Electrochemical Methods: Fundamentals and Applications

✍ Scribed by Allen J. Bard; Larry R. Faulkner

• Publisher: Wiley
• Year: 2000
• Tongue: English
• Leaves: 851
• Edition: 2
• Category: Library

✦ Synopsis

This edition is fully revised to reflect the current state off the field. * Significant additions include ultramicroelectrodes, modified electrodes, and scanning probe methods. * Many chapters have been modified and improved, including electrode kinetics, voltammetric methods, and mechanisms of coupled chemical reactions.

✦ Table of Contents

Cover
PREFACE
CONTENTS
MAJOR SYMBOLS
Chapter 1 Introduction and overview of electrode processes
1.1 Introduction
1.2 Nonfaradaic Processes And The Nature Of The Electrode-Solution Interface
1.5 Semiempirical Treatment Of Nernstian Reactions With Coupled Chemical Reactions
1.6 The Literature Of Electrochemistry
1.7 References
1.8 Problems
Chapter 2 Potentials And Thermodynamics Of Cells
2.1 Basic Electrochemical Thermodynamics
2.2 A More Detailed View Of Interfacial Potential Differences
2.3 Liquid Junction Potentials
2.4 Selective Electrodes
2.5 References
2.6 Problems
Chapter 3 Kinetics Of Electrode Reactions
3.1 Review Of Homogeneous Kinetics
3.2 Essentials Of Electrode Reactions
3.3 Butler-Volmer Model Of Electrode Kinetics
3.4 Implications Of The Butler-Volmer Model For The One-Step, One-Electron Process
3.5 Multistep Mechanisms
3.6 Microscopic Theories Of Charge Transfer
3.7 References
3.8 Problems
Chapter 4 Mass Transfer By Migration And Diffusion
4.1 Derivation Of A General Mass Transfer Equation
4.2 Migration
4.3 Mixed Migration And Diffusion Near An Active Electrode
4.4 Diffusion
4.5 References
4.6 Problems
Chapter 5 Basic Potential Step Methods
5.1 Overview Of Step Experiments
5.2 Potential Step Under Diffusion Control
5.3 Diffusion-Controlled Currents At Ultramicroelectrodes
5.4 Sampled-Current Voltammetry For Reversible Electrode Reactions
5.5 Sampled-Current Voltammetry For Quasireversible And Irreversible Electrode Reactions
5.6 Multicomponent Systems And Multistep Charge Transfers
5.7 Chronoamperometric Reversal Techniques
5.8 Chronocoulometry
5.9 Special Applications Of Ultramicroelectrodes
5.10 References
5.11 Problems
Chapter 6 Potential Sweep Methods
6.1 Introduction
6.2 Nernstian (Reversible) Systems
6.3 Totally Irreversible Systems
6.4 Quasireversible Systems
6.5 Cyclic Voltammetry
6.6 Multicomponent Systems And Multistep Charge Transfers
6.7 Convolutive Or Semi-Integral Techniques
6.8 Cyclic Voltammetry Of The Liquid-Liquid Interface
6.9 REFERENCES
6.10 Problems
Chapter 7 Polarography And Pulse Voltammetry
7.1 Behavior At Polarographic Electrodes
7.2 Polarographic Waves
7.3 Pulse Voltammetry
7.3.1 Tast Polarography and Staircase Voltammetry
7.3.2 Normal Pulse Voltammetry
7.3.3 Reverse Pulse Voltammetry
7.3.4 Differential Pulse Voltammetry
7.3.5 Square Wave Voltammetry
7.3.6 Analysis by Pulse Voltammetry
7.4 References
7.5 Problems
Chapter 8 Controlled-Current Techniques
8.1 Introduction
8.2 General Theory Of Controlledcurrent Methods
8.3 Potential-Time Curves In Constantcurrent Electrolysis
8.4 Reversal Techniques
8.5 Multicomponent Systems And Multistep Reactions
8.6 The Galvanostatic Double Pulse Method
8.7 Charge Step (Coulostatic) Methods
8.8 References
8.9 Problems
Chapter 9 Methods Involving Forced Convection-Hydrodynamic Methods
9.1 Introduction
9.2 Theoretical Treatment Of Convective Systems
9.3 Rotating Disk Electrode
9.4 Rotating Ring And Ring-Disk Electrodes
9.5 Transients At The RDE And RRDE
9.6 Modulated Rde
9.7 Convection At UMEs
9.8 Electrohydrodynamics And Related Phenomena
9.9 References
9.10 Problems
Chapter 10 Techniques Based On Concepts Of Impedance
