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Electrochemical Methods: Fundamentals and Applications 3rd edition [Kõva köide]

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Henry S. White (University of Utah, USA), Larry R. Faulkner (University of Texas at Austin, USA), Allen J. Bard (University of Texas at Austin, USA)

Formaat: Hardback, 1104 pages, kõrgus x laius x paksus: 259x183x64 mm, kaal: 1724 g
Ilmumisaeg: 26-May-2022
Kirjastus: John Wiley & Sons Inc
ISBN-10: 1119334063
ISBN-13: 9781119334064

Teised raamatud teemal:

Electrochemistry & magnetochemistry

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Formaat: Hardback, 1104 pages, kõrgus x laius x paksus: 259x183x64 mm, kaal: 1724 g
Ilmumisaeg: 26-May-2022
Kirjastus: John Wiley & Sons Inc
ISBN-10: 1119334063
ISBN-13: 9781119334064

Teised raamatud teemal:

Electrochemistry & magnetochemistry

Püsilink: https://www.kriso.ee/db/9781119334064.html

Märksõnad:

Electrochemistry

The latest edition of a classic textbook in electrochemistry

The third edition of Electrochemical Methods has been extensively revised to reflect the evolution of electrochemistry over the past two decades, highlighting significant developments in the understanding of electrochemical phenomena and emerging experimental tools, while extending the book's value as a general introduction to electrochemical methods.

This authoritative resource for new students and practitioners provides must-have information crucial to a successful career in research. The authors focus on methods that are extensively practiced and on phenomenological questions of current concern.

This latest edition of Electrochemical Methods contains numerous problems and chemical examples, with illustrations that serve to illuminate the concepts contained within in a way that will assist both student and mid-career practitioner.

Significant updates and new content in this third edition include:

An extensively revised introductory chapter on electrode processes, designed for new readers coming into electrochemistry from diverse backgrounds New chapters on steady-state voltammetry at ultramicroelectrodes, inner-sphere electrode reactions and electrocatalysis, and single-particle electrochemistry Extensive treatment of Marcus kinetics as applied to electrode reactions, a more detailed introduction to migration, and expanded coverage of electrochemical impedance spectroscopy The inclusion of Lab Notes in many chapters to help newcomers with the transition from concept to practice in the laboratory

The new edition has been revised to address a broader audience of scientists and engineers, designed to be accessible to readers with a basic foundation in university chemistry, physics and mathematics. It is a self-contained volume, developing all key ideas from the fundamental principles of chemistry and physics.

Perfect for senior undergraduate and graduate students taking courses in electrochemistry, physical and analytical chemistry, this is also an indispensable resource for researchers and practitioners working in fields including electrochemistry and electrochemical engineering, energy storage and conversion, analytical chemistry and sensors.

Arvustused

"...this third edition of the book that I consider as the Electrochemistry bible is consistent with the evolution and development of electrochemistry in these last twenty years. The new chapters highlight the most recent advances and innovative techniques while the chapters dealing with older electrochemical methods have been lightened.... The authors have made a great job in this third edition to update the book with the electrochemistry currently studied and practiced in laboratories.... Both junior and senior electrochemists, from novices to experts, should have this book available in the laboratory." Estelle Lebčgue, Transition Metal Chemistry (2023) 48:433436 https://doi.org/10.1007/s11243-023-00555-6

Preface

xxi

Major Symbols and Abbreviations

xxv

About the Companion Website

liii

1 Overview of Electrode Processes

(60)

1.1 Basic Ideas

(15)

1.1.1 Electrochemical Cells and Reactions

(2)

1.1.2 Interfacial Potential Differences and Cell Potential

(1)

1.1.3 Reference Electrodes and Control of Potential at a Working Electrode

(1)

1.1.4 Potential as an Expression of Electron Energy

(1)

1.1.5 Current as an Expression of Reaction Rate

(2)

1.1.6 Magnitudes in Electrochemical Systems

(1)

1.1.7 Current--Potential Curves

(7)

1.1.8 Control of Current vs. Control of Potential

(1)

1.1.9 Faradaic and Nonfaradaic Processes

(1)

1.2 Faradaic Processes and Factors Affecting Rates of Electrode Reactions

(6)

1.2.1 Electrochemical Cells---Types and Definitions

(1)

1.2.2 The Electrochemical Experiment and Variables in Electrochemical Cells

(3)

1.2.3 Factors Affecting Electrode Reaction Rate and Current

(2)

1.3 Mass-Transfer-Controlled Reactions

(8)

1.3.1 Modes of Mass Transfer

(1)

1.3.2 Semiempirical Treatment of Steady-State Mass Transfer

(6)

1.4 Semiempirical Treatment of Nernstian Reactions with Coupled Chemical Reactions

(3)

1.4.1 Coupled Reversible Reactions

(1)

