Electrochemical Science and Technology E-Book

Keith Oldham

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 643

Veröffentlichungsjahr: 2011

Beschreibung

Electrochemistry is a discipline of wide scientific and technological interest. Scientifically, it explores the electrical properties of materials and especially the interfaces between different kinds of matter. Technologically, electrochemistry touches our lives in many ways that few fully appreciate; for example, materials as diverse as aluminum, nylon, and bleach are manufactured electrochemically, while the batteries that power all manner of appliances, vehicles, and devices are the products of electrochemical research.  Other realms in which electrochemical science plays a crucial role include corrosion, the disinfection of water, neurophysiology, sensors, energy storage, semiconductors, the physics of thunderstorms, biomedical analysis, and so on.

This book treats electrochemistry as a science in its own right, albeit resting firmly on foundations provided by chemistry, physics, and mathematics. Early chapters discuss the electrical and chemical properties of materials from which electrochemical cells are constructed. The behavior of such cells is addressed in later chapters, with emphasis on the electrodes and the reactions that occur on their surfaces. The role of transport to and from electrodes is a topic that commands attention, because it crucially determines cell efficiency. Final chapters deal with voltammetry, the methodology used to investigate electrode behavior. Interspersed among the more fundamental chapters are chapters devoted to applications of electrochemistry: electrosynthesis, power sources, “green electrochemistry”, and corrosion.

Electrochemical Science and Technology is addressed to all who have a need to come to grips with the fundamentals of electrochemistry and to learn about some of its applications. It will constitute a text for a senior undergraduate or graduate course in electrochemistry. It also serves as a source of material of interest to scientists and technologists in various fields throughout academia, industry, and government – chemists, physicists, engineers, environmentalists, materials scientists, biologists, and those in related endeavors.

This book:

• Provides a background to electrochemistry, as well as treating the topic itself.
• Is accessible to all with a foundation in physical science, not solely to chemists.
• Is addressed both to students and those later in their careers.
• Features web links (through http://www.wiley.com/go/EST to extensive material that is of a more tangential, specialized, or mathematical nature.
• Includes questions as footnotes to support the reader’s evolving comprehension of the material, with fully worked answers provided on the web.
• Provides web access to Excel® spreadsheets which allow the reader to model electrochemical events.
• Has a copious Appendix of relevant data.

Leseprobe

Contents

Cover

Half Title page

Title page

Copyright page

Preface

Chapter 1: Electricity

Electric Charge: The Basis of Electricity

Charges at Rest: Electric Field and Electrical Potential

Capacitance and Conductance: The Effects of Electric Fields on Matter

Mobilities: The Movement of Charged Particles in an Electric Field

Electrical Circuits: Models of Electrochemical Behavior

Alternating Electricity: Sine-Waves and Square-Waves

Summary

Chapter 2: Chemistry

Chemical Reactions: Changes in Oxidation State

Gibbs Energy: The Property that Drives Chemical Reactions

Activity: Restlessness in Chemical Species

Ionic Solutions: The Behavior of Dissolved Ions

Ionic Activity Coefficients: The Debye-Hückel Model

Chemical Kinetics: Rates and Mechanisms of Reactions

Summary

Chapter 3: Electrochemical Cells

Equilibrium Cells: Two Electrochemical Equilibria Generate an Interelectrode Voltage

Cells not at Equilibrium: Interchanges of Chemical and Electrical Energy

Cells with Junctions: Two Ionic Solutions Prevented from Mixing

Summary

Chapter 4: Electrosynthesis

Metal Production: Many Metals are Made or Purified Electrolytically

The Chloralkali Industry: A Bounty of Products from Salt and Water

Organic Electrosynthesis: Nylon from Natural Gas

Electrolysis of Water: Key to the Hydrogen Economy?

