Modern Electrochemistry

by Bockris, J. O'M.; Reddy, Amulya K. N.

• ISBN13: 9780306463242
• ISBN10: 0306463245
• 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. Chapter 10 starts with a detailed description of what happens when light strikes semi-conductor electrodes and splits water, thus providing in hydrogen a clean fuel. There have of course been revolutionary advances here since the First Edition was written. The book also discusses electrochemical methods that may provide the most economical path to many new syntheses - for example, the synthesis of the textile, nylon. The broad area of the breakdown of material in moist air, and its electrochemistry is taken up in the substantial Chapter 12. Another exciting topic covered is the evolution of energy conversion and storage which lie at the cutting edge of clean automobile development. Chapter 14 presents from a fresh perspective a discussion of electrochemical mechanisms in Biology, and Chapter 15 shows how new electrochemical approaches may potentially alleviate many environmental problems.

Table of Contents

Photoelectrochemistry
Introduction	1539	(1)
More on Band Bending at the Semiconductor/Solution Interface	1540	(4)
Introduction	1540	(1)
Why the Potential Difference in a Semiconductor with No Surface States Is Largely Inside the Solid Phase	1541	(1)
Bending the Bands	1542	(2)
Photoexcitation of Electrons by Absorption of Light	1544	(7)
p-Type Photocathodes	1544	(2)
The n-Type Photoanode	1546	(1)
The Rate-Determining Step in Photoelectrochemical Reactions	1547	(2)
``The Schottky Barrier''	1549	(1)
A Theory of the Photocurrent for Semiconductors of Low Surface State Concentration Near the Limiting Current	1549	(2)
What Has Been Learned about Photoelectrochemistry So Far?	1551	(5)
Surface Effects in Photoelectrochemistry	1556	(15)
Introduction	1556	(3)
Surface States	1559	(1)
Introduction	1559	(1)
Determination of Surface States	1560	(2)
What Causes a Surface State?	1562	(2)
The Effect of Surface States on the Distribution of Potential in the Semiconductor Interface	1564	(3)
Kinetic Photoelectrochemical Processes at High Surface State Semiconductors	1567	(3)
Looking Back and Looking Forward at Photoelectrochemistry	1570	(1)
Photoelectrocatalysis	1571	(3)
The Photoelectrochemical Splitting of Water	1574	(5)
The Need for Photoelectrocatalysis	1574	(2)
Could Cheap TiO2 Be Used in the Economic Photoelectrolysis of Water?	1576	(3)
The Photoelectrochemical Reduction of CO2	1579	(2)
Photoelectrochemical Waste Removal	1580	(1)
Retrospect and Prospect for Photoelectrochemistry, Particularly in Respect to the Splitting of Water	1581	(18)
Further Reading	1582	(3)
Appendix 1. A Brief Note on Electroluminescence and Electroreflectance	1585	(1)
Appendix 2. Electrochemical Preparation of Semiconductor Electrodes	1585	(1)
Appendix 3. High-Resolution Techniques in the Study of Semiconductor Surfaces	1586	(13)
Selected Aspects of Organoelectrochemistry
Introduction	1599	(3)
The Modernization of an Ancient Subject	1599	(1)
The Plus and Minus of Using an Electrochemical Route for Synthesis	1600	(2)
Determining the Mechanisms of Organoelectrochemical Reactions	1602	(6)
Introduction	1602	(1)