10.1 Introduction
10.2 Interpretation Of The Faradaic Impedance
10.3 Kinetic Parameters From Impedance Measurements
10.4 Electrochemical Impedance Spectroscopy
10.5 Ac Voltammetry
10.6 Higher Harmonics
10.7 Chemical Analysis By Ac Voltammetry
10.8 Instrumentation For Electrochemical Impedance Spectroscopy
10.9 Analysis Of Data In The Laplace Plane
10.10 References
10.11 Problems
Chapter 11 Bulk Electrolysis Methods
11.1 Classification Of Techniques
11.2 General Considerations In Bulk Electrolysis
11.3 Controlled-Potential Methods
11.4 Controlled-Current Methods
11.5 Electrometric End-Point Detectio
11.6 Flow Electrolysis
11.7 Thin-Layer Electrochemistry
11.8 Stripping Analysis
11.9 References
11.10 Problems
Chapter 12 Electrode Reactions With Coupled Homogeneous Chemical Reactions
12.1 Classification Of Reactions
12.2 Fundamentals Of Theory For Voltammetric And Chronopotentiometric Methods
12.3 Theory For Transient Voltammetry And Chronopotentiometry
12.4 Rotating Disk And Ring-Disk Methods
12.5 Ume Techniques
12.6 Sine Wave Methods
12.7 Controlled-Potential Coulometric Methods
12.8 References
12.9 Problems
Chapter 13 Double-Layer Structure And Adsorption
13.1 Thermodynamics Of The Double Layer
13.2 Experimental Evaluation Of Surface Excesses And Electrical Parameters
13.3 Models For Double-Layer Structure
13.4 Studies At Solid Electrodes
13.5 Extent And Rate Of Specific Adsorption
13.6 Effect Of Adsorption Of Electroinactive Species
13.7 Double-Layer Effects On Electrode Reaction Rates
13.8 References
13.9 Problems
Chapter 14 Electroactive Layers And Modified Electrodes
14.1 Introduction-Intellectual And Technological Motivations
14.2 Types, Preparation, And Properties Of Films And Modified Electrodes
14.3 Electrochemical Responses Of Adsorbed Monolayers
14.4 Overview Of Processes At Modified Electrodes
14.5 Blocking Layers
14.6 Other Methods Of Characterization
14.7 References
14.8 Problems
Chapter 15 Electrochemical Instrumentation
15.1 Operational Amplifiers
15.2 Current Feedback
15.3 Voltage Feedback
15.4 Potentiostats
15.5 Galvanostats
15.6 Difficulties With Potential Control
15.7 Measurement Of Low Currents
15.8 Computer-Controlled Instrumentation
15.9 Troubleshooting Electrochemical Systems
15.10 References
15.11 Problems
Chapter 16 Scanning Probe Techniques
16.1 Introduction
16.2 Scanning Tunneling Microscopy
16.3 Atomic Force Microscopy
16.4 Scanning Electrochemical Microscopy
16.5 References
16.6 Problems
Chapter 17 Spectroelectrochemistry And Other Coupled Characterization Methods
17.1 Ultraviolet And Visible Spectroscopy
17.2 Vibrational Spectroscopy
17.3 Electron And Ion Spectrometry
17.4 Magnetic Resonance Methods
17.5 Quartz Crystal Microbalance
17.6 X-Ray Methods
17.7 References
17.8 Problems
Chapter 18 Photoelectrochemistry And Electrogenerated Chemiluminescence
18.1 Electrogenerated Chemiluminescence
18.2 Photoelectrochemistry At Semiconductors
18.3 Electrochemical Detection Of Photolytic And Radiolytic Products
18.4 References
18.5 Problems
Appendix A Mathematical Methods
А. 1 Solving Differential Equations By The Laplace Transform Technique
A. 2 Taylor Expansions
A. 3 The Error Function And The Gaussian Distribution
A. 4 Leibnitz Rule
A.5 Complex Notation
A. 6 Fourier Series And Fourier Transformation
A. 7 References
A. 8 Problems
Appendix B Digital Simulations Of Electrochemical Problems
B. 1 Setting Up The Model
B. 2 An Example
B. 3 Incorporating Homogeneous Kinetics
B. 4 Boundary Conditions For Various Techniques
B. 5 Simulations In Convective Systems
B. 6 Miscellaneous Digital Simulations
B. 7 References
B. 8 Problems
Appendix C Reference Tables
INDEX
A - E
F - P
Q - Z