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Physical Electrochemistry: Fundamentals, Techniques, and Applications, 2nd Edition

Physical Electrochemistry: Fundamentals, Techniques, and Applications, 2nd Edition

Noam Eliaz , Eliezer Gileadi

ISBN: 978-3-527-34142-9

Sep 2018

394 pages

$108.99

Description

This bestselling textbook on physical electrochemistry caters to the needs of advanced undergraduate and postgraduate students of chemistry, materials engineering, mechanical engineering, and chemical engineering. It is unique in covering both the more fundamental, physical aspects as well as the application-oriented practical aspects in a balanced manner. In addition it serves as a self-study text for scientists in industry and research institutions working in related fields. The book can be divided into three parts: (i) the fundamentals of electrochemistry; (ii) the most important electrochemical measurement techniques; and (iii) applications of electrochemistry in materials science and engineering, nanoscience and nanotechnology, and industry.
The second edition has been thoroughly revised, extended and updated to reflect the state-of-the-art in the field, for example, electrochemical printing, batteries, fuels cells, supercapacitors, and hydrogen storage.

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Preface xvii

Symbols and Abbreviations xix

1 Introduction 1

1.1 General Considerations 1

1.1.1 The Transition from Electronic to Ionic Conduction 1

1.1.2 The Resistance of the Interface can be Infinite 2

1.1.3 Mass-Transport Limitation 2

1.1.4 The Capacitance at the Metal/Solution Interphase 4

1.2 Polarizable and Nonpolarizable Interfaces 4

1.2.1 Phenomenology 4

1.2.2 The Equivalent Circuit Representation 5

Further Reading 7

2 The Potentials of Phases 9

2.1 The Driving Force 9

2.1.1 Definition of the Electrochemical Potential 9

2.1.2 Separability of the Chemical and the Electrical Terms 10

2.2 Two Cases of Special Interest 11

2.2.1 Equilibrium of a Species Between two Phases in Contact 11

2.2.2 Two Identical Phases not at Equilibrium 12

2.3 The Meaning of the Standard Hydrogen Electrode (SHE) Scale 13

Further Reading 15

3 Fundamental Measurements in Electrochemistry 17

3.1 Measurement of Current and Potential 17

3.1.1 The Cell Voltage is the Sum of Several Potential Differences 17

3.1.2 Use of a Nonpolarizable Counter Electrode 17

3.1.3 The Three-Electrode Setup 18

3.1.4 Residual jRS Potential Drop in aThree-Electrode Cell 18

3.2 Cell Geometry and the Choice of the Reference Electrode 19

3.2.1 Types of Reference Electrodes 19

3.2.2 Use of an Auxiliary Reference Electrode for the Study of Fast Transients 20

3.2.3 Calculating the Uncompensated Solution Resistance for a few Simple Geometries 21

3.2.3.1 Planar Configuration 21

3.2.3.2 Cylindrical Configuration 21

3.2.3.3 Spherical Symmetry 22

3.2.4 Positioning the Reference Electrode 22

3.2.5 Edge Effects 24

Further Reading 26

4 Electrode Kinetics: Some Basic Concepts 27

4.1 Relating Electrode Kinetics to Chemical Kinetics 27

4.1.1 The Relation of Current Density to Reaction Rate 27

4.1.2 The Relation of Potential to Energy of Activation 28

4.1.3 Mass-Transport Limitation Versus Charge-Transfer Limitation 30