1.4.2 Coupled Irreversible Chemical Reactions

(2)

1.5 Cell Resistance and the Measurement of Potential

(7)

1.5.1 Components of the Applied Voltage When Current Flows

(2)

1.5.2 Two-Electrode Cells

(1)

1.5.3 Three-Electrode Cells

(1)

1.5.4 Uncompensated Resistance

(3)

1.6 The Electrode/Solution Interface and Charging Current

(10)

1.6.1 The Ideally Polarizable Electrode

(1)

1.6.2 Capacitance and Charge at an Electrode

(1)

1.6.3 Brief Description of the Electrical Double Layer

(2)

1.6.4 Double-Layer Capacitance and Charging Current

(7)

1.7 Organization of this Book

(1)

1.8 The Literature of Electrochemistry

(2)

1.8.1 Reference Sources

(1)

1.8.2 Sources on Laboratory Techniques

(1)

1.8.3 Review Series

(1)

1.9 Lab Note: Potentiostats and Cell Behavior

(3)

1.9.1 Potentiostats

(1)

1.9.2 Background Processes in Actual Cells

(1)

1.9.3 Further Work with Simple RC Networks

(1)

1.10 References

(1)

1.11 Problems

(4)

2 Potentials and Thermodynamics of Cells

(60)

2.1 Basic Electrochemical Thermodynamics

(19)

2.1.1 Reversibility

(3)

2.1.2 Reversibility and Gibbs Free Energy

(1)

2.1.3 Free Energy and Cell emf

(2)

2.1.4 Half-Reactions and Standard Electrode Potentials

(1)

2.1.5 Standard States and Activity

(2)

2.1.6 EMF and Concentration

(2)

2.1.7 Formal Potentials

(1)

2.1.8 Reference Electrodes

(4)

2.1.9 Potential-pH Diagrams and Thermodynamic Predictions

(4)

2.2 A More Detailed View of Interfacial Potential Differences

(11)

2.2.1 The Physics of Phase Potentials

(2)

2.2.2 Interactions Between Conducting Phases

(2)

2.2.3 Measurement of Potential Differences

(1)

2.2.4 Electrochemical Potentials

(3)

2.2.5 Fermi Energy and Absolute Potential

(3)

2.3 Liquid Junction Potentials

(10)

2.3.1 Potential Differences at an Electrolyte--Electrolyte Boundary

(1)

2.3.2 Types of Liquid Junctions

(1)

2.3.3 Conductance, Transference Numbers, and Mobility

(4)

2.3.4 Calculation of Liquid Junction Potentials

(4)

2.3.5 Minimizing Liquid Junction Potentials

100

(1)

2.3.6 Junctions of Two Immiscible Liquids

101

(1)

2.4 Ion-Selective Electrodes

101

(11)

2.4.1 Selective Interfaces

101

(1)

2.4.2 Glass Electrodes

102

(4)

2.4.3 Other Ion-Selective Electrodes

106

(5)

2.4.4 Gas-Sensing ISEs

111

(1)

2.5 Lab Note: Practical Use of Reference Electrodes

112

(1)

2.5.1 Leakage at the Reference Tip

112

(1)

2.5.2 Quasireference Electrodes

112

(1)

2.6 References

113

(3)

2.7 Problems

116

(5)

3 Basic Kinetics of Electrode Reactions

121

(62)

3.1 Review of Homogeneous Kinetics

121

(4)

3.1.1 Dynamic Equilibrium

121

(1)

3.1.2 The Arrhenius Equation and Potential Energy Surfaces

122

(1)

3.1.3 Transition State Theory

123

(2)

3.2 Essentials of Electrode Reactions

125

(1)

3.3 Butler--Volmer Model of Electrode Kinetics

126

(6)

3.3.1 Effects of Potential on Energy Barriers

127

(1)

3.3.2 One-Step, One-Electron Process

127

(3)

3.3.3 The Standard Rate Constant

130

(1)

3.3.4 The Transfer Coefficient

131

(1)

3.4 Implications of the Butler--Volmer Model for the One-Step, One-Electron Process

132

(10)

3.4.1 Equilibrium Conditions and the Exchange Current

133

(1)

3.4.2 The Current--Overpotential Equation

133

(2)

3.4.3 Approximate Forms of the i--n Equation

135

(4)

3.4.4 Exchange Current Plots

139

(1)

3.4.5 Very Facile Kinetics and Reversible Behavior

139

(1)

3.4.6 Effects of Mass Transfer

140

(1)

3.4.7 Limits of Basic Butler--Volmer Equations

141

(1)

3.5 Microscopic Theories of Charge Transfer

142

(26)

3.5.1 Inner-Sphere and Outer-Sphere Electrode Reactions

142

(1)

3.5.2 Extended Charge Transfer and Adiabaticity

143

(3)

