Modern Electrochemistry

Inhaltsangabe7 The Electrified Interface.- 7.1 Electrification of an Interface.- 7.1.1 The Electrode-Electrolyte Interface: The Basis of Electrodics.- 7.1.2 New Forces at the Boundary of an Electrolyte.- 7.1.3 The Interphase Region Has New Properties and New Structures.- 7.1.4 An Electrode Is Like a Giant Central Ion.- 7.1.5 The Consequences of Compromise Arrangements: The Electrolyte Side of the Boundary Acquires a Charge.- 7.1.6 Both Sides of the Interface Become Electrified: The So-Called "Electrical Double Layer".- 7.1.7 Double Layers Are Characteristic of All Phase Boundaries.- 7.1.8 A Look into an Electrified Interface.- Further Reading.- 7.2 Some Problems in Understanding an Electrified Interface.- 7.2.1 What Knowledge Is Required before an Electrified Interface Can Be Regarded as Understood?.- 7.2.2 Predicting the Interphase Properties from the Bulk Properties of the Phases.- 7.2.3 Why Bother about Electrified Interfaces?.- 7.2.4 The Need to Clarify Some Concepts.- 7.2.5 The Potential Difference across Electrified Interfaces.- 7.2.5a What Happens when One Tries to Measure the Absolute Potential Difference across a Single Electrode-Electrolyte Interface.- 7.2.5b The Absolute Potential Difference across a Single Electrified Interface Cannot Be Measured.- 7.2.5c Can One Measure Changes in the Metal-Solution Potential Difference?.- 7.2.5d The Extreme Cases of Ideally Nonpolarizable and Polarizable Interfaces.- 7.2.5e The Development of a Scale of Relative Potential Differences.- 7.2.5f Can One Meaningfully Analyze an Electrode-Electrolyte Potential Difference?.- 7.2.5g A Thought Experiment Involving a Charged Electrode in Vacuum.- 7.2.5h The Test Charge Must Avoid Image Interactions with the Charged Electrode.- 7.2.5i The Outer Potential ? of a Material Phase in Vacuum.- 7.2.5j What is the Relevance of the Outer Potential to Double-Layer Studies?.- 7.2.5k Another Thought Experiment Involving an Uncharged, Dipole- Covered Phase.- 7.2.5l The Dipole Potential Difference M?S? across an Electrode- Electrolyte Interface.- 7.2.5m The Sum of the Potential Differences Due to Charges and Dipoles: The Absolute Electrode-Electrolyte (or Galvani) Potential Difference.- 7.2.5n The Outer, Surface, and Inner Potential Differences.- 7.2.5o An Apparent Contradiction: The Sum of the ??fis across a System of Interfaces Can and the ?? across One Interface Cannot Be Measured.- 7.2.5p What Deeper Understanding Has Been Hitherto Gained Regarding the Absolute Potential Difference Across an Electrified Interface?.- 7.2.6 The Accumulation and Depletion of Substances at an Interface.- 7.2.6a What Would Represent Complete Structural Information Regarding an Electrified Interface?.- 7.2.6b The Concept of Surface Excess.- 7.2.6c Does Knowledge of the Surface Excess Contribute to Knowledge of the Distribution of Species in the Interphase Region?.- 7.2.6d Is the Surface Excess Equivalent to the Amount Adsorbed?.- 7.2.6e Is the Surface Excess Measurable?.- 7.2.6f The Special Position of Mercury in Double-Layer Studies.- Further Reading.- 7.3 The Thermodynamics of Electrified Interfaces.- 7.3.1 The Measurement of Interfacial Tension as a Function of the Potential Difference across the Interface.- 7.3.2 Some Basic Facts about Electrocapillary Curves.- 7.3.3 A Digression on the Electrochemical Potential.- 7.3.3a Definition of Electrochemical Potential.- 7.3.3b Can the Chemical and Electrical Work Be Determined Separately?.- 7.3.3c A Criterion of Thermodynamic Equilibrium between Two Phases: Equality of Electrochemical Potentials.- 7.3.3d Nonpolarizable Interfaces and Thermodynamic Equilibrium.- 7.3.4 Some Thermodynamic Thoughts on Electrified Interfaces.- 7.3.5 Interfacial Tension Varies with Applied Potential: Determination of the Charge Density on the Electrode.- 7.3.6 Electrode Charge Varies with Applied Potential: Determination of the Electrical Capacitance of the Interface.- 7.3.7 The Potential at Which an Electrode Has a Zero Charge.- 7.3.8 Surface Tension Varies wi