Understanding Voltammetry (2nd Edition)

ISBN-10: 1848165862
ISBN-13: 9781848165861
Edition: 2nd 2010 (Revised)
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Description: The power of electrochemical measurements in respect of thermodynamics, kinetics and analysis is widely recognized but the subject can be unpredictable to the novice even if they have a strong physical and chemical background, especially if they  More...

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Book details

Edition: 2nd
Copyright year: 2010
Publisher: World Scientific Publishing Co Pte Ltd
Publication date: 11/29/2010
Binding: Paperback
Pages: 444
Size: 5.75" wide x 8.75" long x 0.85" tall
Weight: 1.386
Language: English

The power of electrochemical measurements in respect of thermodynamics, kinetics and analysis is widely recognized but the subject can be unpredictable to the novice even if they have a strong physical and chemical background, especially if they wish to pursue the study of quantitative measurements further. Accordingly, some significant experiments are perhaps wisely never attempted while the literature is sadly replete with flawed attempts at rigorous voltammetry. This textbook considers how to go about designing, explaining and interpreting experiments centered around various forms of voltammetry (cyclic, microelectrode, hydrodynamic, etc.). The reader is assumed to have attained a knowledge equivalent to Master's level of physical chemistry but no exposure to electrochemistry in general, or voltammetry in particular. While the book is designed to "stand alone", references to important research papers are given to provide an introductory entry into the literature. In comparison to the first edition, two new chapters - transport via migration and nanoelectrochemistry - are added. Minor changes and updates are also made throughout the textbook to facilitate enhanced understanding and greater clarity of exposition.