3.5.3 The Marcus Microscopic Model

146

(6)

3.5.4 Implications of the Marcus Theory

152

(10)

3.5.5 A Model Based on Distributions of Energy States

162

(6)

3.6 Open-Circuit Potential and Multiple Half-Reactions at an Electrode

168

(3)

3.6.1 Open-Circuit Potential in Multicomponent Systems

169

(1)

3.6.2 Establishment or Loss of Nernstian Behavior at an Electrode

170

(1)

3.6.3 Multiple Half-Reaction Currents in i--E Curves

171

(1)

3.7 Multistep Mechanisms

171

(6)

3.7.1 The Primacy of One-Electron Transfers

172

(1)

3.7.2 Rate-Determining, Outer-Sphere Electron Transfer

173

(1)

3.7.3 Multistep Processes at Equilibrium

173

(1)

3.7.4 Nernstian Multistep Processes

174

(1)

3.7.5 Quasireversible and Irreversible Multistep Processes

174

(3)

3.8 References

177

(3)

3.9 Problems

180

(3)

4 Mass Transfer by Migration and Diffusion

183

(24)

4.1 General Mass-Transfer Equations

183

(3)

4.2 Migration in Bulk Solution

186

(1)

4.3 Mixed Migration and Diffusion Near an Active Electrode

187

(6)

4.3.1 Balance Sheets for Mass Transfer During Electrolysis

188

(4)

4.3.2 Utility of a Supporting Electrolyte

192

(1)

4.4 Diffusion

193

(6)

4.4.1 A Microscopic View

193

(3)

4.4.2 Fick's Laws of Diffusion

196

(3)

4.4.3 Flux of an Electroreactant at an Electrode Surface

199

(1)

4.5 Formulation and Solution of Mass-Transfer Problems

199

(5)

4.5.1 Initial and Boundary Conditions in Electrochemical Problems

200

(1)

4.5.2 General Formulation of a Linear Diffusion Problem

201

(1)

4.5.3 Systems Involving Migration or Convection

202

(1)

4.5.4 Practical Means for Reaching Solutions

202

(2)

4.6 References

204

(1)

4.7 Problems

205

(2)

5 Steady-State Voltammetry at Ultramicroelectrodes

207

(54)

5.1 Steady-State Voltammetry at a Spherical UME

207

(7)

5.1.1 Steady-State Diffusion

208

(3)

5.1.2 Steady-State Current

211

(1)

5.1.3 Convergence on the Steady State

211

(1)

5.1.4 Steady-State Voltammetry

212

(2)

5.2 Shapes and Properties of Ultramicroelectrodes

214

(10)

5.2.1 Spherical or Hemispherical UME

215

(1)

5.2.2 Disk UME

215

(6)

5.2.3 Cylindrical UME

221

(1)

5.2.4 Band UME

221

(1)

5.2.5 Summary of Steady-State Behavior at UMEs

222

(2)

5.3 Reversible Electrode Reactions

224

(6)

5.3.1 Shape of the Wave

224

(2)

5.3.2 Applications of Reversible i-E Curves

226

(4)

5.4 Quasireversible and Irreversible Electrode Reactions

230

(9)

5.4.1 Effect of Electrode Kinetics on Steady-State Responses

230

(2)

5.4.2 Total Irreversibility

232

(2)

5.4.3 Kinetic Regimes

234

(1)

5.4.4 Influence of Electrode Shape

234

(1)

5.4.5 Applications of Irreversible i-E Curves

235

(2)

5.4.6 Evaluation of Kinetic Parameters by Varying Mass-Transfer Rates

237

(2)

5.5 Multicomponent Systems and Multistep Charge Transfers

239

(2)

5.6 Additional Attributes of Ultramicroelectrodes

241

(4)

5.6.1 Uncompensated Resistance at a UME

241

(1)

5.6.2 Effects of Conductivity on Voltammetry at a UME

242

(1)

5.6.3 Applications Based on Spatial Resolution

243

(2)

5.7 Migration in Steady-State Voltammetry

245

(3)

5.7.1 Mathematical Approach to Problems Involving Migration

245

(1)

5.7.2 Concentration Profiles in the Diffusion--Migration Layer

246

(2)

5.7.3 Wave Shape at Low Electrolyte Concentration

248

(1)

5.7 A Effects of Migration on Wave Height in SSV

248

(3)

5.8 Analysis at High Analyte Concentrations

251

(2)

5.9 Lab Note: Preparation of Ultramicroelectrodes

253

(4)

5.9.1 Preparation and Characterization of UMEs

254

(1)

5.9.2 Testing the Integrity of a UME

254

(2)

5.9.3 Estimating the Size of a UME

256

(1)

5.10 References

257

(1)

5.11 Problems

258

(3)

