Modern Electrochemistry

by Bockris, J. O'M.; Reddy, Amulya K. N.; Gamboa-Aldeco, Maria

• ISBN13: 9780306461668
• ISBN10: 0306461668
• Edition: 2nd
• Format: Hardcover
• Copyright: 2000-12-01
• Publisher: Plenum Pub Corp

Summary

This long-awaited and thoroughly updated version of the classic text (Plenum Press, 1970) explains the subject of electrochemistry in clear, straightforward language for undergraduates and mature scientists who want to understand solutions. Like its predecessor, the new text presents the electrochemistry of solutions at the molecular level. The Second Edition takes full advantage of the advances in microscopy, computing power, and industrial applications in the quarter century since the publication of the First Edition. Such new techniques include scanning-tunneling microscopy, which enables us to see atoms on electrodes; and new computers capable of molecular dynamics calculations that are used in arriving at experimental values. A description of the electrochemical stage - the high field region near the interface - is the topic of Chapter 6 and involves a complete rewrite of the corresponding chapter in the First Edition, particularly the various happenings which occur with organic molecules which approach surfaces in solution. The chapter on electrode kinetics retains material describing the Butler-Volmer equation from the First Edition, but then turns to many new areas, including electrochemical theories of potential-dependent gas catalysis. Chapter 8 is a new one devoted to explaining how electrochemists deal with the fast-changing nature of the electrode surface. Quantum Mechanics as the basis to electrode kinetics is given an entirely new look - up to and including considerations of bond-breaking reactions.

Table of Contents

The Electrified Interface
Electrification of an Interface	771	(11)
The Electrode/Electrolyte Interface: The Basis of Electrodics	771	(1)
New Forces at the Boundary of an Electrolyte	771	(3)
The Interphase Region Has New Properties and New Structures	774	(1)
An Electrode Is Like a Giant Central Ion	774	(1)
The Consequences of Compromise Arrangements: The Electrolyte Side of the Boundary Acquires a Charge	775	(1)
Both Sides of the Interface Become Electrified: The Electrical Double Layer	775	(3)
Double Layers Are Characteristic of All Phase Boundaries	778	(1)
What Knowledge Is Required Before and Electrified Interface Can Be Regarded as Understood?	778	(2)
Predicting the Interphase Properties from the Bulk Properties of the Phases	780	(1)
Why Bother about Electrified Interfaces?	780	(2)
Experimental Techniques Used in Studying Interfaces	782	(24)
What Type of Information Is Necessary to Gain and Understanding of Interfaces?	782	(1)
The Importance of Working with Clean Surfaces (and Systems)	782	(2)
Why Use Single Crystals/	784	(1)
In Situ vs. Ex Situ Techniques	785	(3)
Ex Situ Techniques	788	(1)
Low-Energy Electron Diffraction (LEED)	788	(6)
X-Ray Photoelectron Spectroscopy (XPS)	794	(3)
In Situ Techniques	797	(1)
Infrared-Reflection Spectroscopy	797	(7)
Radiochemical Methods	804	(2)
The Potential Difference Across Electrified Interfaces	806	(36)
What Happens When One Tries to Measure the Potential Difference Across a Single Electrode/Electrolyte Interface?	806	(5)
Can One Measure Changes in the Metal-Solution Potential Difference?	811	(2)
The Extreme Cases of Idenally Nonpolarizable and Polarizable Interfaces	813	(2)
The Development of a Scale of Relative Potential Differences	815	(2)
