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 SymbolsAuthors IndexSubject Index