4.1.4 The Thickness of the Nernst Diffusion Layer 31

4.2 Methods of Measurement 33

4.2.1 Potential Control Versus Current Control 33

4.2.2 The Need to Measure Fast Transients 35

4.2.3 Polarography and the Dropping Mercury Electrode (DME) 37

4.3 Rotating Electrodes 40

4.3.1 The Rotating Disk Electrode (RDE) 40

4.3.2 The Rotating Cone Electrode (RConeE) 44

4.3.3 The Rotating Ring Disk Electrode (RRDE) 45

Further Reading 47

5 Single-Step Electrode Reactions 49

5.1 The Overpotential, 𝜂 49

5.1.1 Definition and Physical Meaning of Overpotential 49

5.1.2 Types of Overpotential 51

5.2 Fundamental Equations of Electrode Kinetics 52

5.2.1 The Empirical Tafel Equation 52

5.2.2 The Transition-State Theory 53

5.2.3 The Equation for a Single-Step Electrode Reaction 54

5.2.4 Limiting Cases of the General Equation 56

5.3 The Symmetry Factor, 𝛽, in Electrode Kinetics 59

5.3.1 The Definition of 𝛽 59

5.3.2 The Numerical Value of 𝛽 60

5.4 The Marcus Theory of Charge Transfer 61

5.4.1 Outer-Sphere Electron Transfer 61

5.4.2 The Born–Oppenheimer Approximation 62

5.4.3 The Calculated Energy of Activation 63

5.4.4 The Value of 𝛽 and its Potential Dependence 64

5.5 Inner-Sphere Charge Transfer 65

5.5.1 Metal Deposition 65

Further Reading 66

6 Multistep Electrode Reactions 67

6.1 Mechanistic Criteria 67

6.1.1 The Transfer Coefficient, 𝛼, and its Relation to the Symmetry Factor, 𝛽 67

6.1.2 Steady State and Quasi-Equilibrium 69

6.1.3 Calculation of the Tafel Slope 71

6.1.4 Reaction Orders in Electrode Kinetics 74

6.1.5 The Effect of pH on Reaction Rates 77

6.1.6 The Enthalpy of Activation 79

Further Reading 81

7 Specific Examples of Multistep Electrode Reactions 83

7.1 Experimental Considerations 83

7.1.1 Multiple Processes in Parallel 83

7.1.2 The Level of Impurity that can be Tolerated 84

7.2 The Hydrogen Evolution Reaction (HER) 87

7.2.1 Hydrogen Evolution on Mercury 87

7.2.2 Hydrogen Evolution on Platinum 89

7.3 Possible Paths for the Oxygen Evolution Reaction 91

7.4 The Role and Stability of Adsorbed Intermediates 94

7.5 Adsorption Energy and Catalytic Activity 95

Further Reading 96

8 The Electrical Double Layer (EDL) 97

8.1 Models of Structure of the EDL 97

8.1.1 Phenomenology 97

8.1.2 The Parallel-Plate Model of Helmholtz 99

8.1.3 The Diffuse Double Layer Model of Gouy and Chapman 100

8.1.4 The Stern Model 103

8.1.5 The Role of the Solvent at the Interphase 105

Further Reading 107

9 Electrocapillary 109

9.1 Thermodynamics 109

9.1.1 Adsorption and Surface Excess 109

9.1.2 The Gibbs Adsorption Isotherm 111

9.1.3 The Electrocapillary Equation 112

9.2 Methods of Measurement and Some Results 114

9.2.1 The Electrocapillary Electrometer 114

9.2.2 Some Experimental Results 119

9.2.2.1 The Adsorption of Ions 119

9.2.2.2 Adsorption of NeutralMolecules 120

Further Reading 122

10 Intermediates in Electrode Reactions 123

10.1 Adsorption Isotherms for Intermediates Formed by Charge Transfer 123

10.1.1 General 123

10.1.2 The Langmuir Isotherm and its Limitations 123

10.1.3 Application of the Langmuir Isotherm for Charge-Transfer Processes 125

10.1.4 The Frumkin Adsorption Isotherms 126

10.2 The Adsorption Pseudocapacitance Cϕ 127