Can One Meaningfully Analyze and Electrode-Electrolyte Potential Difference?	817	(4)
The Outer Potential ψ of a Material Phase in a Vacuum	821	(1)
The Outer Potential Difference, MΔSψ, between the Metal and the Solution	822	(1)
The Surface Potential, χ, of a Material Phase in a Vacuum	823	(1)
The Dipole Potential Difference MΔSχ across an Electrode-Electrolyte Interface	824	(2)
The Sum of the Potential Differences Due to Charges and Dipoles: The Inner Potential Difference, MΔS&phis;	826	(2)
The Outer, Surface, and Inner Potential Differences	828	(1)
Is the Inner Potential Difference and Absolute Potential Difference?	829	(1)
The Electrochemical Potential, the Total Work from Infinity to Bulk	830	(1)
Definition of Electrochemical Potential	830	(2)
Can the Chemical and Electrical Work Be Determined Separately?	832	(1)
A Criterion of Thermodynamic Equilibrium between Two Phases: Equality of Electrochemical Potentials	833	(1)
Nonpolarizable Interfaces and Thermodynamic Equilibrium	834	(1)
The Electron Work Function, Another Interfacial Potential	834	(3)
The Absolute Electrode Potential	837	(1)
Definition of Absolute Electrode Potential	837	(2)
Is It Possible to Measure the Absolute Potential?	839	(2)
Further Reading	841	(1)
The Accumulation and Depletion of Substances at an Interface	842	(6)
What Would Represent Complet Structural Information on an Electrified Interface?	842	(1)
The Concept of Surface Excess	843	(2)
Is the Surface Excess Equivalent to the Amount Adsorbed?	845	(1)
Does Knowledge of the Surface Excess Contribute to Knowledge of the Distribution of Species in the Interphase Region?	846	(1)
Is the Surface Excess Measurable?	847	(1)
The Thermodynamics of Electrified Interfaces	848	(23)
The Measurement of Interfacial Tension as a Function of the Potential Difference across the Interface	848	(1)
Surface Tension between a Liquid Metal and Solution	848	(1)
Is It Possible to Measure Surface Tension of Solid Metal and Solution Interfaces?	849	(3)
Some Basic Facts about Electrocapillary Curves	852	(2)
Some Thermodynamic Thoughts on Electrified Interfaces	854	(4)
Interfacial Tension Varies with Applied Potential: Determination of the Charge Density on the Electrode	858	(1)
Electrode Charge Varies with Applied Potential: Determination of the Electrical Capacitance of the Interface	859	(2)
The Potential at which and Electrode Has a Zero Charge	861	(1)
Surface Tension Varies with Solution Composition: Determination of the Surface Excess	862	(4)
Summary of Electrocapillary Thermodynamics	866	(3)
Retrospect and Prospect for the Study of Electrified Interfaces	869	(1)
Further Reading	870	(1)
The Structure of Electrified Interfaces	871	(24)
A Look into an Electrified Interface	871	(2)
The Parallel-Plate Condenser Model: The Helmholtz-Perrin Theory	873	(3)
The Double Layer in Trouble: Neither Perfect Parabolas nor Constant Capacities	876	(1)
The Ionic Cloud: The Gouy-Chapman Diffuse-Charge Model of the Double Layer	876	(4)
The Gouy-Chapman Model Provides a Potential Dependence of the Capacitance, but at What Cost?	880	(2)
Some Ions Stuck to the Electrode, Others Scattered in Thermal Disarray: The Stern Model	882	(5)
The Contribution of the Metal to the Double-Layer Structure	887	(3)
The Jellium Model of the Metal	890	(3)
How Important Is the Surface Potential for the Potential of the Double Layer?	893	(1)
Further Reading	894	(1)
Structure at the Interface of the Most Common Solvent: Water	895	(24)
