Electrochemical Kinetics: Theoretical Aspects focuses on the processes, methodologies, reactions, and transformations in electrochemical kinetics.
The book first offers information on electrochemical thermodynamics and the theory of overvoltage. Topics include equilibrium potentials, concepts and definitions, electrical double layer and electrocapillarity, and charge-transfer, diffusion, and reaction overvoltage. Crystallization overvoltage, total overvoltage, and resistance polarization are also discussed.
The text then examines the methods of determining electrochemical reaction mechanisms, including examination of the overall electrode reaction and determination of the type of overvoltage and reaction kinetics. A list of frequently used symbols is also provided.
The book is a valuable reference for readers interested in the study of electrochemical kinetics.

Contenu

Preface to English-Language Edition

Introduction

Electrochemical Thermodynamics
A. Concepts and Definitions
1. Electrode and Cell
2. Electrode and Cell Potential Difference
3. Inner, Outer and Surface Potentials
4. Galvani Potential Difference
5. Volta Potential Difference
6. Equilibrium Potentials
7. Electrode and Cell Reactions
8. Anodic and Cathodic Current, Faraday's Law
9. Overvoltage, Polarization
10. Exchange Current Density
B. Equilibrium Potentials eO
a) Thermodynamic Relations Between Cell Voltage and Energy
b) Metal/Ion Potentials
c) Redox Potentials (Oxidation-Reduction Potentials)
d) Liquid Junction Potentials (Nonequilibrium Potentials)
e) Donnan and Membrane Potentials
C. Electrical Double Layer and Electrocapillarity
1. Theory of the Electrical Double Layer
2. Experimental Values of the Double Layer Capacity
3. Electrocapillarity
4. Lippmann Potentials of Charge-Free Electrodes
5. Billiter Potentials
6. The Absolute Potential
The Theory of Overvoltage
1. The Formulation of Problems in Electrode Kinetics
2. Various Types of Overvoltage
A. Charge-Transfer Overvoltage
1. Definitio n of Charge-Transfer Reaction and of Charge-Transfer Overvoltage
2. Charge-Transfer Overvoltage on Redox Electrodes
3. Charge-Transfer Overvoltage at Complicated Redox Electrodes Preceded or Followed by Reactions at Chemical Equilibrium
4. Charge-Transfer Overvoltage at Metal/Ion Electrodes
5. The Charge-Transfer Overvoltage at Complex Metal/Ion Electrodes with Rapidly Established Preceding or Following (Coupled) Chemica l Equilibrium
6. Charge-Transfer Overvoltage with A Sequence of Several Different Charge-Transfer Reactions
7. Charge-Transfer Resistance
B. Diffusion Overvoltage
1. Definition of the Diffusion Overvoltage
2. Diffusion Overvoltage without Coupled Homogeneou Chemical Equilibrium (Steady State)
3. Diffusion Overvoltage with Coupled Rapid Homogeneous Chemical Equilibria
4. Limiting Diffusion Current Density id
5. Diffusion Overvoltage Under the Condition of Spherical Diffusion
6. The Diffusion Layer
7. Diffusion Resistance Rd with Direct Current
8. Diffusion Impedance Rd with Alternating Current
9. Diffusion Overvoltage d as a Function of Time as a Constant Current Density (Galvanostatic Method)
10. Diffusion Current Density i as a Function of Time at a Given Diffusion Overvoltage (Potentiostatic Method)
11. Diffusion Current at the Dropping Mercury Electrode (Polarographie Currents)
12. Inapplicability of the Diffusion Overvoltage for the Elucidation of Reaction Mechanisms C Reaction Overvoltage
13. Definition of the Reaction Overvoltage r
14. Reaction Overvoltage with a Rate-Determining Homogeneous Reaction in Electrolytes
15. Reaction Overvoltage with a Rate-Determining Heterogeneous Chemical Reaction
16. The Limiting Reaction Current Density
17. Reaction Resistance Rr with Direct Current
18. Reaction Impedance Rr with Alternating Current
19. Time-Dependence of the Reaction Current Density at Constant Reaction Overvoltage (Potentiostatic Condition)
20. Polarographic Kinetic Currents at the Dropping Mercury Electrode
D. Crystallization Overvoltage
1. Definition of the Crystallization Overvoltage cr
2. Basis of a Theory of Crystallization Overvoltage
3. Crystallization Impedance Rc
E. Total Overvoltage
1. Concentration Overvoltage as a Superposition of Diffusion and Reaction Overvoltage
2. Division of the Total Overvoltage into Charge-Transfer, Diffusion, Reaction and Crystallization Overvoltage
3. DC Polarization Resistance Rp
4. AC Polarization Impedance
5. Total Overvoltage with Transient Galvanostatic Processes
6. Total Overvoltage with Transient Potentiostatic Processes
7. Superposition of Diffusion and Charge-Transient Overvoltage in Polarography
8. Faradaic Rectification
85a. Older Definitions of Overvoltage Types
F. Resistance Polarization
1. Definition of Resistance Polarization O
2. Resistance Polarization as a Result of the Current-Dependent Resistance of the Diffusion Layer
3. Resistance Polarization in Surface Films
4. Electrolyte Resistance RQ
Methods of Determining Electrochemical Reaction Mechanisms
1. Statement of Problem
A. Examination of the Overall Electrode Reaction
91 . Examination of the Overall Electrode Reaction
B. Determination of the Type of Overvoltage
a) with Direct Current Measurements
b) Alternating Current Measurements
c) Step Function Measurements
d) Comparison of the Different Methods
C Determination of the Electrochemical Reaction Orders Z0, j and Zr, j
1. Definition of the Electrochemical Reaction Orders
2. Determination of Z0; and Zr, j from the Concentration Dependence of the Cnarge-Transfer Current Density
3. Determination of Z0, and Zr, j from the Concentration Dependence of the Exchange Current Density i0
D. Determination of Chemical Reaction Orders pj of Preceding Rate-Determining Reactions
1. From the Concentration Dependence of the Limiting Reaction Current Density ir
2. From the Shape of the Direct Current vs. Voltage Curve
3. From the Concentration and Frequency Dependence of the Reaction Impedance
4. From the Concentration and Time-Dependence in Step Functions Measurements
E. Determination of the Reaction Kinetics
1. From the Electrochemical Reaction Orders
2. From the Chemical Reaction Orders