Electrochemistry in Nonaqueous Solutions, 2nd Edition

Electrochemistry in Nonaqueous Solutions......Page 5
Contents......Page 7
Preface to the First Edition......Page 13
Preface to the Second Edition......Page 15
Part One: Fundamentals of Chemistry in Nonaqueous Solutions: Electrochemical Aspects......Page 19
1 Properties of Solvents and Solvent Classification......Page 21
1.1.1 Physical Properties of Solvents......Page 26
1.1.2 Chemical Properties of Solvents......Page 31
1.1.3 Structural Aspects of Solvents......Page 35
1.1.4 Toxicity and Hazardous Properties of Solvents......Page 37
1.2 Classification of Solvents......Page 38
1.3 Effects of Solvent Properties on Chemical Reactions: An Outline......Page 40
References......Page 42
2.1 Influence of Ion Solvation on Electrolyte Dissolution......Page 45
2.2.1 Ion–Solvent Interactions Affecting Ion Solvation......Page 47
2.2.2 Structure of Solvated Ions......Page 54
2.2.3 Ultrafast Ion Solvation Dynamics......Page 57
2.3.1 Gibbs Energies of Transfer and Transfer Activity Coefficients of Ions......Page 58
2.3.2 Prediction of Solvent Effects by the Use of Transfer Activity Coefficients......Page 62
2.4 Solvent Effects on the Complexation of Metal Ions......Page 64
2.5 Selective Solvation of Ions in Mixed Solvents......Page 67
2.6 Ion Association and Solvent Permittivities......Page 71
References......Page 77
3.1 Solvent Effects on Acid–base Reactions......Page 81
3.1.1 Acid–Base Reactions in Amphiprotic Solvents of High Permittivity......Page 82
3.1.2 Acid–Base Reactions in Aprotic Solvents of High Permittivity......Page 87
3.1.4 Acid–Base Reactions in Aprotic Solvents of Low Permittivity......Page 97
3.2.1 Definition of pH in Nonaqueous Solutions......Page 98
3.2.2 pH Windows in Nonaqueous Solvents and pH Scales Common to Multisolvents......Page 100
References......Page 104
4.1.1 Fundamentals of Redox Reactions......Page 107
4.1.2 Solvent Effects on Redox Potentials and Redox Reaction Mechanisms......Page 111
4.1.3 Dynamical Solvent Effects on the Kinetics of Redox Reactions......Page 118
4.2 Redox Properties of Solvents and Potential Windows......Page 121
4.3.1 Titrations with Oxidizing Agents......Page 124
4.3.2 Titrations with Reducing Agents......Page 127
References......Page 128
Part Two: Electrochemical Techniques and Their Applications in Nonaqueous Solutions......Page 129
5.1 Classification of Electrochemical Techniques......Page 131
5.2 Fundamentals of Electrode Reactions and Current–Potential Relations......Page 132
5.2.1 Current–Potential Relation for Electron Transfer at the Electrode......Page 133
5.2.2 Current–Potential Relations and Mass Transport......Page 136
5.3 DC Polarography – Methods that Electrolyze Electroactive Species Only Partially (1)......Page 139
5.4 New Types of Polarography – Methods that Electrolyze Electroactive Species Only Partially (2)......Page 147
5.4.1 AC Polarography......Page 148
5.4.3 Pulse Polarography......Page 149
5.5 Voltammetry and Related New Techniques – Methods that Electrolyze Electroactive Species Only Partially (3)......Page 151
5.5.1 Linear Sweep Voltammetry......Page 152
5.5.2 Cyclic Voltammetry......Page 154
5.5.3 Voltammetry at Rotating Disk and Rotating Ring-Disk Electrodes......Page 156
5.5.4 Ultramicroelectrodes......Page 158
5.5.5 Modified Electrodes......Page 159
5.5.6 Other Items Related to Voltammetry......Page 160
5.5.7 Combination of Voltammetry and Nonelectrochemical Methods......Page 162
5.6.1 Controlled-Potential Electrolysis and Controlled-Current Electrolysis......Page 165
5.6.2 Electrogravimetry......Page 167
5.6.3 Coulometry and Coulometric Titrations......Page 168
5.7 Potentiometry – A Method that Does Not Electrolyze Electroactive Species......Page 170
5.7.1 Potentiometric Indicator Electrodes and Reference Electrodes......Page 171
5.7.2 Potentiometric Titrations......Page 175
5.8 Conductimetry – A Method that Is Not Based on Electrode Reactions......Page 176
5.9.1 Application of Operational Amplifiers in Electrochemical Instrumentation......Page 179
References......Page 185
6.1 Basic Techniques of Potentiometry in Nonaqueous Solutions......Page 189
6.1.2 Reference Electrodes for Nonaqueous Solutions......Page 190
6.1.3 Method of Reporting Electrode Potentials in Nonaqueous Solutions (IUPAC Recommendation)......Page 193
6.1.4 Liquid Junction Potential Between Electrolyte Solutions in the Same Solvent......Page 196
6.2.1 IUPAC Method of pH Measurements in Aqueous Solutions......Page 198
6.2.2 Methods of pH Measurements in Nonaqueous and Mixed Solvents......Page 200
6.2.3 Determination of Autoprotolysis Constants......Page 204