An Electrode Is Largely Covered with Adsorbed Water Molecules	895	(1)
Metal-Water Interactions	896	(1)
One Effect of the Oriented Water Molecules in the Electrode Field: Variation of the Interfacial Dielectric Constant	897	(1)
Orientation of Water Molecules on Electrodes: The Three-State Water Model	898	(2)
How Does the Population of Water Species Vary with the Potential of the Electrode?	900	(4)
The Surface Potential gSdipole, Due to Water Dipoles	904	(6)
The Contribution of Adsorbed Water Dipoles to the Capacity of the Interface	910	(2)
Solvent Excess Entropy of the Interface: A Key to Obtaining Structural Information on Interfacial Water Molecules	912	(3)
If Not Solvent Molecules, What Factors Are Responsible for Variation in the Differential Capacity of the Electrified Interface with Potential?	915	(3)
Further Reading	918	(1)
Ionic Adsorption	919	(1)
How Close Can Hydrated Ions Come to a Hydrated Electrode?	919	(49)
What Parameters Determine if an Ion Is Able to Contact Adsorb on an Electrode?	920	(1)
Ion-Electrode Interactions	920	(3)
Solvent Interactions	923	(1)
Lateral Interactions	924	(2)
The Enthalpy and Entropy of Adsorption	926	(3)
Effect of the Electrical Field at the Interface on the Shape of the Adsorbed Ion	929	(2)
Equation of States in Two Dimensions	931	(2)
Isotherms of Adsorption in Electrochemical Systems	933	(3)
A Word about Standard States in Adsorption Isotherms	936	(1)
The Langmuir Isotherm: A Fundamental Isotherm	937	(1)
The Frumkin Isotherm: A Lateral Interaction Isotherm	938	(1)
The Temkin Isotherm: A Heterogeneous Surface Isotherm	938	(3)
The Flory-Huggins-Type Isotherm: A Substitutional Isotherm	941	(1)
Applicability of the Isotherms	941	(3)
An Ionic Isotherm for Heterogeneous Surfaces	944	(11)
Thermodynamic Analysis of the Adsorption Isotherm	955	(4)
Contact Adsorption: Its Influence on the Capacity of the Interface	959	(2)
The Constant-Capacity Region	961	(1)
The Capacitance Hump and the Capacity Minimum	962	(1)
Looking Back	963	(4)
Further Reading	967	(1)
The Adsorption Process of Organic Molecules	968	(16)
The Relevance of Organic Adsorption	968	(1)
Is Adsorption the Only Process that the Organic Molecules Can Undergo?	969	(1)
Identifying Organic Adsorption	970	(1)
The Almost-Null Current	970	(1)
The Parabolic Coverage-Potential Curve	970	(1)
The Maximum of the Coverage-Potential Curve Lies Close to the pzc	971	(1)
Forces Involved in Organic Adsorption	971	(1)
The Parabolic Coverage-Potential Curve	972	(6)
Other Factors Influencing the Adsorption of Organic Molecules on Electrodes	978	(1)
Structure, Size, and Orientation of the Adsorbed Organic Molecules	978	(1)
Electrode Properties	979	(2)
Electrolyte Properties	981	(3)
The Structure of Other Interfaces	984	(22)
The Structure of the Semiconductor-Electrolyte Interface	984	(1)
How Is the Charge Distributed inside a Solid Electrode?	984	(1)
The Band Theory of Crystalline Solids	985	(3)
Conductors, Insulators, and Semiconductors	988	(2)
Some Analogies between Semiconductors and Electrolytic Solutions	990	(2)
The Diffuse-Charge Region Inside and Intrinsic Semiconductor: The Garett-Brattain Space Charge	992	(3)
The Differential Capacity Due to the Space Charge	995	(2)
Impurity Semiconductors, n-Type and p-Type	997	(3)
Surface States: The Semiconductor Analogue of Contact Adsorption	1000	(1)
Colloid Chemistry	1001	(1)
Colloids: The Thickness of the Double Layer and the Bulk Dimenstions Are of the Same Order	1001	(1)
The Interaction of Double Layers and the Stability of Colloids	1002	(3)