10.2.1 Formal Definition of Cϕ and its Physical Understanding 127

10.2.2 The Equivalent-Circuit Representation 129

10.2.3 Calculation of Cϕ as a function of 𝜃 and E 130

Further Reading 133

11 Underpotential Deposition and Single-Crystal Electrochemistry 135

11.1 Underpotential Deposition (UPD) 135

11.1.1 Definition and Phenomenology 135

11.1.2 UPD on Single Crystals 139

11.1.3 Underpotential Deposition of Atomic Oxygen and Hydrogen 141

Further Reading 142

12 Electrosorption 145

12.1 Phenomenology 145

12.1.1 What is Electrosorption? 145

12.1.2 Electrosorption of Neutral Organic Molecules 147

12.1.3 The Potential of Zero Charge, Epzc, and its Importance in Electrosorption 148

12.1.4 TheWork Function and the Potential of Zero Charge 151

12.2 Adsorption Isotherms for Neutral Species 152

12.2.1 General Comments 152

12.2.2 The Parallel-Plate Model of Frumkin et al. 153

12.2.3 The Water Replacement Model of Bockris et al. 155

Further Reading 157

13 Fast Transients, the Time-Dependent Diffusion Equation,and Microelectrodes 159

13.1 The Need for Fast Transients 159

13.1.1 General 159

13.1.2 Small-Amplitude Transients 161

13.1.3 The Sluggish Response of the Electrochemical Interphase 162

13.1.4 How can the Slow Response of the Interphase be Overcome? 162

13.1.4.1 Galvanostatic Transients 162

13.1.4.2 The Double-Pulse GalvanostaticMethod 163

13.1.4.3 The Coulostatic (Charge-Injection) Method 164

13.2 The Diffusion Equation 167

13.2.1 The Boundary Conditions of the Diffusion Equation 167

13.2.1.1 Potential Step, Reversible Case (Chrono-Amperometry) 168

13.2.1.2 Potential Step, High Overpotential Region (Chrono-Amperometry) 171

13.2.1.3 Current Step (Chronopotentiometry) 172

13.3 Microelectrodes 174

13.3.1 The Unique Features of Microelectrodes 174

13.3.2 Enhancement of Diffusion at a Microelectrode 175

13.3.3 Reduction of the Solution Resistance 176

13.3.4 The Choice between Single Microelectrodes and Large Ensembles 176

Further Reading 178

14 Linear Potential Sweep and Cyclic Voltammetry 181

14.1 Three Types of Linear Potential Sweep 181

14.1.1 Very Slow Sweeps 181

14.1.2 Studies of Oxidation or Reduction of Species in the Bulk of the Solution 182

14.1.3 Studies of Oxidation or Reduction of Species Adsorbed on the Surface 182

14.1.4 Double-Layer Charging Currents 183

14.1.5 The Form of the Current–Potential Relationship 185

14.2 Solution of the Diffusion Equations 186

14.2.1 The Reversible Region 186

14.2.2 The High-Overpotential Region 187

14.3 Uses and Limitations of the Linear Potential Sweep Method 188

14.4 Cyclic Voltammetry for Monolayer Adsorption 190

14.4.1 Reversible Region 190

14.4.2 The High-Overpotential Region 192

Further Reading 193

15 Electrochemical Impedance Spectroscopy (EIS) 195

15.1 Introduction 195

15.2 Graphical Representations 200

15.3 The Effect of Diffusion Limitation –TheWarburg Impedance 203

15.4 Advantages, Disadvantages, and Applications of EIS 206

Further Reading 211

16 The Electrochemical Quartz Crystal Microbalance (EQCM) 213

16.1 Fundamental Properties of the EQCM 213

16.1.1 Introduction 213

16.1.2 The EQCM 214

16.1.3 The Effect of Viscosity 217

16.1.4 Immersion in a Liquid 218