Anodic Oxidation of β-Cyanoethyl Ethers	1603	(2)
The Manufacture of Nylon	1605	(3)
Chiral Electrodes	1608	(2)
Optical Activity at Electrodes	1608	(2)
Electro-Organic Syntheses	1610	(2)
Cell Design	1610	(1)
New Electrode Materials	1611	(1)
A Moving Frontier	1612	(1)
Electronically Conducting Organic Polymers	1612	(14)
Introduction	1612	(2)
Ionically Doped Organic Polymers as Semiconductors	1614	(1)
General Properties of Electronically Conducting Organic Polymers	1614	(1)
Status of Polypyrrole	1614	(1)
Use of Polypyrrole in Electrocatalysis	1615	(1)
The Oxidation and Polymerization of the Monomer	1616	(1)
The Structure of the Polypyrrole/Solution Interface	1616	(1)
Relevant Facts	1616	(2)
Structure	1618	(1)
Practical Electrochemical Uses of Electronically Conducting Polymers (see also Section 4.9.2)	1619	(4)
Electronically Conducting Organic Compounds: Problems and the Future	1623	(3)
Designer Electrodes	1626	(11)
Introduction	1626	(2)
Formation of Monolayers of Organic Molecules on Electrodes	1628	(1)
Apparent Catalysis by Redox Couples Introduced into Polymers Attached to Electrodes	1629	(2)
Conclusion	1631	(1)
Further Reading	1631	(6)
Electrochemistry in Materials Science
Charge Transfer, Surface, and Civilization	1637	(44)
Introduction	1637	(1)
A Corroding Metal Is Analogous to a Short-Circuited Energy-Producing Cell	1638	(4)
Mechanism of the Corrosion of Ultrapure Metals	1642	(3)
What Is the Cathodic Reaction in Corrosion?	1645	(1)
Thermodynamics and the Stability of Metals	1646	(3)
Potential-pH (or Pourbaix) Diagrams: Uses and Abuses	1649	(3)
The Corrosion Current and the Corrosion Potential	1652	(3)
The Basic Electrodics of Corrosion in the Absence of Oxide Films	1655	(4)
An Understanding of Corrosion in Terms of Evans Diagrams	1659	(2)
How Corrosion Rates Are Measured	1661	(1)
Method 1: The Weight-Loss Method	1661	(1)
Method 2: Electrochemical Approach	1662	(4)
Impedance Bridge Version of the Stern-Geary Approach	1666	(1)
Other Methods	1666	(1)
The Mechanisms of the Corrosion Reactions Involving the Dissolution of Iron	1666	(1)
Something about the Mechanisms of the Anodic Dissolution of Iron	1667	(3)
The Mechanisms of Hydrogen Evolution (HER) on Iron (A Cathodic Partner Reaction in Corrosion often Met in Acid Solution)	1670	(2)
The Mechanism of Oxygen Reduction on Iron	1672	(1)
Where We Are Now: Looking Back at the Beginning	1673	(1)
Some Common Examples of Corrosion	1674	(5)
Further Reading	1679	(2)
Inhibiting Corrosion	1681	(28)
Introduction	1681	(1)
Cathodic and Anodic Protection	1681	(1)
Corrosion Inhibition by the Addition of Substances to the Electrolytic Environment of a Corroding Metal	1682	(2)
Corrosion Prevention by Charging the Corroding Metal with Electrons from an External Source	1684	(4)
Anodic Protection	1688	(1)
Organic Inhibition: the Fuller Story	1689	(4)
Relations between the Structure of the Organic Molecule and Its Ability to Inhibit Corrosion	1693	(2)
Toward a Designer Inhibitor	1695	(4)
Polymer Films as an Aspect of Corrosion Inhibition	1699	(1)
Nature of the Metal Surface in Corrosion Inhibition	1700	(3)
Green Inhibitors	1703	(2)
Looking Back on Some Methods by Which We Are Able to Inhibit Corrosion	1705	(3)