Sols and Gels	1005	(1)
Double Layers Between Phases Moving Relative to Each Other	1006	(29)
The Phenomenology of Mobile Electrified Interfaces: Electrokinetic Properties	1006	(2)
The Relative Motion of One of the Phases Constituting and Electrified Interface Produces a Streaming Current	1008	(3)
A Potential Difference Applied Parallel to an Electrified Interface Produces an Electro-osmotic Motion of One of the Phases Relative to the Other	1011	(1)
Electrophoresis: Moving Solid Particles in a Stationary Electrolyte	1012	(3)
Further Reading	1015	(1)
Exercises	1015	(5)
Problems	1020	(10)
Micro Research Problems	1030	(1)
Appendix 6.1	1031	(4)
Electrodics
Introduction	1035	(7)
Some Things One Has to Know About Interfacial Electron Transfer: It's Both Electrical and Chemical	1035	(1)
Uni-electrodes, Pairs of Electrodes in Cells and Devices	1036	(1)
The Three Possible Electrochemical Devices	1036	(1)
The Driven Cell (or Substance Producer)	1036	(3)
The Fuel Cell (or Electricity Producer)	1039	(1)
The Electrochemical Undevice: An Electrode that Consumes Itself while Wasting Energy	1040	(1)
Some Special Characteristics of Electrochemical Reactions	1041	(1)
Electron Transfer Under an Interfacial Electric Field	1042	(25)
A Two-Way Traffic Across the Interface: Equilibrium and the Exchange Current Density	1047	(2)
The Interface Out of Equilibrium	1049	(3)
A Quantitative Version of the Dependence of the Electrochemical Reaction Rate on Overpotential: The Butler-Volmer Equation	1052	(2)
The Low Overpotential Case	1054	(1)
The High Overpotential Case	1054	(1)
Polarizable and Nonpolarizable Interfaces	1055	(2)
The Equilibrium State for Charge Transfer at the Metal/Solution Interface Treated Thermodynamically	1057	(1)
The Equilibrium Condition: Kinetic Treatment	1058	(1)
The Equilibrium Condition: Nernst's Thermodynamic Treatment	1058	(4)
The Final Nernst Equation and the Question of Signs	1062	(2)
Why Is Nernst's Equation of 1904 Still Useful?	1064	(1)
Looking Back to Look Forward	1065	(2)
Further Reading	1067	(1)
A More Detailed Look at Some Quantities in the Butler - Volmer Equation	1067	(7)
Does the Structure of the Interphasial Region Influence the Electrochemical Kinetics There?	1068	(3)
What About the Theory of the Symmetry Factor, β?	1071	(1)
The Interfacial Concentrations May Depend on Ionic Transport in the Electrolyte	1072	(1)
Further-Reading	1073	(1)
Electrode Kinetics Involving the Semiconductor/solution Interface	1074	(17)
Introduction	1074	(1)
General	1074	(1)
The n-p Junction	1075	(7)
The Current-Potential Relation at a Semiconductor. Electrolyte Interface (Negligible Surface States)	1082	(4)
Effect of Surface States on Semiconductor Electrode Kinetics	1086	(1)
The Use of n-and p-Semiconductors for Thermal Reactions	1086	(2)
The Limiting Current in Semiconductor Electrodes	1088	(1)
Photoactivity of Semiconductor Electrodes	1089	(1)
Further Reading	1090	(1)
Techniques of Electrode Kinetics	1091	(75)
Preparing the Solution	1091	(3)
Preparing the Electrode Surface	1094	(1)
Real Area	1095	(2)
Microelectrodes	1097	(1)
The Situation	1097	(1)
Lessening Diffusion Control by the Use of a Microelectrode	1098	(1)
Reducing Ohmic Errors by the Use of Microelectrodes	1099	(1)
The Downside of Using Microelectrodes	1100	(1)
Arrays	1100	(2)
The Far-Ranging Applications of Microelectrodes	1102	(1)
Thin-Layer Cells	1103	(1)
Which Electrode System Is Best?	1103	(1)
The Measurement Cell	1104	(1)
General Arrangement	1104	(3)
