Electrochemistry in nonaqueous solutions / K. Izutsu.

Format:

Book

Author/Creator:

Izutsu, Kōsuke, 1933-

Language:

English

Subjects (All):

Electrochemistry.

Nonaqueous solvents.

Physical Description:

xiv, 346 pages : illustrations ; 25 cm

Place of Publication:

Weinheim : Wiley-VCH, 2002.

Contents:

Part I Fundamentals of Chemistry in Non-Aqueous Solutions: Electrochemical Aspects

1 Properties of Solvents and Solvent Classification 3

1.1 Properties of Solvents 4

1.1.1 Physical Properties of Solvents 4

1.1.2 Chemical Properties of Solvents 13

1.1.3 Structural Aspects of Solvents 16

1.1.4 Toxicity and Hazardous Properties of Solvents 18

1.2 Classification of Solvents 19

1.3 Effects of Solvent Properties on Chemical Reactions (an Outline) 21

2 Solvation and Complex Formation of Ions and Behavior of Electrolytes 25

2.1 Influence of Ion Solvation on Electrolyte Dissolution 25

2.2 Some Fundamental Aspects of Ion-Solvation 27

2.2.1 Ion-Solvent Interactions Affecting Ion Solvation 27

2.2.2 Structure of Solvated Ions 34

2.2.3 Ultrafast Ion-Solvation Dynamics 37

2.3 Comparison of Ionic Solvation Energies in Different Solvents and Solvent Effects on Ionic Reactions and Equilibria 38

2.3.1 Gibbs Energies of Transfer and Transfer Activity Coefficients of Ions 38

2.3.2 Prediction of Solvent Effects by the Use of Transfer Activity Coefficients 42

2.4 Solvent Effects on the Complexation of Metal Ions 44

2.5 Selective Solvation of Ions in Mixed Solvents 47

2.6 Ion Association and Solvent Permittivities 50

3 Acid-Base Reactions in Non-Aqueous Solvents 59

3.1 Solvent Effects on Acid-Base Reactions 59

3.1.1 Acid-Base Reactions in Amphiprotic Solvents of High Permittivit 61

3.1.2 Acid-Base Reactions in Aprotic Solvents of High Permittivity 64

3.1.3 Acid-Base Reactions in Amphiprotic Solvents of Low Permittivity 75

3.1.4 Acid-Base Reactions in Aprotic Solvents of Low Permittivity 75

3.2 pH-Scales in Non-Aqueous Solutions 76

3.2.1 Definition of pH in Non-Aqueous Solutions 76

3.2.2 pH Windows in Non-Aqueous Solvents and pH Scales Common to Multi Solvents 78

4 Redox Reactions in Non-Aqueous Solvents 85

4.1 Solvent Effects on Various Types of Redox Reactions 85

4.1.1 Fundamentals of Redox Reactions 85

4.1.2 Solvent Effects on Redox Potentials and Redox Reaction Mechanisms 88

4.1.3 Dynamical Solvent Effects on the Kinetics of Redox Reactions 96

4.2 Redox Properties of Solvents and Potential Windows 99

4.3 Redox Titrations in Non-Aqueous Solutions 102

4.3.1 Titrations with Oxidizing Agents 102

4.3.2 Titrations with Reducing Agents 105

Part II Electrochemical Techniques and Their Applications in Non-Aqueous Solutions

