Understanding Voltammetry: : Problems and Solutions

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Understanding Voltammetry: : Problems and Solutions

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  • 製本 Hardcover:ハードカバー版/ページ数 253 p.
  • 言語 ENG,ENG
  • 商品コード 9781848167308
  • DDC分類 541.37076

Full Description


The field of electrochemical measurement, with respect to thermodynamics, kinetics and analysis, is widely recognised but the subject can be unpredictable to the novice, even if they have a strong physical and chemical background, especially if they wish to pursue quantitative measurements. Accordingly, some significant experiments are, perhaps wisely, never attempted, while the literature is sadly replete with flawed attempts at rigorous voltammetry.This book presents problems and worked solutions for a wide range of theoretical and experimental subjects in the field of voltammetry. The reader is assumed to have knowledge up to a Master's level of physical chemistry, but no exposure to electrochemistry in general, or voltammetry in particular, is required. The problems included range in difficulty from senior undergraduate to research level, and develop important practical approaches in voltammetry.The problems presented in the earlier chapters focus on the fundamental theories of thermodynamics, electron transfer and diffusion. Voltammetric experiments and their analysis are then considered, including extensive problems on both macroelectrode and microelectrode voltammetry. Convection, hydrodynamic electrodes, homogeneous kinetics, adsorption and electroanalytical applications are discussed in the later chapters, as well as problems on two rapidly developing fields of voltammetry: weakly supported media and nanoscale electrodes.There is huge interest in the experimental procedure of voltammetry at present, and yet no dedicated question and answer book with exclusive voltammetric focus exists, in spite of the inherent challenges of the subject. This book aims to fill that niche.