More on Luggin Capillaries and Tips	1107	(1)
Reference Electrodes	1108	(3)
Keeping the Current Uniform on an Electrode	1111	(1)
Apparatus Design Arising from the Needs of the Electronic Instrumentation	1112	(1)
Further Reading	1113	(2)
Measuring the Electrochemical Reaction Rate as a Function of Potential (at Constant Concentration and Temperature)	1115	(6)
Temperature Control in Electrochemical Kinetics	1121	(1)
The Dependence of Electrochemical Reaction Rates on Temperature	1122	(1)
Electrochemical Reaction Rates as a Function of the System Pressure	1123	(1)
The Equations	1123	(2)
What Is the Point of Measuring System Pressure Effects?	1125	(2)
Impedance Spectroscopy	1127	(1)
What Is Impedance Spectroscopy?	1127	(1)
Real and Imaginary Impedance	1128	(1)
The Impedance of a Capacitor in Series with a Resistor	1129	(2)
Applying ac Impedance Methods to Obtain Information on Electrode Processes	1131	(2)
The Warburg Impedance	1133	(1)
The Simplest ``Real'' Electrochemical Interface	1133	(2)
The Impedance (or Cole--Cole) Plot	1135	(1)
Calculating Exchange Current Densities and Rate Constants from Impedance Plots	1136	(1)
Impedance Spectroscopy for More Complex Interfacial Situations	1136	(2)
Cases in which Impedance Spectroscopy Becomes Limited	1138	(1)
Rotating Disk Electrode	1139	(1)
General	1139	(4)
Are Rotating Disk with Ring Electrodes Still Useful in the Twenty-first Century	1143	(1)
Other Unusual Electrodes Shapes	1144	(1)
Spectroscopic Approaches to Electrode Kinetics	1145	(1)
General	1145	(2)
FTIR Spectroscopy and Mechanisms on Electrode	1147	(1)
Ellipsometry	1147	(1)
What Is Ellipsometry?	1147	(1)
Is Ellipsometry Any Use in Electrochemistry?	1148	(1)
Some Understanding as to How Ellipsometry Works	1149	(3)
Ellipsometric Spectroscopy	1152	(1)
How Can Ellipsometry Be So Sensitive?	1153	(1)
Does Ellipsometry Have a Downside?	1154	(1)
Isotopic Effects	1154	(2)
Use of Isotopic Effects in the Determination of Electro-Organic Reaction Mechanisms	1156	(1)
Atomic-Scale In Situ Microscopy	1157	(2)
Use of Computers in Electrochemistry	1159	(1)
Computational	1159	(1)
Computer Simulation	1160	(2)
Use of Computer Simulation to Solve Differential Equations Pertaining to Diffusion Problems	1162	(1)
Use of Computers to Control Experiments: Robotization of Suitable Experiments	1162	(1)
Pattern Recognition Analysis	1162	(2)
Further Reading	1164	(2)
Multistep Reactions	1166	(27)
The Difference between Single-Step and Multistep Electrode Reactions	1166	(1)
Terminology in Multistep Reactions	1167	(1)
The Catalytic Pathway	1167	(1)
The Electrochemical Desorption Pathway	1168	(1)
Rate-Determining Steps in the Cathodic Hydrogen Evolution Reaction	1168	(1)
Some Ideas on Queues, or Waiting Lines	1169	(2)
The Overpotential η Is Related to the Electron Queue at an Interface	1171	(1)
A Near-Equilibrium Relation between the Current Density and Overpotential for a Multistep Reaction	1172	(3)
The Concept of a Rate-Determining Step	1175	(5)
Rate-Determining Steps and Energy Barriers for Multistep Reactions	1180	(2)
How Many Times Must the Rate-Determining Step Take Place for the Overall Reaction to Occur Once? The Stoichiometric Number ν	1182	(5)
The Order of an Electrodic Reaction	1187	(3)
Blockage of the Electrode Surface during Charge Transfer: The Surface-Coverage Factor	1190	(2)
Further Reading	1192	(1)
The Intermediate Radical Concentration, &thetas; and Its Effect on Electrode Kinetics	1193	(8)
Heat of Adsorption Independent of Coverage	1193	(1)