16.1.5 Scales of Roughness 218

16.2 Impedance Analysis of the EQCM 219

16.2.1 The Extended Equation for the Frequency Shift 219

16.2.2 Other Factors Influencing the Frequency Shift 220

16.3 Uses of the EQCM as a Microsensor 220

16.3.1 Advantages and Limitations 220

16.3.2 Some Applications of the EQCM 222

Further Reading 225

17 Corrosion 227

17.1 The Definition of Corrosion 227

17.2 Corrosion Costs 230

17.3 Thermodynamics of Corrosion 232

17.3.1 Introduction and Important Terms 232

17.3.2 Electrode Potentials and the Standard Electromotive Force (EMF) Series 236

17.3.3 The Dependence of Free Energy on the Equilibrium Constant and Cell Potential 241

17.3.4 The Nernst Equation 241

17.3.5 The Potential–pH (Pourbaix) Diagrams 242

17.4 Kinetics of Corrosion 252

17.4.1 Introduction and Important Terms 252

17.4.2 Two Limiting Cases of the Butler–Volmer Equation: Tafel Extrapolation and Polarization Resistance 255

17.4.3 Corrosion Rate 257

17.4.4 The Mixed-Potential Theory and the Evans Diagrams 257

17.4.5 Passivation and its Breakdown 264

17.5 Corrosion Measurements 270

17.5.1 Non-Electrochemical Tests 270

17.5.2 Electrochemical Tests 272

17.5.2.1 Open-Circuit Potential (OCP) Measurements 272

17.5.2.2 Polarization Tests 273

17.5.2.3 Linear Polarization Resistance (LPR) 277

17.5.2.4 Zero-Resistance Ammetry (ZRA) 277

17.5.2.5 Electrochemical Noise (EN) Measurements 278

17.5.2.6 Electrochemical Hydrogen Permeation Tests 279

17.5.3 Complementary Surface-Sensitive Analytical Characterization Techniques 284

17.6 Forms of Corrosion 286

17.6.1 Uniform (General) Corrosion 286

17.6.2 Localized Corrosion 289

17.6.2.1 Crevice Corrosion 289

17.6.2.2 Filiform Corrosion 291

17.6.2.3 Pitting Corrosion 291

17.6.3 Intergranular Corrosion 293

17.6.3.1 Sensitization 293

17.6.3.2 Exfoliation 294

17.6.4 Dealloying 295

17.6.5 Galvanic (Bimetallic) Corrosion 295

17.6.6 Environmentally Induced Cracking (EIC)/Environment-Assisted Cracking (EAC) 297

17.6.6.1 Hydrogen Embrittlement (HE) 297

17.6.6.2 Hydrogen-Induced Blistering 299

17.6.6.3 Hydrogen Attack 299

17.6.6.4 Stress Corrosion Cracking (SCC) 300

17.6.6.5 Corrosion Fatigue (CF) 303

17.6.7 Erosion Corrosion 304

17.6.8 Microbiological Corrosion (MIC) 305

17.7 Corrosion Protection 308

17.7.1 Cathodic Protection 308

17.7.1.1 Cathodic Protection with Sacrificial Anodes 308

17.7.1.2 Impressed-Current Cathodic Protection (ICCP) 310

17.7.2 Anodic Protection 312

17.7.3 Corrosion Inhibitors 313

17.7.4 Coatings 315

17.7.5 Other Mitigation Practices 320

Further Reading 321

18 Electrochemical Deposition 323

18.1 Electroplating 323

18.1.1 Introduction 323

18.1.2 The Fundamental Equations of Electroplating 324

18.1.3 Practical Aspects of Metal Deposition 325

18.1.4 Hydrogen Evolution as a Side Reaction 326

18.1.5 Plating of Noble Metals 327

18.1.6 Current Distribution in Electroplating 328

18.1.6.1 Uniformity of Current Distribution 328

18.1.6.2 The Faradaic Resistance (RF) and the Solution Resistance (RS) 328

18.1.6.3 The DimensionlessWagner Number 329

18.1.6.4 Kinetically Limited Current Density 333

18.1.7 Throwing Power 334

18.1.7.1 Macro Throwing Power 334

18.1.7.2 Micro Throwing Power 334

18.1.8 The Use of Additives 336