Further Reading	1708	(1)
The Protection of Aluminum by Transition Metal Additions	1709	(10)
Introduction	1709	(1)
Some Facts Relevant to the Transition Metal Effect on Inhibiting A1 Corrosion	1710	(5)
The Model by Which Tiny Concentrations of Transition Metal Ions Retard Corrosion of A1	1715	(4)
Passivation	1719	(9)
Introduction	1719	(2)
Some Definitions	1721	(1)
The Nature of the Passive Layer	1721	(5)
Structure of the Passive Film	1726	(1)
Depassivation	1726	(1)
Effects of Marine Organisms on Passive Layers	1727	(1)
Localized Corrosion	1728	(6)
Introduction	1728	(1)
The Initiation Mechanisms	1729	(1)
Forming a Pit or Crevice	1729	(1)
A Clamp on a Plain Piece of Metal	1729	(1)
Pits in Stainless Steel	1730	(1)
Events in Pits	1731	(1)
Modeling	1731	(2)
Further Reading	1733	(1)
Electrochemical Aspects of the Effect of Hydrogen on Metal	1734	(20)
Hydrogen Diffusion into a Metal	1734	(2)
The Preferential Diffusion of Absorbed Hydrogen to Regions of Stress in a Metal	1736	(3)
Hydrogen Can Crack Open a Metal Surface	1739	(3)
Surface Instability and the Internal Decay of Metals: Stress-Corrosion Cracking	1742	(5)
Practical Consequences of Stress-Corrosion Cracking	1747	(1)
Surface Instability and Internal Decay of Metals: Hydrogen Embrittlement	1747	(7)
What is the Direct Experimental Evidence for Very High Pressures in Voids in Metals?	1754	(8)
Introduction	1754	(1)
A Partial Experimental Verification of High Pressures in Metal Voids	1755	(2)
Indirect Measurement of High Pressures in Voids	1757	(2)
Damage Caused Internally in Metals by the Presence of H (and H2) at Varying Overpotentials	1759	(2)
Further Reading	1761	(1)
Fatigue	1762	(1)
The Preferential Flotation of Minerals: An Application of the Mixed Potential Concept	1763	(3)
Description	1763	(3)
At the Cutting Edge of Corrosion Research: The Use of STM and ATM	1766	(3)
Application	1766	(3)
A Laser-Based Technique for the Quantitative Measurement of H in Local Areas	1769	(2)
Description	1769	(2)
Other Methods of Examining Local Corrosion	1771	(1)
Description	1771	(1)
Further Reading	1772	(1)
A Bird's Eye View of Corrosion	1772	(17)
Description	1772	(3)
Further Reading	1775	(14)
Conversion and Storage of Electrochemical Energy
Introduction	1789	(1)
A Brief History of Fuel Cells	1790	(4)
Efficiency	1794	(8)
Maximum Intrinsic Efficiency in Electrochemical Conversion of the Energy of a Chemical Reaction to Electric Energy	1794	(4)
Actual Efficiency of an Electrochemical Energy Converter	1798	(1)
Physical Interpretation of the Absence of the Carnot Efficiency Factor in Electrochemical Energy Conversion	1799	(2)
Cold Combustion	1801	(1)
Kinetics of Fuel Cell Reactions	1802	(9)
Making V near Ve Is the Central Problem of Electrochemical Energy Conversion	1802	(4)
Electrochemical Parameters That Must Be Optimized for Good Energy Conversion	1806	(2)
The Power Output of an Electrochemical Energy Converter	1808	(2)
The Electrochemical Engine	1810	(1)
Electrodes Burning Oxygen from Air	1811	(1)
Porous Electrode	1811	(3)
Special Configurations of Electrodes in Electrochemical Energy Converters	1811	(3)
Types of Fuel Cells	1814	(12)
What Is Known So Far about Fuel Cells-Electrochemical Energy Converters	1814	(1)
