Table of Contents
Techniques and Mechanisms in Electrochemistry
Preface
Contents
List of Symbols
1¡ª Introduction to Modern Electrochemistry
1.1¡ªStructure of Surfaces
1.1.1¡ªStructure of the Solid Electrode
1.1.2¡ªThe Structure of the Electrified Interface
1.1.3¡ªAdsorption on the Electrode Surface
1.2¡ªElectron Transfer
1.2.1¡ªThermodynamic Considerations
1.2.2¡ªRate of Electron Transfer
1.2.3¡ªRate of Transport of Solution Species
1.3¡ªReaction Mechanisms
1.3.1¡ªHomogeneous Electrochemical Mechanisms
1.3.2¡ªElectrochemical Mechanisms with Adsorbed Intermediates
1.3.3¡ªThe Direct Detection of Intermediates
Further Reading
2¡ª Techniques Giving Mechanistic Information
2.1¡ªSurface Specific Processes-In Situ Techniques
2.1.1¡ªElectrocapillarity
2.1.2¡ªLinear Sweep Voltammetry and Cyclic Voltammetry
2.1.3¡ªScanning Tunnelling Microscopy
2.1.4¡ªScanning Tunnelling Spectroscopy
2.1.5¡ªAtomic Force Microscopy
2.1.6¡ªInfrared Spectroscopy
2.1.6.1¡ªTransmission
2.1.6.2¡ªInternal Reflectance (Attenuated Total Reflectance ATR)
2.1.6.3¡ªExternal Reflectance
2.1.6.4¡ªElectrically Modulated Infrared Spectroscopy, (EMIRS)
2.1.6.5¡ªPolarisation Modulation Infrared Reflection-Absorption Spectroscopy (PM IRRAS
or IRRAS)
2.1.6.6¡ªIn-Situ Fourier transform Unfrared Spectroscopy
2.1.7¡ªThe Raman Spectroscopies
2.1.8¡ªEllipsometry
2.1.9¡ªX-Ray Spectroscopies
2.1.9.1¡ªX-Ray Diffraction
2.1.9.2¡ªSurface Extended X-Ray Absorption Fine Structure (SEXAFS)
2.1.9.3¡ªLong Period X-Ray Standing Waves (XSW)
2.1.9.4¡ªSpecular X-Ray Reflection
2.1.10¡ªAC Techniques
2.2¡ª In Situ Probes of the Near-Electrode Region
2.2.1¡ªChronoamperometry, Chronocoulometry and the Butler¨CVolmer Equation
2.2.2¡ªVoltammetry
2.2.3¡ªThe Controlled-Convection Techniques: The Rotating Disc and Rotating Ring-
Disc Electrodes
2.2.4¡ªElectron Paramagnetic Resonance
2.2.4.1¡ªThe g-factor
2.2.4.2¡ªHyperfine Splitting
2.2.5¡ªUV-Visible Spectroelectrochemistry
2.2.6¡ªThe Electrochemical Quartz Crystal Microbalance
2.2.7¡ªFTIR and Related Techniques
2.2.7.1¡ªTransmittance
2.2.7.2¡ªExternal Reflectance
2.2.8¡ªMass Spectrometry Techniques ¨C DEMS
2.3¡ªEx Situ Emersion Techniques
2.3.1¡ªStructural and Analytical Methods
2.3.2¡ªMass Spectrometric Techniques
References
Further Reading
3¡ª Examples of the Application of Electrochemical Methods
3.1¡ª The Cyclic Voltammogram of Platinum in Acid Solution
3.1.1¡ªThe Hydride Region
3.1.2¡ªThe Oxide Region
3.1.3¡ªThe Voltammetry of Single-Crystal Platinum Electrodes
3.2¡ªThe Electro-Oxidation of Methanol at Platinum in Acid Solution
3.2.1¡ªMethanol Oxidation at a Smooth Polished Polycrystalline Platinum Electrode
3.3¡ªThe Electrochemical Reduction of CO[sub(2)]
3.3.1¡ªThe Direct Reduction of CO[sub(2)] in Non-Aqueous Solvents
3.3.2¡ªThe Catalysed Reduction of CO[sub(2)]
3.4¡ªReactive Film Formation on Electrodes
3.4.1¡ªOxide Formation on Metals: The Nature of the Passive Film on Iron
3.4.2¡ªConducting Polymers
3.3.2.1¡ªStructure
3.3.2.2¡ªStatic Measurements
3.3.2.3¡ªDynamic Properties
3.5¡ªAdsorbed Films for the Promotion of Enzyme Electrochemistry
References
Further Reading
Index