Table of Contents

Publisher's Foreword                               v
Glossary of Symbols and Abbreviations xiii
1 Equilibrium Electrochemistry and the 1 (34)
Nernst Equation
1.1 Cell Thermodynamics 1 (1)
1.2 The Nernst Equation 2 (1)
1.3 The Nernst Equation 3 (2)
1.4 The Nernst Equation 5 (1)
1.5 Theory of the Nernst Equation 5 (2)
1.6 The Debye--Huckel Limiting Law 7 (3)
1.7 Cell Reaction and Equilibrium Constant 10 (1)
1.8 Cell Reaction and Equilibrium Constant 11 (1)
1.9 Cell Reaction and Solubility Product 12 (1)
1.10 Cell Reaction and pKa 13 (1)
1.11 Cell Thermodynamics and Temperature 14 (1)
1.12 Cell Thermodynamics and Temperature 15 (1)
1.13 Cell Energetics 16 (1)
1.14 Cell EMF and pH 17 (1)
1.15 Cell Reaction and Equilibria 18 (1)
1.16 Cell Reaction and Kw 19 (1)
1.17 Cell Reaction and Disproportionation 20 (1)
1.18 Fuel Cell Energetics 21 (1)
1.19 Fuel Cell Energetics 22 (1)
1.20 The Influence of Temperature on the 23 (1)
Self-Ionisation of Water
1.21 Cell Reaction and Complexation 24 (2)
1.22 Reference Electrodes 26 (1)
1.23 Formal Potentials 27 (1)
1.24 Formal Potentials 28 (1)
1.25 Standard Potentials and pH 29 (1)
1.26 Standard Potentials and pH 30 (1)
1.27 Standard Potentials and pH 31 (4)
2 Electrode Kinetics 35 (22)
2.1 Faraday's Laws of Electrolysis 35 (1)
2.2 Electrodeposition 36 (3)
2.3 Tafel Analysis: One-Electron Processes 39 (1)
2.4 Tafel Analysis: Electrochemically 39 (2)
Reversible Processes
2.5 Tafel Analysis: Mass Transport 41 (1)
Correction
2.6 Tafel Analysis: Two-Electron Processes 42 (3)
2.7 The Butler--Volmer Equation and the 45 (1)
Nernst Equation
2.8 The Hydrogen Evolution Reaction 46 (1)
2.9 Requirement for Supporting Electrolyte 47 (2)
2.10 Frumkin Corrections 49 (2)
2.11 Marcus Theory and Standard 51 (1)
Electrochemical Rate Constants
2.12 Marcus Theory and Butler--Volmer 52 (2)
Kinetics
2.13 Marcus Theory and the Role of Solvent 54 (1)
2.14 Marcus Theory and the Inverted Region 55 (2)
3 Diffusion 57 (10)
3.1 Fick's Laws of Diffusion 57 (1)
3.2 Fick's Laws of Diffusion 58 (1)
3.3 Diffusion Distances 59 (1)
3.4 The Cottrell Equation 60 (2)
3.5 Derivation of the Cottrell Equation 62 (4)
3.6 Diffusion and Root-Mean-Square 66 (1)
Displacement
4 Cyclic Voltammetry at Macroelectrodes 67 (24)
4.1 Cyclic Voltammetry: Electrochemically 67 (2)
Reversible Voltammetry
4.2 Cyclic Voltammetry: Electrochemically 69 (2)
Irreversible Voltammetry
4.3 Reversible vs Irreversible Voltammetry 71 (1)
4.4 Voltammetric Diagnostics 72 (1)
4.5 Voltammetry and Scan Rate Effects 73 (2)
4.6 Ferrocene Voltammetry 75 (1)
4.7 Ferrocene Voltammetry 75 (1)
4.8 Features of Cyclic Voltammograms 76 (1)
4.9 Derivation of the Randles--Sevcik 77 (4)
Equation
4.10 Reversible Two-Electron Transfer 81 (1)
4.11 The Influence of pH on Cyclic 82 (2)
Voltammetry
4.12 The Scheme of Squares 84 (2)
4.13 The EE-Comproportionation Mechanism 86 (5)
5 Voltammetry at Microelectrodes 91 (20)
5.1 Steady-State Concentration Profile in 91 (2)
Spherical Space
5.2 Current Transients at a Spherical 93 (1)
Electrode
5.3 Linear vs Convergent Diffusion 94 (1)
5.4 Dissolution of Microparticles 95 (2)
5.5 Steady-State Limiting Current at a 97 (1)
Microdisc
5.6 Microdisc vs Planar Electrode 98 (1)
5.7 The Shoup--Szabo Equation 98 (2)
5.8 Steady-State Electrolysis 100 (1)
5.9 Effect of Unequal Diffusion 101 (1)
Coefficients
5.10 Temperature Effects on Steady-State 101 (2)
Currents
5.11 ECE Mechanism at a Microdisc 103 (2)
Electrode
5.12 EC' Mechanism at a Microdisc 105 (1)
Electrode
5.13 Size Effects on Half-Wave Potentials 106 (1)
5.14 Extracting Parameters from Microdisc 107 (2)
Chronoamperometry
5.15 Extracting Parameters from Microdisc 109 (2)
Chronoamperometry
6 Voltammetry at Heterogeneous Surfaces 111 (12)