General Aspects of the Practical Fuel Cells	1815	(1)
The Cells	1815	(1)
Efficiency of Energy Conversion and the Tafel Equation	1816	(1)
Alkaline Fuel Cells	1817	(1)
Phosphoric Acid Fuel Cells	1818	(3)
High-Temperature Fuel Cells	1821	(3)
Solid Polymer Electrolyte Fuel Cell	1824	(2)
Electrochemical Engines for Vehicular Transportation	1826	(11)
The Electrochemical Engine	1826	(1)
The Re-former	1827	(3)
Development of the Proton-Exchange Membrane Fuel Cell for Use in Automotive Transportation	1830	(1)
General	1830	(1)
Fundamental Research that Underlay Development of this Cell	1830	(5)
The Electric Car Schematic	1835	(1)
A Chord of Continuity	1835	(2)
Hybrids Involving Fuel Cells, Batteries, etc	1837	(1)
Direct MeOH Fuel Cells	1838	(1)
General Development of a Fuel Cell-Based Technology	1839	(3)
Fuel Cell Power Plants	1839	(1)
Household Energy	1840	(1)
Vehicular Transportation	1840	(1)
Railways	1840	(1)
Seagoing Vessels	1841	(1)
Aircraft	1841	(1)
Industry	1841	(1)
Space	1842	(1)
The Second Fuel Cell Principle	1842	(3)
Midway: The Need to Reduce Massive CO2 Emissions from Man-Made Sources	1845	(1)
Fuel Cells: The Summary	1846	(5)
Further Reading	1849	(2)
Electrochemical Energy Storage	1851	(3)
Introduction	1851	(3)
A Few Highlights in the Development of Batteries	1854	(1)
History	1854	(1)
Properties of Electrochemical Energy Storers	1855	(4)
The Discharge Plot	1855	(1)
The Ragone Plot	1856	(1)
Measures of Battery Performance	1857	(2)
Charging and Discharging a Battery	1859	(1)
Some Individual Batteries	1859	(21)
Introduction	1859	(1)
Classical Batteries	1860	(1)
Lead-Acid	1860	(1)
Nickel-Cadmium	1861	(1)
Zinc-Manganese Dioxide	1862	(8)
Modern Batteries	1870	(1)
Zinc-Air	1870	(2)
Nickel-Metal Hydride	1872	(2)
Li	1874	(3)
Some Batteries for Special Purposes	1877	(3)
The View Ahead with Batteries	1880	(1)
General	1880	(1)
Electrochemical Capacitors as Energy Storers	1881	(5)
Introduction	1881	(3)
Can the Energy Storage Possibilities with Electrochemical Condensers be Greatly Increased?	1884	(1)
Projected Uses of Electrochemical Capacitors	1885	(1)
Batteries: An Overview	1886	(17)
Further Reading	1888	(15)
Bioelectrochemistry
Bioelectrodics	1903	(7)
Introduction	1903	(1)
Useful Preliminaries	1904	(1)
Size	1904	(3)
Why Should Electrochemists Be Interested in Amino Acids, Proteins, and DNA?	1907	(1)
Cells, Membranes, and Mitochondria	1908	(2)
Membrane Potentials	1910	(8)
Preliminary	1910	(4)
Simplistic Theories of Membrane Potentials	1914	(1)
Modern Approaches to the Theory of Membrane Potentials	1915	(3)
Electrical Conduction in Biological Organisms	1918	(4)
Electronic	1918	(3)
Protonic	1921	(1)
The Electrochemical Mechanisms of the Nervous System: An Unfinished Section	1922	(11)
General	1922	(2)
Facts	1924	(3)
The Rise and Fall of the Theory of the Spike Potential	1927	(6)
Interfacial Electron Transfer in Biological Systems	1933	(17)
Introduction	1933	(1)
Adsorption of Proteins onto Metals from Solution	1933	(4)
Electron Transfer from Modified Metals to Dissolved Protein in Solution	1937	(5)
Electron Transfer from Biomaterials to Simple Redox Ions in Solution	1942	(2)
