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.
Inhalt
Preface to English-Language Edition
Introduction
1. 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
40. Theory of the Electrical Double Layer
41. Experimental Values of the Double Layer Capacity
42. Electrocapillarity
43. Lippmann Potentials of Charge-Free Electrodes
44. Billiter Potentials
45. The Absolute Potential
2. The Theory of Overvoltage
46. The Formulation of Problems in Electrode Kinetics
47. Various Types of Overvoltage
A. Charge-Transfer Overvoltage
48. Definitio n of Charge-Transfer Reaction and of Charge-Transfer Overvoltage
49. Charge-Transfer Overvoltage on Redox Electrodes
50. Charge-Transfer Overvoltage at Complicated Redox Electrodes Preceded or Followed by Reactions at Chemical Equilibrium
51. Charge-Transfer Overvoltage at Metal/Ion Electrodes
52. The Charge-Transfer Overvoltage at Complex Metal/Ion Electrodes with Rapidly Established Preceding or Following (Coupled) Chemica l Equilibrium
53. Charge-Transfer Overvoltage with A Sequence of Several Different Charge-Transfer Reactions
54. Charge-Transfer Resistance
B. Diffusion Overvoltage
55. Definition of the Diffusion Overvoltage
56. Diffusion Overvoltage without Coupled Homogeneou Chemical Equilibrium (Steady State)
57. Diffusion Overvoltage with Coupled Rapid Homogeneous Chemical Equilibria
58. Limiting Diffusion Current Density id
59. Diffusion Overvoltage Under the Condition of Spherical Diffusion
60. The Diffusion Layer
61. Diffusion Resistance Rd with Direct Current
62. Diffusion Impedance Rd with Alternating Current
63. Diffusion Overvoltage d as a Function of Time as a Constant Current Density (Galvanostatic Method)
64. Diffusion Current Density i as a Function of Time at a Given Diffusion Overvoltage (Potentiostatic Method)
65. Diffusion Current at the Dropping Mercury Electrode (Polarographie Currents)
66. Inapplicability of the Diffusion Overvoltage for the Elucidation of Reaction Mechanisms C Reaction Overvoltage
67. Definition of the Reaction Overvoltage r
68. Reaction Overvoltage with a Rate-Determining Homogeneous Reaction in Electrolytes
69. Reaction Overvoltage with a Rate-Determining Heterogeneous Chemical Reaction
70. The Limiting Reaction Current Density
71. Reaction Resistance Rr with Direct Current
72. Reaction Impedance Rr with Alternating Current
73. Time-Dependence of the Reaction Current Density at Constant Reaction Overvoltage (Potentiostatic Condition)
74. Polarographic Kinetic Currents at the Dropping Mercury Electrode
D. Crystallization Overvoltage
75. Definition of the Crystallization Overvoltage cr
76. Basis of a Theory of Crystallization Overvoltage
77. Crystallization Impedance Rc
E. Total Overvoltage
78. Concentration Overvoltage as a Superposition of Diffusion and Reaction Overvoltage
79. Division of the Total Overvoltage into Charge-Transfer, Diffusion, Reaction and Crystallization Overvoltage
80. DC Polarization Resistance Rp
81. AC Polarization Impedance
82. Total Overvoltage with Transient Galvanostatic Processes
83. Total Overvoltage with Transient Potentiostatic Processes
84. Superposition of Diffusion and Charge-Transient Overvoltage in Polarography
85. Faradaic Rectification
85a. Older Definitions of Overvoltage Types
F. Resistance Polarization
86. Definition of Resistance Polarization O
87. Resistance Polarization as a Result of the Current-Dependent Resistance of the Diffusion Layer
88. Resistance Polarization in Surface Films
89. Electrolyte Resistance RQ
3. Methods of Determining Electrochemical Reaction Mechanisms
90. 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
105. Definition of the Electrochemical Reaction Orders
106. Determination of Z0; and Zr, j from the Concentration Dependence of the Cnarge-Transfer Current Density
107. 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
108. From the Concentration Dependence of the Limiting Reaction Current Density ir
109. From the Shape of the Direct Current vs. Voltage Curve
110. From the Concentration and Frequency Dependence of the Reaction Impedance
111. From the Concentration and Time-Dependence in Step Functions Measurements
E. Determination of the Reaction Kinetics
112. From the Electrochemical Reaction Orders
113. From the Chemical Reaction Orders
List of Frequently Used Symbols
Authors Index
Subject Index