Heat of Adsorption Dependent on Coverage	1194	(1)
Frumkin and Temkin	1195	(1)
Consequences from the Frumkin-Temkin Isotherm	1195	(2)
When Should One Use the Frumkin-Temkin Isotherms in Kinetics Rather than the Simple Langmuir Approach?	1197	(1)
Are the Electrode Kinetics Affected in Circumstances under which ΔG&thetas; Varies with &thetas;?	1197	(4)
Further Reading	1201	(1)
The Reactivity of Crystal Planes of Differing Orientation	1201	(10)
Introduction	1201	(1)
Single Crystals and Planes of Specific Orientation	1201	(2)
Another Preliminary: The Voltammogram as the Arbiter of a Clean Surface	1203	(2)
Examples of the Different Degrees of Reactivity Caused by Exposing Different Planes of Metal Single Crystals to the Solution	1205	(4)
General Assessment of Single-Crystal Work in Electrochemistry	1209	(1)
Roots of the Work on Kinetics at Single-Crystal Planes	1210	(1)
Further Reading	1210	(1)
Transport in the Electrolyte Effects Charge Transfer at the Interface	1211	(46)
Ionics Looks after the Material Needs of the Interface	1211	(2)
How the Transport Flux Is Linked to the Charge-Transfer Flux: The Flux-Equality Condition	1213	(2)
Appropriations from the Theory of Heat Transfer	1215	(1)
A Qualitative Study of How Diffusion Affects the Response of an Interface to a Constant Current	1216	(2)
A Quantitative Treatment of How Diffusion to an Electrode Affects the Response with Time of an Interface to a Constant Current	1218	(3)
The Concept of Transition Time	1221	(4)
Convection Can Maintain Steady Interfacial Concentrations	1225	(5)
The Origin of Concentration Overpotential	1230	(2)
The Diffusion Layer	1232	(3)
The Limiting Current Density and Its Practical Importance	1235	(2)
Polarography: The Dropping-Mercury Electrode	1237	(9)
The Steady-State Current-Potential Relation under Conditions of Transport Control	1246	(1)
The Diffusion-Activation Equation	1247	(1)
The Concentration of Charge Carriers at the Electrode	1247	(1)
Current as a Function of Overpotential: Interfacial and Diffusion Control	1248	(2)
The Reciprocal Relation	1250	(1)
Reversible and Irreversible Reactions	1251	(1)
Transport-Controlled Deelectronation Reactions	1252	(1)
What Is the Effect of Electrical Migration on the Limiting Diffusion Current Density?	1253	(3)
Some Summarizing Remarks on the Transport Aspects of Electrodics Further Reading	1256	(1)
How to Determine the Stepwise Mechanisms of Electrodic Reactions	1257	(18)
Why Bother about Determinin a Mechanism?	1257	(1)
What Does It Mean: ``To Determine the Mechanism of an Electrode Reaction''?	1258	(1)
The Overall Reaction	1258	(1)
The Pathway	1259	(1)
The Rate-Determining Step	1260	(3)
The Mechanism of Reduction of O2 on Iron at Intermediate pH's	1263	(6)
Mechanism of the Oxidation of Methanol	1269	(4)
Further Reading	1273	(1)
The Importance of the Steady State in Electrode Kinetics	1274	(1)
Electrocatalysis	1275	(18)
Introduction	1275	(2)
At What Potential Should the Relative Power of Electrocatalysts Be Compared?	1277	(3)
How Electrocatalysis Works	1280	(4)
Volcanoes	1284	(2)
Is Platinum the Best Catalyst?	1286	(1)
Bioelectrocatalysis	1287	(1)
Enzymes	1287	(2)
Immobilization	1289	(1)
Is the Heme Group in Most Enzymes Too Far Away from the Metal for Enzymes to Be Active in Electrodes?	1289	(2)
Practical Applications of Enzymes on Electrodes	1291	(1)
Further Reading	1292	(1)
The Electrogrowth of Metals on Electrodes	1293	(55)
The Two Aspects of Electrogrowth	1293	(1)
The Reaction Pathway for Electrodeposition	1294	(2)
