Electrochemical Kinetics

Electrochemical Kinetics

Theoretical Aspects

1st Edition - January 1, 1967

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  • Author: Klaus J. Vetter
  • eBook ISBN: 9781483266398

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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.

Table of Contents

  • Preface to English-Language Edition


    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

Product details

  • No. of pages: 486
  • Language: English
  • Copyright: © Academic Press 1967
  • Published: January 1, 1967
  • Imprint: Academic Press
  • eBook ISBN: 9781483266398

About the Author

Klaus J. Vetter

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