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7 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 with Solution Composition: Determination of the Surface Excess.- 7.3.9 Reflections on Electrocapillary Thermodynamics.- 7.3.10 Retrospect and Prospect in the Study of Electrified Interfaces.- Further Reading.- 7.4 The Structure of Electrified Interfaces.- 7.4.1 The Parallel-Plate Condenser Model: The Helmholtz-Perrin Theory.- 7.4.2 The Double Layer in Trouble: Neither Perfect Parabolas nor Constant Capacities.- 7.4.3 The Ionic Cloud: The Gouy-Chapman Diffuse-Charge Model of the Double Layer.- 7.4.4 Ions under Thermal and Electric Forces near an Electrode.- 7.4.5 A Picture of the Potential Drop in the Diffuse Layer.- 7.4.6 An Experimental Test of the Gouy-Chapman Model: Potential Dependence of the Capacitance, but at What Cost?.- 7.4.7 Some Ions Stuck to the Electrode, Others Scattered in Thermal Disarray: The Stern Model.- 7.4.8 A Consequence of the Stern Picture: Two Potential Drops across an Electrified Interface.- 7.4.9 Another Consequence of the Stern Model: An Electrified Interface Is Equivalent to Two Capacitors in Series.- 7.4.10 The Relative Contributions of the Helmholtz-Perrin and Gouy-Chapman Capacities.- 7.4.11 Some Questions Regarding the Sticking of Ions to the Electrode.- 7.4.12 An Electrode Is Largely Covered with Adsorbed Water Molecules.- 7.4.13 Metal-Water Interactions.- 7.4.14 The Orientation of Water Molecules on Charged Electrodes.- 7.4.15 How Close Can Hydrated Ions Come to a Hydrated Electrode?.- 7.4.16 Is It Only Desolvated Ions which Contact-Adsorb on the Electrode?.- 7.4.17 The Free-Energy Change for Contact Adsorption.- 7.4.18 What Determines the Degree of Contact Adsorption?.- 7.4.19 How Is Contact Adsorption Measured?.- 7.4.20 Contact Adsorption, Specific Adsorption, or Superequivalent Adsorption.- 7.4.21 Contact Adsorption: Its Influence of the Capacity of the Interface.- 7.4.22 Looking Back to Look Forward.- 7.4.23 The Complete Capacity-Potential Curve.- 7.4.24 The Constant-Capacity Region.- 7.4.24a The So-Called "Double Layer" Is a Double Layer.- 7.4.24b The Dielectric Constant of the Water between the Metal and the Outer Heimholtz Plane.- 7.4.24c The Position of the Outer Heimholtz Plane and an Interpretation of the Constant Capacity.- 7.4.25 The Capacitance Hump.- 7.4.26 How Does the Population of Contact-Adsorbed Ions Change with Electrode Charge?.- 7.4.27 The Test of the Population Law for Contact-Adsorbed Ions.- 7.4.28 The Lateral-Repulsion Model for Contact Adsorption.- 7.4.29 Flip-Flop Water on Electrodes.- 7.4.30 Calculation of the Potential Difference Due to Water Dipoles.- 7.4.31 The Excess of Flipped Water Dipoles over Flopped Water Dipoles.- 7.4.32 The Contribution of Adsorbed Water Dipoles to the Capacity of the Interface.- Further Reading.- 7.5 The Competition between Water and Organic Molecules at the Electrified Interfaces.- 7.5.1 The Relevance of Organic Adsorption.- 7.5.2 The Forces Involved in Organic Adsorption.- 7.5.3 Does Organic Adsorption Depend on Electrode Charge?.- 7.5.4 The Examination of the Water Flip-Flop Model for Simple Cases of Organic Adsorption.- 7.5.5 At What Potential Does Maximum Organic Adsorption Occur?.- Further Reading.- 7.6 Electrified Interfaces at Metals Other than Mercury.- Further Reading.- 7.7 The Structure of the Semiconductor-Electrolyte Interface.- 7.7.1 How Is the Charge Distributed inside a Solid Electrode?.- 7.7.2 The Band Theory of Crystalline Solids.- 7.7.3 Conductors, Insulators, and Semiconductors.- 7.7.4 Some Analogies between Semiconductors and Electrolytic Solutions.- 7.7.5 The Diffuse-Charge Region inside an Intrinsic Semiconductor: The Garrett-Brattain Space Charge.- 7.7.6 The Differential Capacity Due to the Space Charge.- 7.7.7 Impurity Semiconductors, n Type and p Type.- 7.7.8 Surface States: The Semiconductor Analogue of Contact Adsorption.- 7.7.9 Semiconductor Elec…