6.3.1 Acid–Base Reactions in Nonaqueous Solvents......Page 206
6.3.3 Complex Formation Reactions in Nonaqueous Solutions......Page 210
6.3.4 Redox Reactions in Nonaqueous Solutions......Page 212
6.3.6 Potentiometric Study of Ion Solvation – Applications that Compare Electrode Potentials in Different Solvents......Page 214
6.4 Liquid Junction Potentials between Different Solvents......Page 219
References......Page 224
7.1.1 Molar Conductivity of Dilute Solutions of Symmetrical Strong Electrolytes......Page 227
7.1.2 Molar Conductivity and Association Constants of Symmetrical Weak Electrolytes......Page 228
7.1.3 Molar Conductivity and the Formation of Triple Ions......Page 231
7.1.4 Conductivity of Solutions of Symmetrical Strong Electrolytes at Moderate to High Concentrations......Page 232
7.1.5 Molar Conductivity and Ion Association of Asymmetric Electrolytes......Page 234
7.2.1 Stokes' Law and Walden's Rule – Role of Ultrafast Solvent Dynamics......Page 235
7.2.2 Method for the Determination of Limiting Molar Conductivities of Ions......Page 239
7.3.1 Study of the Behavior of Electrolytes (Ionophores)......Page 240
7.3.2 Conductimetric Studies of Acid–Base Equilibria......Page 245
References......Page 248
8.1.1 Experimental Apparatus for Nonaqueous Systems......Page 251
8.1.2 Solvents and Supporting Electrolytes......Page 254
8.2.1 Polarographic Reductions of Metal Ions......Page 255
8.2.2 Polarography and Voltammetry of Metal Complexes......Page 265
8.2.3 Polarography and Voltammetry of Anions......Page 269
8.2.4 Electrode Reactions of Dissolved Oxygen, Dissolved Hydrogen, Carbon Dioxide and Solvated Electrons......Page 271
8.3.1 Reductions of Organic Compounds......Page 273
8.3.2 Oxidation of Organic Compounds......Page 286
8.4.1 Digital Simulation in Cyclic Voltammetry......Page 292
8.4.2 Ultramicroelectrodes in Cyclic Voltammetry......Page 293
8.4.3 Low-Temperature Electrochemistry and Cyclic Voltammetry......Page 295
8.5 Voltammetry of Isolated Nanoparticle Solutions (Nanoelectrochemistry)......Page 296
References......Page 299
9.1 Use of Electrolytic and Coulometric Techniques in Nonaqueous Solutions......Page 305
9.2.1 Spectroelectrochemistry......Page 307
9.2.2 Electrochemical-ESR Method......Page 314
9.2.3 Electrochemical Mass Spectroscopy......Page 317
9.2.5 Use of Scanning Electrochemical Microscopy......Page 319
References......Page 322
10 Purification of Solvents and Tests for Impurities......Page 325
10.1 Effects of Solvent Impurities on Electrochemical Measurements......Page 326
10.2 Procedures for the Purification of Solvents......Page 327
10.3 Tests for Purity of Solvents......Page 329
10.4 Purification Methods for Solvents in Common Use......Page 332
References......Page 338
11.1.1 Solubility and Conductivity of Supporting Electrolytes......Page 339
11.1.2 Potential Windows and Supporting Electrolytes......Page 342
11.1.3 Influences of Supporting Electrolytes on Electrode Reactions in Nonaqueous Solutions......Page 344
11.2 Methods for Preparing and Purifying Supporting Electrolytes......Page 346
References......Page 348
12.1 Batteries Using Nonaqueous Solutions – Lithium Batteries......Page 351
12.2.1 Electrochemical Double-Layer Capacitors and Pseudocapacitors......Page 355
12.2.2 Aluminum Electrolytic Capacitors......Page 357
12.3 Conducting Polymers and Electrochemistry in Nonaqueous Solutions......Page 358
12.4 Electrochemiluminescence (ECL)......Page 361
12.5 Electrochemical Reduction of CO2 in Nonaqueous Solutions......Page 364
12.6 Use of Acetonitrile in Electrowinning and Electrorefining of Copper......Page 367
12.7 Electrodeposition of Metals and Semiconductors from Nonaqueous Solutions......Page 369
References......Page 370
Part Three: Electrochemistry in New Solvent Systems......Page 373
13.1 Introduction......Page 375
13.2.1 General Aspects of Supercritical Fluids......Page 376
13.2.2 Electrochemical Aspects of Supercritical Fluids......Page 380
13.3 Ionic Liquids......Page 382
13.3.1 Physical, Chemical and Electrochemical Properties of ILs......Page 384
13.3.2 Voltammetry in ILs......Page 390
13.3.3 Applications of ILs in Electrochemical Technologies......Page 394
13.3.4 Risks of ILs and Their Decomposition......Page 397
References......Page 399
14.1.1 Fundamentals of Electrochemistry at the ITIES......Page 403
14.1.2 Practical Applications of Electrochemistry at the ITIES......Page 410
14.1.3 Three-Phase Electrochemistry......Page 412
14.2.1 Fundamentals......Page 413
14.2.3 Potential Windows and Voltammograms......Page 415
References......Page 417
Index......Page 419