5 Overview of Electrochemical Techniques 109

5.1 Classification of Electrochemical Techniques 109

5.2 Fundamentals of Electrode Reactions and Current-Potential Relations 110

5.2.1 Current-Potential Relation for Electron Transfer at the Electrode 111

5.2.2 Current-Potential Relations and Mass Transport 114

5.3 DC Polarography - Methods that Electrolyze Electroactive Species Only Partially (1) 117

5.4 New Types of Polarography - Methods that Electrolyze Electroactive Species Only Partially (2) 125

5.4.1 AC Polarography 125

5.4.2 SW Polarography 127

5.4.3 Pulse Polarography 127

5.5 Voltammetry and Related New Techniques - Methods that Electrolyze Electroactive Species Only Partially (3) 129

5.5.1 Linear Sweep Voltammetry 130

5.5.2 Cyclic Voltammetry 132

5.5.3 Voltammetry at Rotating Disk and Rotating Ring-Disk Electrodes 133

5.5.4 Ultramicroelectrodes 135

5.5.5 Modified Electrodes 136

5.5.6 Combination of Voltammetry and Non-Electrochemical Methods 137

5.5.7 Voltammetry at the Interface Between Two Immiscible Electrolyte Solutions 140

5.6 Electrogravimetry and Coulometry - Methods that Completely Electrolyze Electroactive Species 143

5.6.1 Controlled-Potential Electrolysis and Controlled-Current Electrolysis 143

5.6.2 Electrogravimetry 145

5.6.3 Coulometry and Coulometric Titrations 146

5.7 Potentiometry - A Method that Does Not Electrolyze Electroactive Species 148

5.7.1 Potentiometric Indicator Electrodes and Reference Electrodes 149

5.7.2 Potentiometric Titrations 153

5.8 Conductimetry - A Method that is Not Based on Electrode Reactions 154

5.9 Electrochemical Instrumentation - Roles of Operational Amplifiers and Microcomputers 157

5.9.1 Application of Operational Amplifiers in Electrochemical Instrumentation 158

5.9.2 Applications of Personal Computers in Electrochemical Instrumentation 163

6 Potentiometry in Non-Aqueous Solutions 167

6.1 Basic Techniques of Potentiometry in Non-Aqueous Solutions 167

6.1.1 Potentiometric Indicator Electrodes for Non-Aqueous Solutions 168

6.1.2 Reference Electrodes for Non-Aqueous Solutions 168

6.1.3 Method of Reporting Electrode Potentials in Non-Aqueous Solutions (IUPAC Recommendation) 171

6.1.4 Liquid Junction Potential Between Electrolyte Solutions in the Same Solvent 174

6.2 pH Measurements in Non-Aqueous Solutions 176

6.2.1 pH Measurements in Aqueous Solutions 176

6.2.2 Methods of pH Measurements in Non-Aqueous and Mixed Solvents 177

6.2.3 Determination of Autoprotolysis Constants 181

6.3 Applications of Potentiometry in Non-Aqueous Solutions 183

6.3.1 Acid-Base Reactions in Non-Aqueous Solvents 183

6.3.2 Precipitation Reactions in Non-Aqueous Solutions 186

6.3.3 Complex Formation Reactions in Non-Aqueous Solutions 186

6.3.4 Redox Reactions in Non-Aqueous Solutions 188

6.3.5 Potentiometric Characterization of Solvents 190

6.3.6 Potentiometric Study of Ion Solvation - Applications that Compare Electrode Potentials in Different Solvents 191

6.4 Liquid Junction Potentials between Different Solvents 194

7 Conductimetry in Non-Aqueous Solutions 201

7.1 Dissociation of Electrolytes and Electrolytic Conductivity 201

7.1.1 Molar Conductivity of Dilute Solutions of Symmetrical Strong Electrolytes 201

7.1.2 Molar Conductivity and Association Constants of Symmetrical Weak Electrolytes 202

7.1.3 Molar Conductivity and the Formation of Triple Ions 205

7.1.4 Conductivity of Solutions of Symmetrical Strong Electrolytes at Moderate to High Concentrations 206

7.1.5 Molar Conductivity and Ion Association of Asymmetric Electrolytes 208

7.2 Ionic Conductivities and Solvents 209

7.2.1 Stokes' Law and Walden's Rule - Role of Ultrafast Solvent Dynamics 209

7.2.2 Method for the Determination of Limiting Molar Conductivities of Ions 212

7.3 Applications of Conductimetry in Non-Aqueous Solutions 216

7.3.1 Study of the Behavior of Electrolytes (Ionophores) 216

7.3.2 Conductimetric Studies of Acid-Base Equilibria 218

8 Polarography and Voltammetry in Non-Aqueous Solutions 223

8.1 Basic Experimental Techniques in Non-Aqueous Solutions 223

8.1.1 Experimental Apparatus for Non-Aqueous Systems 223

8.1.2 Solvents and Supporting Electrolytes 226

8.2 Polarography and Voltammetry of Inorganic Species 227

8.2.1 Polarographic Reductions of Metal Ions 227

8.2.2 Polarography and Voltammetry of Metal Complexes 237

8.2.3 Polarography and Voltammetry of Anions 241

8.2.4 Electrode Reactions of Dissolved Oxygen, Dissolved Hydrogen, Carbon Dioxide, and Solvated Electrons 242

8.3 Polarography and Voltammetry of Organic Compounds 244

8.3.1 Reduction of Organic Compounds 244

8.3.2 Oxidation of Organic Compounds 255

8.4 Cyclic Voltammetry for Electrochemical Studies in Non-Aqueous Solutions 260

8.4.1 Digital Simulation in Cyclic Voltammetry 260

8.4.2 Ultramicroelectrodes in Cyclic Voltammetry 261

8.4.3 Low Temperature Electrochemistry and Cyclic Voltammetry 263

9 Other Electrochemical Techniques in Non-Aqueous Solutions 269

9.1 Use of Electrolytic and Coulometric Techniques in Non-Aqueous Solutions 269

9.2 Combination of Electrochemical and Nonelectrochemical Techniques 271

9.2.1 Spectroelectrochemistry 271

9.2.2 Electrochemical-ESR Method 276

9.2.3 Electrochemical Mass Spectroscopy 279

9.2.4 Use of Electrochemical Quartz Crystal Microbalance (EQCM) 281

9.2.5 Use of Scanning Electrochemical Microscopy (SECM) 281

10 Purification of Solvents and Tests for Impurities 287

10.1 Effects of Solvent Impurities on

Electrochemical Measurements 288

10.2 Procedures for the Purification of Solvents 289

10.3 Tests for Purity of Solvents 291

10.4 Purification Methods for Solvents in Common Use 294

11 Selection and Preparation of Supporting Electrolytes 301

11.1 Selection of Supporting Electrolytes for Electrochemical Measurements 301

11.1.1 Solubility and Conductivity of Supporting Electrolytes 301

11.1.2 Potential Windows and Supporting Electrolytes 304

11.1.3 Influences of Supporting Electrolytes on Electrode Reactions in Non-Aqueous Solutions 306

11.2 Methods for Preparing and Purifying Supporting Electrolytes 308

12 Use of Non-Aqueous Solutions in Modern Electrochemical Technologies 313

12.1 New Batteries Using Non-Aqueous Solutions (Lithium Batteries) 313

12.2 New Capacitors Using Non-Aqueous Solutions 316

12.2.1 Supercapacitors 316

12.2.2 Aluminum Electrolytic Capacitors 316

12.3 Conducting Polymers and Electrochemistry in Non-Aqueous Solutions 318

12.4 Electrochemical Reduction of CO[subscript 2] in Non-Aqueous Solvents 321

12.5 Use of Acetonitrile in Electrowinning and Electrorefining of Copper 323

12.6 Electrodeposition of Metals from Non-Aqueous Solutions 324

12.7 Electrochemical Use of Supercritical Fluids and Ionic Liquids as Benign Solvents 326

12.7.1 Supercritical Fluid Solvents 326

12.7.2 Room-temperature Ionic Liquids 328.

Notes:

Includes bibliographical references and index.

ISBN:

3527305165

OCLC:

49238825