Stepwise Dehydration of an Ion: the Surface Diffusion of Adions	1296	(5)
The Half-Crystal Position	1301	(1)
Deposition on an Ideal Surface: The Resulting Nucleation	1302	(3)
Values of the Minimum Nucleus Size Necessary for Continued Growth	1305	(1)
Rate of an Electrochemical Reaction Dependent on 2D Nucleation	1306	(1)
Surface Diffusion to Growth Sites	1307	(3)
Residence Time	1310	(2)
The Random Thermal Displacement	1312	(1)
Underpotential Deposition	1313	(1)
Introduction	1313	(1)
Some Examples	1313	(2)
What Are the Causes of Underpotential Deposition?	1315	(1)
Some Devices for Building Lattices from Adions: Screw Dislocations and Spiral Growths	1316	(8)
Microsteps and Macrosteps	1324	(3)
How Steps from a Pair of Screw Dislocations Interact	1327	(1)
Crystal Facets Form	1328	(6)
Pyramids	1334	(1)
Deposition on Single-Crystal and Polycrystalline Substrates	1334	(1)
How the Diffusion of Ions in Solution May Affect Electrogrowth	1335	(1)
About the Variety of Shapes Formed in Electrodeposition	1336	(2)
Dendrites	1338	(1)
Organic Additives and Electrodeposits	1339	(1)
Material Failures Due to H Co-deposition	1340	(1)
Would Deposition from Nonaqueous Solutions Solve the Problems Associated with H Co-deposition?	1341	(1)
Breakdown Potentials for Certain Organic Solvents	1341	(3)
Molten Salt Systems Avoid Hydrogen Codeposition	1344	(1)
``Nonaqueous.''	1344	(1)
Advantages of Molten Salts as Solvents for Electrodeposition	1344	(1)
Photostimulated Electrodeposition of Metals on Semiconductors	1345	(1)
Surface Preparation: The Established Superiority of Electrochemical Techniques	1345	(1)
Electrochemical Nanotechnology	1345	(3)
Current--Potential Laws For Electrochemical Systems	1348	(22)
The Potential Difference across and Electrochemical System	1348	(2)
The Equilibrium Potential Difference across an Electrochemical Cell	1350	(1)
The Problem with Tables of Standard Electrode Potentials	1351	(5)
Are Equilibrium Cell Potential Differences Useful?	1356	(5)
Electrochemical Cells: A Qualitative Discussion of the Variation of Cell Potential with Current	1361	(3)
Electrochemical Cells in Action: Some Quantitative Relations between Cell Current and Cell Potential	1364	(6)
The Electrochemical Activation of Chemical Reactions	1370	(4)
Further Reading	1374	(1)
Electrochemical Reactions That Occur without Input of Electrical Energy	1374	(6)
Introduction	1374	(1)
Electroless Metal Deposition	1374	(2)
Heterogeneous ``Chemical'' Reactions in Solutions	1376	(1)
Electrogenerative Synthesis	1377	(1)
Magnetic Induction	1378	(1)
Further Reading	1379	(1)
The Electrochemical Heart	1380	(21)
Further Reading	1382	(19)
Transients
Introduction	1401	(8)
The Evolution of Short Time Measurements	1401	(2)
Another Reason for Making Transient Measurements	1403	(4)
Is there a Downside for Transients?	1407	(1)
General Comment on Factors in Achieving Successful Transient Measurements	1407	(2)
Galvanostatic Transients	1409	(3)
How They Work	1409	(2)
Chronopotentiometry	1411	(1)
Open-Circuit Decay Method	1412	(2)
The Mathematics	1412	(2)
Potentiostatic Transients	1414	(2)
The Method	1414	(2)
Other Matters Concerning Transients	1416	(6)
Reversal Techniques	1416	(1)
Summary of Transient Methods	1417	(1)
``Totally Irreversible,'' etc: Some Aspects of Terminology	1418	(2)
The Importance of Transient Techniques	1420	(2)
Cyclic Voltammetry	1422	(16)
Introduction	1422	(2)
Beginning of Cyclic Voltammetry	1424	(1)
The Range of the Cyclic Voltammetric Technique	1425	(1)
