Electrochemistry of Immobilized Particles and Droplets (eBook)

Experiments with Three-Phase Electrodes

Fritz Scholz, Uwe Schröder, Rubin Gulaboski, Antonio Doménech-Carbó (Autoren)

eBook Download: PDF

2014 | 2nd ed. 2015
XV, 327 Seiten
Springer International Publishing (Verlag)
978-3-319-10843-8 (ISBN)

Infos

This second edition of a successful and highly-accessed monograph has been extended by more than 100 pages. It includes an enlarged coverage of applications for materials characterization and analysis. Also a more detailed description of strategies for determining free energies of ion transfer between miscible liquids is provided. This is now possible with a 'third-phase strategy' which the authors explain from theoretical and practical points of view. The book is still the only one detailing strategies for solid state electroanalysis. It also features the specific potential of the techniques to use immobilized particles (for studies of solid materials) and of immobilized droplets of immiscible liquids for the purpose of studying the three-phase electrochemistry of these liquids. This also includes studies of ion transfer between aqueous and immiscible non-aqueous liquids. The bibliography of all published papers in this field of research has been expanded from 318 to now 444 references in this second edition. Not only are pertinent references provided at the end of each chapter, but the complete list of the cited literature is also offered as a separate chapter for easy reference.

Inhalt

Foreword to the First Edition 6
Preface to the Second Edition 8
Preface to the First Edition 10
Contents 14
Chapter 1: Earlier Developed Techniques 17
1.1 Solid Materials 19
1.1.1 Compact Electrodes 19
Electrography 20
1.1.2 Electrochemistry of Suspensions and Colloids 20
Noncolloidal Suspensions 20
Colloidal Solutions 22
1.1.3 Paste and Composite Electrodes 23
1.1.4 Sandwich Electrodes 25
1.2 Immiscible Liquids and Solutions 25
Chapter 2: Electrodes with Immobilized Particles and Droplets: Three-Phase Electrodes 27
References 33
Chapter 3: The Experiment 34
3.1 Electrodes, Electrolytes, and Electrochemical Cells 34
3.1.1 Electrodes 34
3.1.2 Electrolytes and Electrochemical Cells 36
3.2 Immobilization of Particles 37
3.3 Attachment of Droplets 39
3.3.1 Attachment of Single Droplets 40
3.3.2 Attachment of Arrays of Microdroplets 41
3.4 The Electrochemical Measurement 43
References 45
Chapter 4: Hyphenated Techniques 48
4.1 Optical Techniques and Spectroelectrochemistry 49
4.1.1 In Situ Spectroscopy 49
4.1.2 In Situ Light Microscopy and Microscopic Spectroelectrochemistry 51
In Situ Incident Light Microscopy 52
In Situ Transmission Light Microscopy 57
4.1.3 In Situ Electron Spin Resonance Spectroscopy 59
4.1.4 Ex Situ Spectroscopy 62
Scanning Electron Microscopy and X-Ray Electron Probe Microanalysis 63
4.2 Atomic Force Microscopy and Scanning Tunneling Microscopy 63
4.3 Scanning Electrochemical Microscopy 74
4.4 Electrochemical Quartz Crystal Microbalance 75
4.5 In Situ X-Ray Diffraction 79
4.6 In Situ Calorimetry 81
References 92
Chapter 5: Immobilized Particles 96
5.1 Metals and Alloys 99
5.1.1 Abrasive Voltammetry of Metals and Alloys 99
5.1.2 Age Determination 103
5.1.3 Solution Analysis by Electrochemical Analysis of a Solid Precipitate 109
5.2 Minerals and Pigments 110
5.2.1 Phase Identification 110
5.2.2 Quantitative Determination of a Phase in a Phase Mixture 121
5.2.3 Quantitative Analysis of the Composition of a Phase 127
5.2.4 Determination of Thermodynamic Data of Minerals 130
5.3 Solid Solutions: Identification and Quantitative Analysis 132
5.3.1 The Solid Solution System CuS-CuSe 133
5.3.2 The Solid Solution System AgCl-AgBr 135
5.3.3 Solid Solutions of Metal Hexacyanometalates 136