Theoretical Aspects of Electron Transfer from Solid Proteins to Ions in Solution	1944	(1)
Conduction and Electron Transfer in Biological Systems: Retrospect and Prospect	1944	(4)
Further Reading	1948	(2)
Electrochemical Communication in Biological Organisms	1950	(7)
Introduction	1950	(3)
Chemical Signaling	1953	(1)
Electrical Signaling	1954	(1)
Introduction	1954	(1)
Sensitivity of Biological Organisms to Minute Electric Field Strengths	1955	(1)
Signaling	1955	(1)
Carcinogenesis	1955	(2)
Enzymes as Electrodes	1957	(7)
Preliminary	1957	(3)
What Are Enzymes?	1960	(1)
Electrodes Carrying Enzymes	1960	(3)
The Electrochemical Enzyme-Catalyzed Oxidation of Styrene	1963	(1)
Metabolism	1964	(5)
An Abnormally Efficient Process of Energy Conversion	1964	(1)
Williams Model	1965	(2)
Development of the Fuel Cell Model in Biological Energy Conversion	1967	(1)
Distribution and Storage	1968	(1)
Electrochemical Aspects of Some Bioprocesses	1969	(7)
Introduction	1969	(1)
Superoxide as a Pretoxin	1970	(1)
Cardiovascular Diseases	1970	(1)
The Effects of Electromagnetic Radiation on Biological Organisms	1971	(3)
Microbial Effects	1974	(1)
Bactericidal	1974	(1)
Fuel-Cell Related	1975	(1)
Electrochemical Growth of Bones and Related Phenomena	1975	(1)
Electroanalgesia	1976	(1)
Other Effects	1976	(1)
Monitoring Neurotransmitters in the Intact Brain and Other Single-Cell Studies	1976	(3)
Introduction	1976	(3)
Summary: Medical Effects, Brain, and Single-Cell Experiments	1979	(10)
Further Reading	1980	(9)
Environmentally Oriented Electrochemistry
The Environmental Situation	1989	(3)
The Electrochemical Advantage	1992	(1)
Global Warming	1993	(11)
Facts	1993	(3)
The Solar-Hydrogen Solution	1996	(1)
The Ideas	1996	(3)
The Electrochemistry of Water Splitting	1999	(3)
The Electrolysis of Sea Water	2002	(1)
Superelectrolyzers	2003	(1)
Photoelectrochemical Splitting of Water	2004	(1)
Large-Scale Solar-Hydrogen Production	2004	(4)
Solar-Hydrogen Farms	2004	(4)
The Electrochemical Transport System	2008	(4)
Introduction	2008	(2)
Electrochemically Powered Cars	2010	(1)
The Fuel Cell	2011	(1)
The Fixing of CO2	2012	(10)
Introduction	2012	(1)
The Possible Reduction Product	2013	(1)
Reduction of CO2 on Metals	2013	(2)
The Mechanism of CO2 Reduction	2015	(2)
Photoelectrochemical Reduction of CO2	2017	(2)
Conversion of an Organic Compound in Photoelectrochemical Fixing	2019	(1)
Prospects in the Electrochemical Reduction of CO2	2020	(2)
Removal of Wastes	2022	(16)
Introduction	2022	(1)
Waste Water	2023	(1)
Sulfur Dioxide	2023	(1)
Removal of Metals: Aquifers	2024	(1)
The Destruction of Nitrates	2025	(1)
Electrochemical Treatment of Low-Level, Nuclear Wastes	2026	(2)
Mediator-Aided Destruction of Organic Wastes (Particularly Toxic, Organic Waste)	2028	(3)
Bactericidal Effects	2031	(1)
The Special Problem of H2S	2031	(1)
Introduction	2031	(1)
Electrochemical Decomposition of H2S	2031	(2)
Photoelectrochemical Decomposition of H2S	2033	(1)
Electrochemical Sewage Disposal	2033	(2)
Electrochemical Decontamination of Soil	2035	(1)
Introduction	2035	(1)
The Mechanism	2035	(1)
Experimental Work	2036	(1)
Summary on Soil Remediation	2037	(1)
Retrospect and Prospect	2038	(1)
A Parting Word	2039	(3)
Further Reading	2042
Index	xxv