Selective Membranes: A Quiet Revolution in Small-Scale Inorganic Electrosynthesis

Summary

Chapter 5: Electrochemical Power

Types of Electrochemical Power Source: Primary or Secondary Batteries, Fuel Cells

Battery Characteristics: Quantifying the Properties of Batteries

Primary Batteries: The Leclanché Cell and its Successors

Secondary Batteries: Charge, Discharge, Charge, Discharge, Charge, …

Fuel Cells: Limitless Electrical Energy in Principle, Many Problems in Practice

Summary

Chapter 6: Electrodes

Electrode Potentials: The Reference Electrode is the Key

Standard Electrode Potentials: They are Related to Standard Gibbs Energies

The Nernst Equation: How Activities Influence Electrode Potentials

Electrochemical Series: Elaboration into Pourbaix Diagrams

Working Electrodes: Constructed from Many Materials in Many Shapes and Sizes

Summary

Chapter 7: Electrode Reactions

Faraday’s Law: Necessities for an Electrode Reaction

Kinetics of a Simple Electron Transfer: The Butler-Volmer Equation

Multi-step Electrode Reactions: Studying Kinetics to Elucidate Mechanisms

Summary

Chapter 8: Transport

Flux Density: Solutes in Motion Obey Conservation Laws

Three Transport Modes: Migration, Diffusion and Convection

Migration: Ions Moving in Response to an Electric Field

Diffusion: Fick’s Two Important Laws

Diffusion and Migration: They May Cooperate Or Oppose

Convection: Transport Controlled by Hydrodynamics

Fluxes at Electrodes and in the Bulk: Transport Coefficients

Summary

Chapter 9: Green Electrochemistry

Sensors for Pollution Control: Keeping Watch on Contaminant Levels

Stripping Analysis: Assaying Pollutants in Water at Nanomolar Levels

Electrochemical Purification of Water: Getting the Nasties Out

Electrochemistry of Biological Cells: Nerve Impulses

Summary

Chapter 10: Electrode Polarization

Three Causes of Electrode Polarization: Sign Conventions and Graphs

Ohmic Polarization: Countered by Adding Supporting Electrolyte

Kinetic Polarization: Currents Limited by Electrode Reaction Rates

Transport Polarization: Limiting Currents

Multiple Polarizations: The Big Picture

Polarizations in Two- and Three-Electrode Cells: The Potentiostat

Summary

Chapter 11: Corrosion

Vulnerable Metals: Corrosive Environments

Corrosion Cells: Two Electrodes on the Same Interface

Electrochemical Studies: Corrosion Potential and Corrosion Current

Concentrated Corrosion: Pits and Crevices

Fighting Corrosion: Protection and Passivation

Extreme Corrosion: Stress Cracking, Embrittlement, and Fatigue

Summary

Chapter 12: Steady-State Voltammetry

Features of Voltammetry: Purpose and Classification

Microelectrodes and Macroelectrodes: Size Matters

Steady-State Potential-Step Voltammetry: Reversibility

The Disk Microelectrode: Convenient Experimentally, Awkward to Model

Rotating Disk Voltammetry: A Spinning Disk Electrode without and with a Ring

Shapes of Reversible Voltammograms: Waves, Peaks and Hybrids

Summary

Chapter 13: The Electrode Interface

Double Layers: Three Models of Capacitance

Adsorption: Invasion of the Interface

The Interface in Voltammetry: Nonfaradaic Current, Frumkin Effects

Nucleation and Growth: Bubbles and Crystals

Summary

Chapter 14: Other Interfaces

Semiconductor Electrodes: Capturing the Energy of Light with Photochemistry

Phenomena at Liquid|Liquid Interfaces: Transfers Across “ITIES”

Electrokinetic Phenomena: The Zeta Potential

Summary

Chapter 15: Electrochemistry with Periodic Signals

Nonfaradaic Effects of A.C.: Measuring Conductance and Capacitance

Faradaic Effects of A.C.: Impedance, Harmonics, Rectification

Equivalent Circuits: Deciphering the Impedance

AC Voltammetry: Discriminating Against Capacitive Current

Fourier-Transform Voltammetry: The Harmonic Response to an A.C. Signal

Summary

Chapter 16: Transient Voltammetry

Modeling Transient Voltammetry: Mathematics, Algorithms, or Simulations

Potential-Step Voltammetry: Single, Double and Multiple

Pulse Voltammetries: Normal, Differential and Square

Ramped Potentials: Linear-Scan Voltammetry and Cyclic Voltammetry

Multiple Electron Transfers: The EE Scheme

Chemistry Combined with Electrochemistry: A Plethora of Mechanistic Possibilities

