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Written by two of the world's leading authorities in the field of electrochemistry, this book comprehensively addresses workhorse electrochemical reactions that serve as the basis of modern research for alternative energy solutions.
Provides an accessible and readable summary on the use of electrochemical techniques and the applications of electrochemical concepts to functional molecular-level systems
Includes a new chapter on proton coupled electron transfer, a completely revamped chapter on molecular catalysis of electrochemical reactions, and added sections throughout the book
Bridges a gap and strengthens the relationship between electrochemists, molecular and biomolecular chemists--showing a variety of functions that may be obtained by multi-component systems designed using the paradigms of both chemistries
Auteur
JEAN-MICHEL SAVÉANT is a Professor of Chemistry at Denis Diderot University of Paris, France, a member of the French Academy of Sciences, and a foreign associate of the National Academy of Sciences of the USA. CYRILLE COSTENTIN is a Professor of Chemistry at Denis Diderot University of Paris, France.
Texte du rabat
PROVIDES AN UPDATE ON ELECTRON TRANSFER CHEMISTRY USING ELECTROCHEMICAL PRINCIPLES AND SERVES AS A ROADMAP TO THE FIELD OF ELECTROCHEMISTRY Written by two of the world's leading authorities in the field of electrochemistry, this book comprehensively addresses workhorse electrochemical reactions that serve as the basis of modern research for alternative energy solutions. It updates the previous edition and adds substantial new information throughoutmost of which concerns proton-coupled electron transfer reactions and molecular catalysis of electrochemical reactionsand includes extended appendices for the reader. Elements of Molecular and Biomolecular Electrochemistry: An Electrochemical Approach to Electron Transfer Chemistry, 2nd Edition??offers chapters covering such topics as: single electron transfer at an electrode; coupling of electrode electron transfers with homogeneous chemical reactions; coupling between electron transfer and heavy atom-bond breaking and formation; proton-coupled electron transfers; molecular catalysis of electrochemical reactions; and enzymatic catalysis of electrochemical reactions. It is a handy, single source of key information, and will be invaluable in the research of alternative energy sources in the years to come.
Contenu
Preface xv
1 Single-Electron Transfer at an Electrode 1
1.1 Introduction 1
1.2 Cyclic Voltammetry of Fast Electron Transfers: Nernstian Waves 2
1.2.1 One-Electron Transfer to Molecules Attached to the Electrode Surface 2
1.2.2 One-Electron Transfer to Free-moving Molecules 6
1.3 Technical Aspects 10
1.3.1 The Cyclic Voltammetry Experiment Faradaic and Double-Layer Charging Currents. Ohmic Drop 10
1.3.2 Other Techniques. Convolution 21
1.4 Electron Transfer Kinetics 29
1.4.1 Introduction 29
1.4.2 ButlerVolmer Law and MarcusHushLevich (MHL) Model 31
1.4.3 Extraction of Electron Transfer Kinetics from Cyclic Voltammetric Signals. Comparison with Other Techniques 46
1.4.4 Experimental Testing of the Electron Transfer Models 59
1.5 Successive One-Electron Transfers vs. Two-Electron Transfers 64
1.5.1 Introduction 64
1.5.2 Cyclic Voltammetric Responses: Convolution 66
1.5.3 Response of Molecules Containing Identical and Independent Reducible or Oxidizable Groups 72
1.5.4 An Example of the Predominating Role of Solvation: The Oxidoreduction of Carotenoids 72
1.5.5 An Example of the Predominating Role of Structural Changes: The Reduction of trans-2,3-Dinitro-2-butene 75
References 77
2 Coupling of Electrode Electron Transfers with Homogeneous Chemical Reactions 81
2.1 Introduction 81
2.2 Establishing the Mechanism and Measuring the Rate Constants for Homogeneous Reactions by Means of Cyclic Voltammetry and Potential Step Chronoamperometry 83
2.2.1 The EC Mechanism 83
2.2.2 The CE Mechanism 97
2.2.3 The Square Scheme Mechanism 99
2.2.4 The ECE and DISP Mechanisms 100
2.2.5 Electrodimerization 107
2.2.6 Homogeneous Catalytic Reaction Schemes 113
2.2.6.1 Homogeneous Electron Transfer as the Rate-Determining Step 114
2.2.6.2 Homogeneous Catalytic EC Mechanism 117
2.2.6.3 Deactivation of the Mediator 120
2.2.7 Electrodes as Catalysts: Electron-transfer Catalyzed Reactions 122
2.2.8 Numerical Computations: Simulations, Diagnostic Criteria, Working Curves 125
2.3 Product Distribution in Preparative Electrolysis 129
2.3.1 Introduction 129
2.3.2 General Features 130
2.3.3 Product Distribution Resulting from Competition Between Follow-Up Reactions 133
2.3.4 The ECEDISP Competition 135
2.3.5 Other Reactions Schemes 136
2.4 Classification and Examples of Electron-Transfer Coupled Chemical Reactions 137
2.4.1 Coupling of Single Electron Transfer with AcidBase Reactions 137
2.4.2 Electrodimerization 146
2.4.3 Electropolymerization 150
2.4.4 Reduction of Carbon Dioxide 151
2.4.5 H-Atom Transfer vs. Electron + Proton Transfer 153
2.4.6 The SRN1 Substitution: Electrodes and Electrons as Catalysts 157
2.4.7 Conformational Changes, Isomerization and Electron Transfer 162
2.5 Redox Properties of Transient Radicals 167
2.5.1 Introduction 167
2.5.2 The Direct Electrochemical Approach 167
2.5.3 Laser Flash Electron Injection 172
2.5.4 Photomodulation Voltammetry 176
2.6 Electrochemistry as a Trigger for Radical Chemistry or for Ionic Chemistry 177
References 179
3 Coupling Between Electron Transfer and Heavy Atom-Bond Breaking and Formation 183
3.1 Introduction 183
3.2 Dissociative Electron Transfer 185
3.2.1 Thermodynamics: Microscopic Reversibility 185
3.2.2 The Morse Curve Model 188
3.2.3 Values of the Symmetry Factor and Variation with the Driving Force 193
3.2.4 Entropy of Activation 195
3.3 Interactions Between Fragments in the Product Cluster 196
3.3.1 Influence on the Dynamics of Dissociative Electron Transfers 197
3.3.2 A Typical Example: Dissociative Electron Transfer to Carbon Tetrachloride 198 3.3.3 Stabilities of Ion-radica...