
Cyclic and Linear Sweep Voltammetry Using Microdisc Electrodes | p. 176 |
Steady-State Voltammetry at the Microdisc Electrode | p. 186 |
Microelectrodes versus Macroelectrodes | p. 187 |
Ultrafast Cyclic Voltammetry: Megavolts per Second Scan Rates | p. 191 |
Ultrasmall Electrodes: Working at the Nanoscale | p. 192 |
Voltammetry at Heterogeneous Surfaces | p. 197 |
Partially Blocked Electrodes | p. 197 |
Microelectrode Arrays | p. 213 |
Voltammetry at Highly Ordered Pyrolytic Graphite Electrodes | p. 219 |
Electrochemically Heterogeneous Electrodes | p. 223 |
Electrodes Covered with Porous Films | p. 226 |
Voltammetric Particle Sizing | p. 229 |
Scanning Electrochemical Microscopy (SECM) | p. 233 |
Cyclic Voltammetry: Coupled Homogeneous Kinetics and Adsorption | p. 239 |
Homogeneous Coupled Reactions: Notation and Examples | p. 239 |
Modifying Fick's Second Law to Allow for Chemical Reaction | p. 241 |
Cyclic Voltammetry and the EC Reaction | p. 242 |
How Do the Parameters K1 and ∧ Emerge? | p. 246 |
Cyclic Voltammetry and the EC2 Reaction | p. 249 |
Examples of EC and EC2 Processes | p. 252 |
ECE Processes | p. 260 |
ECE versus DISP | p. 268 |
The CE Mechanism | p. 270 |
The EC' (Catalytic) Mechanism | p. 272 |
Adsorption | p. 274 |
Voltammetric Studies of Droplets and Solid Particles | p. 283 |
Hydrodynamic Electrodes | p. 291 |
Convection | p. 291 |
Modifying Fick's Laws to Allow for Convection | p. 293 |
The Rotating Disc Electrode: An Introduction | p. 294 |
The Rotating Disc Electrode - Theory | p. 295 |
Osborne Reynolds (1842-1912) | p. 299 |
The Rotating Disc Electrode - Further Theory | p. 299 |
Chronoamperometry at the Rotating Disc Electrode: An Illustration of the Value of Simulation | p. 306 |
The Rotating Disc and Coupled Homogeneous Kinetics | p. 309 |
The Channel Electrode: An Introduction | p. 312 |
The Channel Electrode: The Levich Equation Derived | p. 315 |
Channel Flow Cells and Coupled Homogeneous Kinetics | p. 316 |
Chronoamperometry at the Channel Electrode | p. 322 |
The Channel Electrode is not 'Uniformly Accessible' | p. 324 |
Channel Microelectrodes | p. 325 |
Channel Microband Electrode Arrays for Mechanistic Electrochemistry | p. 327 |
The High Speed Channel Electrode | p. 331 |
Hydrodynamic Electrodes Based on Impinging jets | p. 333 |
Sonovoltammetry | p. 335 |
Voltammetry for Electroanalysis | p. 347 |
Potential Step Voltammetric Techniques | p. 347 |
Differential Pulse Voltammetry | p. 348 |
Square Wave Voltammetry | p. 350 |
Stripping Voltammetry | p. 351 |
Sono-electroanalysis | p. 358 |
Voltammetry in Weakly Supported Media: Migration and Other Effects | p. 367 |
Potentials and Fields in Fully Supported Voltammetry | p. 367 |
The Distribution of Ions Around a Charged Electrode | p. 370 |
The Electrode-Solution Interface: Beyond the Gouy-Chapman Theory | p. 375 |
Double Layer Effect on Electrode Kinetics: Frumkin Effects | p. 379 |
A.N. Frumkin | p. 381 |
Transport by Diffusion and by Migration | p. 382 |
Measurement of Ion Mobilities | p. 384 |
Liquid Junction Potentials | p. 386 |
Chronoamperometry and Cyclic Voltammetry in Weakly Supported Media | p. 389 |
Voltammetry at the Nanoscale | p. 397 |
Transport to Particles Supported on an Electrode | p. 397 |
Nanoparticle Voltammetry: The Transport Changes as the Electrode Shrinks in Size | p. 405 |
Altered Chemistry at the Nanoscale | p. 414 |
Appendix: Simulation of Electrode Processes | p. 419 |
Fick's First and Second Laws | p. 419 |
Boundary Conditions | p. 420 |
Finite Difference Equations | p. 420 |
Backward Implicit Method | p. 421 |
Conclusion | p. 423 |
Index | p. 425 |
Table of Contents provided by Ingram. All Rights Reserved. |
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