Controlling Current Instead of Potential: Chronopotentiometry

Summary

Appendix

Glossary: Symbols, Abbreviations, Constants, Definitions, and Units

Absolute and Relative Permittivities: Also Some Dipole Moments

Properties of Liquid Water: SI Values at T° and p°

Conductivities and Resistivities: Assorted Charge Carriers

Elements with Major Importance in Electrochemistry: Properties

Transport Properties: Mostly of Ions in Water

Standard Gibbs Energies: Key to Calculating ΔE° and E° Values

Standard Electrode Potentials: Some Examples

Index

ELECTROCHEMICAL SCIENCE AND TECHNOLOGYFundamentals and Applications

This edition first published 2012© 2012 John Wiley & Sons, LtdReprinted with corrections 2013

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Library of Congress Cataloging-in-Publication Data

Oldham, Keith B.Electrochemical science and technology: fundamentals and applications / Keith B. Oldham, Jan C. Myland,Alan M. Bond.p. cm.Includes bibliographical references and index.ISBN 978-0-470-71085-2 (cloth) – ISBN 978-0-470-71084-5 (pbk.) – ISBN 978-1-119-96588-6 (ePDF) –ISBN 978-1-119-96599-2 (oBook) – ISBN 978-1-119-96684-5 (ePub.) – ISBN 978-1-119-96685-2 (Mobi)1. Electrochemistry. I. Myland, Jan C. II. Bond, A. M. (Alan Maxwell), 1946- III. Title.QD553.O42 2011541’.37–dc232011037230

A catalogue record for this book is available from the British Library.

Print ISBN: 9780470710852 (HB)

Print ISBN: 9780470710845 (PB)

Preface

This book is addressed to all who have a need to come to grips with the fundamentals of electrochemistry and to learn about some of its applications. It could serve as a text for a graduate, or senior undergraduate, course in electrochemistry at a university or college, but this is not the book’s sole purpose.

The text treats electrochemistry as a scientific discipline in its own right, not as an offshoot of physical or analytical chemistry. Though the majority of its readers will probably be chemists, the book has been carefully written to serve the needs of scientists and technologists whose background is in a discipline other than chemistry. Electrochemistry is a quantitative science with a strong reliance on mathematics, and this text does not shy away from the mathematical underpinnings of the subject.

To keep the size and cost of the book within reasonable bounds, much of the more tangential material has been relegated to “Webs” – internet documents devoted to a single topic – that are freely accessible from the publisher’s website at www.wiley.com/go/EST. By this device, we have managed largely to avoid the “it can be shown that” statements that frustrate readers of many textbooks. Other Webs house worked solutions to the many problems that you will find as footnotes scattered throughout the pages of Electrochemical Science and Technology. Another innovation is the provision of Excel® spreadsheets to enable the reader to construct accurate cyclic (and other) voltammograms; see Web#1604 and Web#1635 for details.

It was in 1960 that IUPAC (the International Union of Pure and Applied Chemistry) officially adopted the SI system of units, but electrochemists have been reluctant to abandon centimeters, grams and liters. Here, with some concessions to the familiar units of concentration, density and molar mass, we adopt the SI system almost exclusively. IUPAC’s recommendations for symbols are not always adhered to, but (on pages 195 and 196) we explain how our symbols differ from those that you may encounter elsewhere. On the same pages, we also address the thorny issue of signs.

Few references to the original literature will be found in this book, but we frequently refer to monographs and reviews, in which literature citations are given. We recommend Chapter IV of F. Scholz (Ed.), Electroanalytical Methods: guide to experiments and applications 2E, Springer, 2010, for a comprehensive listing of the major textbooks, monographs and journals that serve electrochemistry.

The manuscript has been carefully proofread but, nevertheless, errors and obscurities doubtless remain. If you discover any such anomalies, we would appreciate your bringing it to our attention by emailing [email protected]. A list of errata will be maintained on the book’s website, www.wiley.com/go/EST.

Electrochemical Science and Technology: fundamentals and applications has many shortcomings of which we are aware, and doubtless others of which we are ignorant, and for which we apologize. We are pleased to acknowledge the help and support that we have received from Tunde Bond, Steve Feldberg, Hubert Girault, Bob de Levie, Florian Mansfeld, David Rand, members of the Electrochemistry Group at Monash University, the Natural Sciences and Engineering Research Council of Canada, the Australian Research Council, and the staff at Wiley’s Chichester office.

July 2011

Keith B.OldhamJan C. MylandAlan M. Bond