Cyclic Voltammetry: Its Limitations	1426	(1)
The Acceptable Sweep Rate Range	1427	(1)
What Would Make a Sweep Rate Too Fast?	1427	(1)
What Would Make a Sweep Rate Too Slow?	1427	(1)
The Shape of the Peaks in Potential-Sweep Curves	1428	(3)
Quantitative Calculation of Kinetic Parameters from Potential-Sweep Curves	1431	(1)
Some Examples	1432	(2)
The Role of Nonaqueous Solutions in Cyclic Voltammetry	1434	(1)
Two Difficulties in Cyclic Voltammetric Measurements	1434	(4)
How Should Cyclic Voltammetry Be Regarded?	1438	(1)
Linear Sweep Voltammetry for Reactions that Include Simple Adsorbed Intermediates	1438	(17)
Potentiodynamic Relations that Account for the Role of Adsorbed Intermediates	1438	(4)
Further Reading	1442	(13)
Some Quantum-Oriented Electrochemistry
Setting the Scene	1455	(3)
A Preliminary Discussion: Absolute or Vacuum-Scale Potentials	1457	(1)
Chemical Potentials and Energy States of ``Electrons in Solution''	1458	(15)
The ``Fermi Energy'' of Electrons in Solution	1458	(3)
The Electrochemical Potential of Electrons in Solution and Their Quantal Energy States	1461	(1)
The Importance of Distribution Laws	1462	(1)
Distribution of Energy States in Solution: Introduction	1463	(1)
The Gaussian Distribution Law	1464	(3)
The Boltzmannian Distribution	1467	(2)
The Distribution Function for Electrons in Metals	1469	(2)
The Density of States in Metals	1471	(1)
Further Reading	1472	(1)
Potential Energy Surfaces and Electrode Kinetics	1473	(16)
Introduction	1473	(2)
The Basic Potential Energy Diagram	1475	(4)
Electrode Potential and the Potential Energy Curves	1479	(1)
A Simple Picture of the Symmetry Factor	1479	(5)
Is the β in the Butler-Volmer Equation Independent of Over-potential?	1484	(1)
How Bonding of Surface Radicals to the Electrode Produces Electrocatalysis	1484	(3)
Harmonic and Anharmonic Curves	1487	(1)
How Many Dimensions?	1488	(1)
Tunneling	1489	(7)
The Idea	1489	(1)
Equations of Tunneling	1490	(2)
The WKB Approximation	1492	(2)
The Need for Receiver States	1494	(1)
Other Approaches to Quantum Transitions and Some Problems	1494	(1)
Tunneling through Adsorbed Layers at Electrodes and in Biological Systems	1495	(1)
Some Alternative Concepts and Their Terminology	1496	(3)
Introduction	1496	(1)
Outer Shell and Inner Shell Reactions	1496	(1)
Electron-Transfer and Ion-Transfer Reactions	1497	(1)
Adiabatic and Nonadiabatic Electrode Reactions	1497	(2)
A Quantum Mechanical Description of Electron Transfer	1499	(12)
Electron Transfer	1499	(5)
The Frank-Condon Principle in Electron Transfer	1504	(1)
What Happens if the Movements of the Solvent-Ion Bonds Are Taken as a Simple Harmonic? An Aberrant Expression for Free Energy Activation in Electron Transfer	1504	(3)
The Primacy of Tafel's Law in Experimental Electrode Kinetics	1507	(4)
Four Models of Activation	1511	(7)
Origin of the Energy of Activation	1511	(1)
Weiss-Marcus: Electrostatic	1512	(2)
George and Griffith's Thermal Model	1514	(1)
Fluctuations of the Ground State Model	1515	(1)
The Librator Fluctuation Model	1516	(1)
The Vibron Model	1517	(1)
Bond-Breaking Reactions	1518	(3)
Introduction	1518	(3)
A Quantum Mechanical Formulation of the Electrochemical Current Density	1521	(1)
Equations	1521	(1)
A Retrospect and Prospect For Quantum Electrochemistry	1522	(4)
Discussion	1522	(1)
Further Readings	1523	(3)
Appendix. The Symmetry Factor: Do We Understand It?	1526
A.1. Introduction: Gurney--Butler	1526	(2)
A.2. Activationless and Barrierless	1528	(1)
A.3. The Dark Side of β	1529
Index	xxix