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伏安法是 基本的测量电阻的手段，也是电分析化学中 基本及简单的检测手段之一，在科学研究和生产实践中有广泛的应用。卡普顿编著的《伏安法教程（第2版）》作为一本教材，详细地介绍了各种伏安法实验的设计和应用，并对伏安法中可能遇到的难点给出了严谨的解决方案。本书 版系畅销教材，第二版在 版的基础上增加了两章，以便读者 好的学习、理解。这套教材和习题，原版十分畅销，中科院长春应化所的彭章泉博士曾写信给作者，觉得此书 好，拜读了10遍以上。 的万立俊研究员认为此书 好，是物理化学领域的 图书。

Preface

1 Equilibrium Electrochemistry and the Nernst Equation

1.1 Chemical Equilibrium

1.2 Electrochemical Equilibrium: Introduction

1.3 Electrochemical Equilibrium: Electron Transfer at the

Solution-Electrode Interface

1.4 Electrochemical Equilibrium: The Nernst Equation

1.5 Walther Hermann Nernst

1.6 Reference Electrodes and the Measurement of Electrode Potentials

1.7 The Hydrogen Electrode as a Reference Electrode

1.8 Standard Electrode Potentials and Formal Potentials

1.9 Formal Potentials and Experimental Voltammetry

1.10 Electrode Processes: Kinetics vs. Thermodynamics

2 Electrode Kinetics

2.1 Currents and Reaction Fluxes

2.2 Studying Electrode Kinetics Requires Three Electrodes

2.3 Butler-Volmer Kinetics

2.4 Standard Electrochemical Rate Constants and Formal Potentials

2.5 The Need for Supporting Electrolyte

2.6 The Tafel Law

2.7 Julius Tafel

2.8 Multistep Electron Transfer Processes

2.9 Tafel Analysis and the Hydrogen Evolution Reaction

2.10 B. StanleyPons

2.11 Cold Fusion -- The Musical!

2.12 Why Are Some Standard Electrochemical Rate Constants Large

but Others Slow? The Marcus Theory of Electron Transfer: An

Introduction

2.13 Marcus Theory: Taking it Further. Inner and Outer Sphere

Electron Transfer

2.14 Marcus Theory: Taking it Further. Adiabatic and Non-Adiabatic

Reactions

2.15 Marcus Theory: Taking it Further. Calculating the Gibbs Energy

of Activation

2.16 Relationship between Marcus Theory and Butler-Volmer Kinetics

2.17 Marcus Theory and Experiment. Success!

3 Diffusion

3.1 Fick's 1st Law of Diffusion

3.2 Fick's 2nd Law of Diffusion

3.3 The Molecular Basis of Fick's Laws

3.4 How Did Fick Discover His Laws?

3.5 The Cottrell Equation: Solving Fick's 2nd Law

3.6 The Cottrell Problem: The Case of Unequal Diffusion Coefficients

3.7 The Nernst Diffusion Layer

3.8 Mass Transfer vs. Electrode Kinetics: Steady-State

Current-Voltage Waveshapes

3.9 Mass Transport Corrected Tafel Relationships

4 Cyclic Voltammetry at Macroelectrodes

4.1 Cyclic Voltammetry: The Experiment

4.2 Cyclic Voltammetry: Solving the Transport Equations

4.3 Cyclic Voltammetry: Reversible and Irreversible Kinetics

4.4 What Dictates 'Reversible' and'Irreversible' Behaviour?

4.5 Reversible and Irreversible Behaviour: The Effect of Voltage Scan

Rate

4.6 Reversible versus Irreversible Voltammetry: A Summary

4.7 The Measurement of Cyclic Voltammograms: Three Practical

Considerations

4.8 The Effect of Unequal Diffusion Coefficients, DA ~- D8

4.9 Multiple Electron Transfer: Reversible Electrode Kinetics

4.10 Multiple Electron Transfer: Irreversible Electrode Kinetics

4.11 The Influence of pH on Cyclic Voltammetry

4.12 The Scheme of Squares

4.13 Simultaneous Two-Electron Transfer in Electrode Kinetics? . . .

5 Voltammetry at Microelectrodes

5.1 The Cottrell Equation for a Spherical or Hemispherical Electrode

5.2 Potential Step Transients at Microdisc Electrodes

5.3 Microelectrodes Have Large Current Densities and Fast Response

Times

5.4 Applications of Potential Step Chronoamperometry Using

Microdisc Electrodes