6.1 Graphitic Electrodes 111 (2)
6.2 Carbon Nanotubes and Their Reactivity 113 (1)
6.3 Highly Ordered Pyrolytic Graphite and 114 (1)
the Influence of Defects
6.4 Advantages of Arrays 115 (1)
6.5 Diffusional `Cases' 116 (1)
6.6 Geometry of a Regular Array 117 (2)
6.7 Analysis of Diffusion to Electrode 119 (2)
Arrays
6.8 Partially Blocked Electrodes 121 (2)
7 Cyclic Voltammetry: Coupled Homogeneous 123 (36)
Kinetics and Adsorption
7.1 EE Mechanism and Comproportionation 123 (1)
7.2 EE mechanism: The Reduction of 124 (2)
[(η6-C6Me6)2Ru][BF4]2
7.3 EC2 Mechanism: The Reduction of the 126 (2)
2,6-Diphenyl Pyrylium Cation
7.4 Analysis of an Unknown Reaction 128 (2)
Mechanism
7.5 EC Mechanism: Diethyl Maleate 130 (3)
7.6 ECE Mechanism: p-chlorobenzonitrile 133 (2)
7.7 ECE vs DISP 1: Voltammetry of 135 (2)
Fluorescein
7.8 Reduction of Anthracene in DMF 137 (3)
7.9 CE Mechanism 140 (2)
7.10 EC' Mechanism 142 (1)
7.11 EC' Mechanism: Cysteine and 143 (2)
Ferrocyanide
7.12 EC' Mechanism: Oxygen and 145 (1)
Anthraquinone
7.13 Chronoamperometry of Adsorbed Species 146 (1)
7.14 Voltammetry of an Ideal Adsorbed 147 (3)
Species
7.15 Non-Ideal Adsorbed Species 150 (3)
7.16 Irreversible Electron Transfer and 153 (4)
Adsorbed Redox Species
7.17 Voltammetry of 157 (2)
Ferrocyanide/Ferricyanide
8 Hydrodynamic Electrodes 159 (24)
8.1 Channel Electrodes and Limiting 159 (1)
Currents
8.2 Channel Electrodes and Reynolds Number 160 (1)
8.3 Flow to Rotating Discs and in Channels 161 (1)
8.4 Channel Electrodes and ECE Processes 162 (2)
8.5 Channel Electrodes and ECE Processes 164 (3)
8.6 Channel Electrodes and Entry Length 167 (1)
8.7 Channel Electrodes and Diffusion 167 (2)
Coefficients
8.8 Channel Electrodes and Current 169 (1)
Distribution
8.9 Wall-Jet Electrodes and Current 170 (1)
Distribution
8.10 Wall-Jet Electrodes and Diffusion 170 (2)
Coefficients
8.11 Wall-Jet Electrode and a DISP 1 172 (1)
Process
8.12 Wall-Jet Electrode and EC Processes 173 (4)
8.13 Sono-Voltammetry 177 (1)
8.14 Rotating Disc Electrodes and 178 (1)
Reynolds Number
8.15 Wall-Jet and Rotating Disc Electrodes 178 (2)
8.16 Rotating Disc Electrodes and ECE 180 (3)
Processes
9 Voltammetry for Electroanalysis 183 (28)
9.1 Electrochemical Sizing of Gold 183 (2)
Surfaces
9.2 Differential Pulse Voltammetry 185 (1)
9.3 Square-Wave Voltammetry 186 (1)
9.4 Square-Wave Voltammetry and Dissolved 187 (1)
Oxygen
9.5 Stripping Voltammetry 188 (1)
9.6 Analysis of DNA 189 (2)
9.7 The Clark Cell 191 (2)
9.8 Calibration and Limits of Detection 193 (2)
9.9 Enzyme Electrodes 195 (1)
9.10 Glucose Biosensors 196 (2)
9.11 Detection of Vitamin B12 198 (2)
9.12 The Anodic Stripping Voltammetry of 200 (2)
Industrial Effluent
9.13 Adsorptive Stripping Voltammetry at 202 (3)
Carbon Nanotube Modified Electrodes
9.14 Surface Modified Electrodes 205 (3)
9.15 Electron Transfer Rates at Carbon 208 (3)
Electrodes
10 Voltammetry in Weakly Supported Media: 211 (22)
Migration and Other Effects
10.1 Coulomb's Law 211 (1)
10.2 The Nernst--Planck Equation 212 (3)
10.3 Migration and the Electric Field 215 (2)
10.4 Transport Numbers and Liquid 217 (3)
Junction Potentials
10.5 Transport Numbers and the Hittorf 220 (1)
Method
10.6 The Gouy--Chapman Equation 221 (4)
10.7 Ohmic Drop 225 (2)
10.8 The Zero-Field Approximation 227 (1)
10.9 Self-Supported Reduction of the 228 (5)
Cobaltocenium Cation
11 Voltammetry at the Nanoscale 233 (16)
11.1 Debye Length vs Diffusion Layer 233 (2)
Thickness
11.2 Altered Electrode Kinetics and 235 (1)
Reactivity at the Nanoscale
11.3 Nanoparticles: Case 4 Behaviour 236 (2)
11.4 `Coulomb Staircase' Effects 238 (1)
11.5 Ultrafast `Single Molecule' 239 (3)
Voltammetry
11.6 Thin-Layer Effects in Nanoscale 242 (2)
Voltammetry
11.7 Voltammetry in a Nanochannel 244 (5)
Index 249