18.1.9 The Microstructure of Electrodeposits and the Evolution of Intrinsic Stresses 339

18.1.10 Pulse Plating 341

18.1.11 Plating from Nonaqueous Solutions 343

18.1.11.1 Statement of the Problem 343

18.1.11.2 Methods of Plating Al 345

18.1.12 Electroplating of Alloys 346

18.1.12.1 General Observations 346

18.1.12.2 Some Specific Examples 349

18.1.13 The Mechanism of Charge Transfer in Metal Deposition 351

18.1.13.1 Metal Ions Crossing the Interphase Carry the Charge across it 351

18.2 Electroless Deposition of Metals 352

18.2.1 Some Fundamental Aspects of Electroless Plating of Metals and Alloys 352

18.2.2 The Activation Process 353

18.2.3 The Reducing Agent 353

18.2.4 The Complexing Agent 354

18.2.5 The Mechanism of Electroless Deposition 354

18.2.6 Advantages and Disadvantages of Electroless Plating Compared to Electroplating 357

18.3 Electrophoretic Deposition (EPD) 358

Further Reading 361

19 Electrochemical Nanotechnology 363

19.1 Introduction 363

19.2 Nanoparticles and Catalysis 363

19.2.1 Surfaces and Interfaces 364

19.2.2 The Vapor Pressure of Small Droplets and the Melting Point of Solid NPs 365

19.2.3 TheThermodynamic Stability andThermal Mobility of NPs 368

19.2.4 Catalysts 368

19.2.5 The Effect of Particle Size on Catalytic Activity 369

19.2.6 Nanoparticles Compared to Microelectrodes 370

19.2.7 The Need for High Surface Area 371

19.3 Electrochemical Printing 372

19.3.1 Electrochemical Printing Processes 373

19.3.2 Nanoelectrochemistry Using Micro- and Nano-Electrodes/Pipettes 379

Further Reading 384

20 Energy Conversion and Storage 387

20.1 Introduction 387

20.2 Batteries 388

20.2.1 Classes of Batteries 388

20.2.2 TheTheoretical Limit of Energy per UnitWeight 390

20.2.3 How is the Quality of a Battery Defined? 391

20.2.4 Primary Batteries 392

20.2.4.1 Why DoWe Need Primary Batteries? 392

20.2.4.2 The Leclanché and the Alkaline Batteries 392

20.2.4.3 The Li–Thionyl Chloride Battery 393

20.2.4.4 The Lithium–Iodine Solid-State Battery 395

20.2.5 Secondary Batteries 396

20.2.5.1 Self-Discharge and Specific Energy 396

20.2.5.2 Battery Stacks Versus Single Cells 396

20.2.5.3 Some Common Types of Secondary Batteries 397

20.2.5.4 The Li-ion Battery 402

20.2.5.5 Metal–Air Batteries 408

20.2.6 Batteries-Driven Electric Vehicles 409

20.2.7 The Polarity of Batteries 410

20.3 Fuel Cells 412

20.3.1 The Specific Energy of Fuel Cells 412

20.3.2 The Phosphoric Acid Fuel Cell (PAFC) 412

20.3.3 The Direct Methanol Fuel Cell (DMFC) 415

20.3.4 The Proton Exchange Membrane Fuel Cell (PEMFC) 418

20.3.5 The Alkaline Fuel Cell (AFC) 420

20.3.6 High-Temperature Fuel Cells 421

20.3.6.1 The Solid Oxide Fuel Cell (SOFC) 421

20.3.6.2 The Molten Carbonate Fuel Cell (MCFC) 422

20.3.7 Porous Gas Diffusion Electrodes 423

20.3.8 Fuel-Cell-Driven Vehicles 426

20.3.9 Criticism of the Fuel Cells Technology 427

20.4 Supercapacitors 428

20.4.1 Electrostatic Considerations 428

20.4.2 The Energy Stored in a Capacitor 429

20.4.3 The Essence of Supercapacitors 430

20.4.4 Advantages of Supercapacitors 432

20.4.5 Barriers for Supercapacitors 435

20.4.6 Applications of Supercapacitors 435

20.5 Hydrogen Storage 436

Further Reading 443

Index 445