5.5 Double Potential Step Microdisc Chronoamperometry Exploring

the Diffusion Coefficient of Electrogenerated Species

5.6 Cyclic and Linear Sweep Voltammetry Using Microdisc Electrode~

5.7 Steady-State Voltammetry at the Microdisc Electrode

5.8 Microelectrodes versus Macroelectrodes

5.9 Ultrafast Cyclic Voltammetry: Megavolts per Second Scan Rates .

5.10 Ultrasmall Electrodes: Working at the Nanoscale

6 Voltammetry at Heterogeneous Surfaces

6.1 Partially Blocked Electrodes

6.2 Microelectrode Arrays

6.3 Voltammetry at Highly Ordered Pyrolytic Graphite Electrodes..

6.4 Electrochemically Heterogeneous Electrodes

6.5 Electrodes Covered with Porous Films

616 Voltammetric Particle Sizing

6.7 Scanning ElectrochemicaIMicroscopy (SECM)

7 Cyclic Voltammetry: Coupled Homogeneous Kinetics and Adsorption

7.1 Homogeneous Coupled Reactions: Notation and Examples . . .

7.2 Modifying Fick's Second Law to Mlow for Chemical Reaction . .

7.3 Cyclic Voltammetry and the EC Reaction

7.4 How Do the Parameters KI and A Emerge?

7.5 Cyclic Voltammetry and the EC2 Reaction

7.6 Examples of EC and EC2 Processes

7.7 ECE Processes

7.8 ECEversus DISP

7.9 The CE Mechanism

7.10 The ECI (Catalytic) Mechanism

7.11 Adsorption

7.12 Voltammetric Studies of Droplets and Solid Particles

8 Hydrodynamic Electrodes

8.1 Convection

8.2 Modifying Fick's Laws to Allow for Convection

8.3 The Rotating Disc Electrode: An Introduction

8.4 The Rotating Disc Electrode-- Theory

8.5 Osborne Reynolds (1842-1912)

8.6 The Rotating Disc Electrode-- Further Theory

8.7 Chronoamperometry at the Rotating Disc Electrode: An

Illustration of the Value of Simulation

8.8 The Rotating Disc and Coupled Homogeneous Kinetics

8.9 The Channel Electrode: An Introduction

8.10 The Channel Electrode: The Levich Equation Derived

8.11 Channel Flow Cells and Coupled Homogeneous Kinetics

8.12 Chronoamperometry at the Channel Electrode

8.13 The Channel Electrode is not 'Uniformly Accessible' .

8.14 Channel Microelectrodes

8.15 Channel Microband Electrode Arrays for Mechanistic

Electrochemistry

8.16 The High Speed Channel Electrode

8.17 Hydrodynamic Electrodes Based on Impinging iets

8.18 Sonovoltammetry

9 Voltammetry for Electroanalysis

9.1 Potential Step Voltammetric Techniques

9.2 Differential Pulse Voltammetry .

9.3 Square Wave Voltammetry

9.4 Stripping Voltammetry

9.5 Sono-electroanalysis

10 Voltammetry in Weakly Supported Media: Migration and Other Effects

10.1 Potentials and Fields in Fully Supported Voltammetry

10.2 The Distribution of Ions Around a Charged Electrode

10.3 The Electrode-Solution Interface: Beyond the Gouy-Chapman

Theory

10.4 Double Layer Effect on Electrode Kinetics: Frumkin Effects . . .

10.5 A.N. Frumkin ,

10.6 Transport by Diffusion and by Migration

10.7 Measurement of Ion Mobilities

10.8 Liquid Junction Potentials

10.9 Chronoamperometry and Cyclic Voltammetry in Weakly

Supported Media

11 Voltammetry at the Nanoscale

11.1 Transport to Particles Supported on an Electrode

11.2 Nanoparticle Voltammetry: The Transport Changes as the

Electrode Shrinks in Size

11.3 Altered Chemistry at the Nanoscale

Appendix: Simulation of Electrode Processes

A.1 Fick's First and Second Laws

A.2 Boundary Conditions

A.3 Finite Difference Equations

A.4 Backward Implicit Method

A.5 Conclusion

Index

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