Preface
Equilibrium Electrochemistry and the Nernst Equation
Chemical Equilibrium
Electrochemical Equilibrium: Introduction
Electrochemical Equilibrium: Electron Transfer at the Solution-Electrode Interface
Electrochemical Equilibrium: The Nernst Equation
Walther Hermann Nernst
Reference Electrodes and the Measurement of Electrode Potentials
The Hydrogen Electrode as a Reference Electrode
Standard Electrode Potentials and Formal Potentials
Formal Potentials and Experimental Voltammetry
Electrode Processes: Kinetics vs. Thermodynamics
Electrode Kinetics
Currents and Reaction Fluxes
Studying Electrode Kinetics Requires Three Electrodes
Butler-Volmer Kinetics
Standard Electrochemical Rate Constants and Formal Potentials
The Need for Supporting Electrolyte
The Tafel Law
Julius Tafel
Multistep Electron Transfer Processes
Tafel Analysis and the Hydrogen Evolution Reaction
B. Stanley Pons
Cold Fusion - The Musical!
Why Are Some Standard Electrochemical Rate Constants Large but Others Slow? The Marcus Theory of Electron Transfer: An Introduction
Marcus Theory: Taking it Further. Inner and Outer Sphere Electron Transfer
Marcus Theory: Taking it Further. Adiabatic and Non-Adiabatic Reactions
Marcus Theory: Taking it Further. Calculating the Gibbs Energy of Activation
Relationship between Marcus Theory and Butler-Volmer Kinetics
Marcus Theory and Experiment. Success!
Diffusion
Fick's 1st Law of Diffusion
Fick's 2nd Law of Diffusion
The Molecular Basis of Fick's Laws
How Did Fick Discover His Laws?
The Cottrell Equation: Solving Fick's 2nd Law
The Cottrell Problem: The Case of Unequal Diffusion Coefficients
The Nernst Diffusion Layer
Mass Transfer vs. Electrode Kinetics: Steady-State Current-Voltage Waveshapes
Mass Transport Corrected Tafel Relationships
Cyclic Voltammetry at Macroelectrodes
Cyclic Voltammetry: The Experiment
Cyclic Voltammetry: Solving the Transport Equations
Cyclic Voltammetry: Reversible and Irreversible Kinetics
What Dictates 'Reversible' and 'Irreversible' Behaviour?
Reversible and Irreversible Behaviour: The Effect of Voltage Scan Rate
Reversible versus Irreversible Voltammetry: A Summary
The Measurement of Cyclic Voltammograms: Three Practical Considerations
The Effect of Unequal Diffusion Coefficients, D<sub>A</sub> &#8800; D<sub>B</sub>
Multiple Electron Transfer: Reversible Electrode Kinetics
Multiple Electron Transfer: Irreversible Electrode Kinetics
The Influence of pH on Cyclic Voltammetry
The Scheme of Squares
Simultaneous Two-Electron Transfer in Electrode Kinetics?
Voltammetry at Microelectrodes
The Cottrell Equation for a Spherical or Hemispherical Electrode
Potential Step Transients at Microdisc Electrodes
Microelectrodes Have Large Current Densities and Fast Response Times
Applications of Potential Step Chronoamperometry Using Microdisc Electrodes
Double Potential Step Microdisc Chronoamperometry Exploring the Diffusion Coefficient of Electrogenerated Species
Cyclic and Linear Sweep Voltammetry Using Microdisc Electrodes
Steady-State Voltammetry at the Microdisc Electrode
Microelectrodes versus Macroelectrodes
Ultrafast Cyclic Voltammetry: Megavolts per Second Scan Rates
Ultrasmall Electrodes: Working at the Nanoscale
Voltammetry at Heterogeneous Surfaces
Partially Blocked Electrodes
Microelectrode Arrays
Voltammetry at Highly Ordered Pyrolytic Graphite Electrodes
Electrochemically Heterogeneous Electrodes
Electrodes Covered with Porous Films
Voltammetric Particle Sizing
Scanning Electrochemical Microscopy (SECM)
Cyclic Voltammetry: Coupled Homogeneous Kinetics and Adsorption
Homogeneous Coupled Reactions: Notation and Examples
Modifying Fick's Second Law to Allow for Chemical Reaction
Cyclic Voltammetry and the EC Reaction
How Do the Parameters K<sub>1</sub> and &#8743; Emerge?
Cyclic Voltammetry and the EC<sub>2</sub> Reaction
Examples of EC and EC<sub>2</sub> Processes
ECE Processes
ECE versus DISP
The CE Mechanism
The EC' (Catalytic) Mechanism
Adsorption
Voltammetric Studies of Droplets and Solid Particles
Hydrodynamic Electrodes
Convection
Modifying Fick's Laws to Allow for Convection
The Rotating Disc Electrode: An Introduction
The Rotating Disc Electrode - Theory
Osborne Reynolds (1842-1912)
The Rotating Disc Electrode - Further Theory
Chronoamperometry at the Rotating Disc Electrode: An Illustration of the Value of Simulation
The Rotating Disc and Coupled Homogeneous Kinetics
The Channel Electrode: An Introduction
The Channel Electrode: The Levich Equation Derived
Channel Flow Cells and Coupled Homogeneous Kinetics
Chronoamperometry at the Channel Electrode
The Channel Electrode is not 'Uniformly Accessible'
Channel Microelectrodes
Channel Microband Electrode Arrays for Mechanistic Electrochemistry
The High Speed Channel Electrode
Hydrodynamic Electrodes Based on Impinging jets
Sonovoltammetry
Voltammetry for Electroanalysis
Potential Step Voltammetric Techniques
Differential Pulse Voltammetry
Square Wave Voltammetry
Stripping Voltammetry
Sono-electroanalysis
Voltammetry in Weakly Supported Media: Migration and Other Effects
Potentials and Fields in Fully Supported Voltammetry
The Distribution of Ions Around a Charged Electrode
The Electrode-Solution Interface: Beyond the Gouy-Chapman Theory
Double Layer Effect on Electrode Kinetics: Frumkin Effects
A.N. Frumkin
Transport by Diffusion and by Migration
Measurement of Ion Mobilities
Liquid Junction Potentials
Chronoamperometry and Cyclic Voltammetry in Weakly Supported Media
Voltammetry at the Nanoscale
Transport to Particles Supported on an Electrode
Nanoparticle Voltammetry: The Transport Changes as the Electrode Shrinks in Size
Altered Chemistry at the Nanoscale
Appendix: Simulation of Electrode Processes
Fick's First and Second Laws
Boundary Conditions
Finite Difference Equations
Backward Implicit Method
Conclusion
Index

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