techniques and mechanisms in electrochemistry 1994 - hammett

Techniques and Mechanisms in Electrochemistry
P.A. Christensenand A. Hamnett
Department of Chemistry University
of Newcastle upon Tyne

Kluwer Academic Publishers 1994

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Library of Congress Cataloging-in-Publication data
Christensen, P.A., 1960–
Techniques and mechanisms in electrochemistry / P.A. Christensen
and A. Hamnett. 1st ed.
p
. cm.
Includes bibliographical references and index.
ISBN 0-7514-0129-3 (PB : acid-free)
1. Electrochemistry. 2. Surface chemistry. I. Hamnett, A.
II. Title.
QD553.C59 1993
541.3'7 dc20 93-11366

Techniques and Mechanisms in Electrochemistry

by Christensen, P. A.; Hamnett, A.
Table of Contents


Techniques and Mechanisms in Electrochemistry


Preface


Contents

List of Symbols


1— Introduction to Modern Electrochemistry


1.1—Structure of Surfaces


1.1.1—Structure of the Solid Electrode


1.1.2—The Structure of the Electrified Interface


1.1.3—Adsorption on the Electrode Surface


1.2—Electron Transfer


1.2.1—Thermodynamic Considerations


1.2.2—Rate of Electron Transfer


1.2.3—Rate of Transport of Solution Species

1.3—Reaction Mechanisms


1.3.1—Homogeneous Electrochemical Mechanisms


1.3.2—Electrochemical Mechanisms with Adsorbed Intermediates


1.3.3—The Direct Detection of Intermediates


Further Reading


2— Techniques Giving Mechanistic Information


2.1—Surface Specific Processes-In Situ Techniques


2.1.1—Electrocapillarity


2.1.2—Linear Sweep Voltammetry and Cyclic Voltammetry


2.1.3—Scanning Tunnelling Microscopy

2.1.4—Scanning Tunnelling Spectroscopy


2.1.5—Atomic Force Microscopy


2.1.6—Infrared Spectroscopy


2.1.6.1—Transmission


2.1.6.2—Internal Reflectance (Attenuated Total Reflectance ATR)


2.1.6.3—External Reflectance


2.1.6.4—Electrically Modulated Infrared Spectroscopy, (EMIRS)


2.1.6.5—Polarisation Modulation Infrared Reflection-Absorption Spectroscopy (PM-
IRRAS or IRRAS)


2.1.6.6—In-Situ Fourier transform Unfrared Spectroscopy

2.1.7—The Raman Spectroscopies


2.1.8—Ellipsometry


2.1.9—X-Ray Spectroscopies


2.1.9.1—X-Ray Diffraction


2.1.9.2—Surface Extended X-Ray Absorption Fine Structure (SEXAFS)


2.1.9.3—Long Period X-Ray Standing Waves (XSW)


2.1.9.4—Specular X-Ray Reflection


2.1.10—AC Techniques


2.2— In Situ Probes of the Near-Electrode Region


2.2.1—Chronoamperometry, Chronocoulometry and the Butler–Volmer Equation

2.2.2—Voltammetry


2.2.3—The Controlled-Convection Techniques: The Rotating Disc and Rotating Ring-
Disc Electrodes


2.2.4—Electron Paramagnetic Resonance


2.2.4.1—The g-factor


2.2.4.2—Hyperfine Splitting


2.2.5—UV-Visible Spectroelectrochemistry


2.2.6—The Electrochemical Quartz Crystal Microbalance


2.2.7—FTIR and Related Techniques


2.2.7.1—Transmittance


2.2.7.2—External Reflectance

2.2.8—Mass Spectrometry Techniques – DEMS


2.3—Ex Situ Emersion Techniques


2.3.1—Structural and Analytical Methods


2.3.2—Mass Spectrometric Techniques


References


Further Reading


3— Examples of the Application of Electrochemical Methods


3.1— The Cyclic Voltammogram of Platinum in Acid Solution


3.1.1—The Hydride Region


3.1.2—The Oxide Region

3.1.3—The Voltammetry of Single-Crystal Platinum Electrodes


3.2—The Electro-Oxidation of Methanol at Platinum in Acid Solution


3.2.1—Methanol Oxidation at a Smooth Polished Polycrystalline Platinum Electrode


3.3—The Electrochemical Reduction of CO[sub(2)]


3.3.1—The Direct Reduction of CO[sub(2)] in Non-Aqueous Solvents


3.3.2—The Catalysed Reduction of CO[sub(2)]


3.4—Reactive Film Formation on Electrodes


3.4.1—Oxide Formation on Metals: The Nature of the Passive Film on Iron


3.4.2—Conducting Polymers


3.3.2.1—Structure

3.3.2.2—Static Measurements


3.3.2.3—Dynamic Properties


3.5—Adsorbed Films for the Promotion of Enzyme Electrochemistry


References


Further Reading


Index