Electrochemical Kinetics

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.

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 εO

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 ηd 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 ηr

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 ηcr

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 ηΩ

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