5.3.4 Solid Solutions of Oxides 141
5.4 Organometallics and Organic Compounds 141
5.4.1 Voltammetry of Organometallic Compounds 143
5.4.2 Voltammetry of Organic Compounds 154
5.4.3 Voltammetry of Organic Pigments and Hybrid Materials 160
5.4.4 Overview of Studied Compounds 165
5.5 Electrochemically Initiated Chemical Reactions of Solid Particles 167
5.5.1 Electrochemically Initiated Isomerizations 167
5.5.2 Electrochemically Initiated Substitutions 171
5.6 Assessing Structure-Property Relationships 177
5.6.1 Solid Metal Hexacyanometalates 177
5.6.2 The Stability Constants of Metal Dithiocarbamate Complexes and Their Structure 180
5.7 Assessing Kinetic Properties of Electrochemical Dissolution Reactions 183
5.8 The Electrochemistry of Single Particles 188
5.9 Chemical and Enzymatic Conversion of Immobilized Particles 192
5.9.1 In Situ Studies 192
5.9.2 Ex Situ Studies 194
5.10 The Screening of Electrocatalysts 197
5.11 Theoretical Aspects of the Voltammetry of Immobilized Particles 197
5.11.1 Staircase Voltammetry with Finite Diffusion Space 198
5.11.2 The Propagation of a Redox Reaction Through Microcrystals 200
5.11.3 The Effect of the Electrolyte Concentration on the Voltammetric Response of Insertion Electrodes 204
5.11.4 Solid-State Voltammetry at a Three-Phase Junction 206
5.11.5 The Effect of Crystal Size and Shape on Electrochemical Signals 210
5.11.6 Redox Mixed Phases and Miscibility Gaps 214
5.11.7 Electrochemically Driven Formation of Bilayered Systems 219
References 223
Chapter 6: Immobilized Droplets 240
6.1 The Electrochemistry of Redox Liquids 244
6.1.1 Electrochemically Driven Ion Transfer Reactions 246
6.1.2 Voltammetric Study of Chemically Facilitated Ion Transfer Processes Across the Liquid-Liquid Interface 253
6.1.3 Photochemical and Chemical Reactions at Immobilized Microdroplets of Redox Liquids 255
6.2 The Electrochemistry of Compounds Dissolved in Droplets 263
6.2.1 The Determination of Standard Gibbs Energies of Transfer of Anions 268
The Transfer of Chiral Ions Across the Water-Chiral Organic Liquid Interface 272
6.2.2 The Determination of Standard Gibbs Energies of Transfer of Cations 275
Standard Gibbs Energies of Transfer of Cations Determined by Utilizing the Reduction of Iodine 277
6.2.3 The Determination of Standard Gibbs Energies of Transfer of Anions and Cations Between Miscible Solvents: The ``Third Ph... 279
6.3 Theoretical Models for the Voltammetry of Immobilized Droplets 283
6.3.1 Droplets of Organic Solvents with Dissolved Electroactive Compound 283
Semi-infinitive Planar Diffusion Model 283
A Convolutive Model for Cyclic Voltammetry in a Thin Organic Layer 286
Modeling Cyclic Voltammograms at a Conic Drop Three-Phase Electrode 288
Uncompensated Resistance and Charge Transfer Kinetics 292
The Effect of Migration 296
6.3.2 Droplets of Electroactive Liquids 298
Numerical Modeling of Three Possible Mechanisms 298
Cyclic Voltammetry Response of Partially Blocked Electrodes 301
6.3 Conclusions 303
References 307
Bibliography 311
Index 337

Produkt-Details

• Erscheint lt. Verlag: 27.11.2014
• Zusatzinfo: XV, 327 p. 231 illus., 10 illus. in color.
• Verlagsort: Cham
• Sprache: englisch
• Themenwelt: Naturwissenschaften ► Chemie ► Physikalische Chemie
• Themenwelt: Naturwissenschaften ► Physik / Astronomie
• Themenwelt: Technik ► Maschinenbau
• Schlagworte: Electrochemistry of Immobilized Droplets • Electrochemistry of Immobilized Particles • Electrodes with Immobilized Droplets • Electrodes with Immobilized Particles • Ion Transfer Between Liquid Phases • Solid-state Electroanalysis • Three-phase Electrochemistry • Three-phase Electrodes
• ISBN-10: 3-319-10843-3 / 3319108433
• ISBN-13: 978-3-319-10843-8 / 9783319108438