6 Transient Methods Based on Potential Steps

261

(50)

6.1 Chronoamperometry Under Diffusion Control

261

(14)

6.1.1 Linear Diffusion at a Plane

262

(3)

6.1.2 Response at a Spherical Electrode

265

(2)

6.1.3 Transients at Other Ultramicroelectrodes

267

(3)

6.1.4 Information from Chronoamperometric Results

270

(1)

6.1.5 Microscopic and Geometric Areas

271

(4)

6.2 Sampled-Transient Voltammetry for Reversible Electrode Reactions

275

(4)

6.2.1 A Step to an Arbitrary Potential

276

(1)

6.2.2 Shape of the Voltammogram

277

(1)

6.2.3 Concentration Profiles When R Is Initially Absent

278

(1)

6.2.4 Simplified Current--Concentration Relationships

279

(1)

6.2.5 Applications of Reversible i-E Curves

279

(1)

6.3 Sampled-Transient Voltammetry for Quasireversible and Irreversible Electrode Reactions

279

(10)

6.3.1 Effect of Electrode Kinetics on Transient Behavior

280

(2)

6.3.2 Sampled-Transient Voltammetry for Reduction of O

282

(2)

6.3.3 Sampled Transient Voltammetry for Oxidation of R

284

(1)

6.3.4 Totally Irreversible Reactions

285

(2)

6.3.5 Kinetic Regimes

287

(1)

6.3.6 Applications of Irreversible i--E Curves

287

(2)

6.4 Multicomponent Systems and Multistep Charge Transfers

289

(1)

6.5 Chronoamperometric Reversal Techniques

290

(4)

6.5.1 Approaches to the Problem

292

(1)

6.5.2 Current--Time Responses

293

(1)

6.6 Chronocoulometry

294

(6)

6.6.1 Large-Amplitude Potential Step

295

(1)

6.6.2 Reversal Experiments Under Diffusion Control

296

(3)

6.6.3 Effects of Heterogeneous Kinetics

299

(1)

6.7 Cell Time Constants at Microelectrodes

300

(3)

6.8 Lab Note: Practical Concerns with Potential Step Methods

303

(3)

6.8.1 Preparation of the Electrode Surface at a Microelectrode

303

(2)

6.8.2 Interference from Charging Current

305

(1)

6.9 References

306

(1)

6.10 Problems

307

(4)

7 Linear Sweep and Cyclic Voltammetry

311

(44)

7.1 Transient Responses to a Potential Sweep

311

(2)

7.2 Nernstian (Reversible) Systems

313

(12)

7.2.1 Linear Sweep Voltammetry

313

(8)

7.2.2 Cyclic Voltammetry

321

(4)

7.3 Quasireversible Systems

325

(4)

7.3.1 Linear Sweep Voltammetry

326

(1)

7.3.2 Cyclic Voltammetry

326

(3)

7.4 Totally Irreversible Systems

329

(3)

7.4.1 Linear Sweep Voltammetry

329

(3)

7.4.2 Cyclic Voltammetry

332

(1)

7.5 Multicomponent Systems and Multistep Charge Transfers

332

(2)

7.5.1 Multicomponent Systems

332

(1)

7.5.2 Multistep Charge Transfers

333

(1)

7.6 Fast Cyclic Voltammetry

334

(2)

7.7 Convolutive Transformation

336

(3)

7.8 Voltammetry at Liquid--Liquid Interfaces

339

(5)

7.8.1 Experimental Approach to Voltammetry

340

(1)

7.8.2 Effect of Interfacial Potential on Composition

341

(1)

7.8.3 Voltammetric Behavior

341

(3)

7.9 Lab Note: Practical Aspects of Cyclic Voltammetry

344

(3)

7.9.1 Basic Experimental Conditions

344

(1)

7.9.2 Choice of Initial and Final Potentials

345

(2)

7.9.3 Deaeration

347

(1)

7.10 References

347

(2)

7.11 Problems

349

(6)

8 Polarography, Pulse Voltammetry, and Square-Wave Voltammetry

355

(34)

8.1 Polarography

355

(6)

8.1.1 The Dropping Mercury Electrode

355

(1)

8.1.2 The Ilkovic Equation

356

(1)

8.1.3 Polarographic Waves

357

(1)

8.1.4 Practical Advantages of the DME

358

(1)

8.1.5 Polarographic Analysis

358

(1)

8.1.6 Residual Current and Detection Limits

359

(2)

8.2 Normal Pulse Voltammetry

361

(6)

8.2.1 Implementation

362

(1)

8.2.2 Renewal at Stationary Electrodes

363

(1)

8.2.3 Normal Pulse Polarography

364

(2)

8.2.4 Practical Application

366

(1)

8.3 Reverse Pulse Voltammetry

367

(2)

8.4 Differential Pulse Voltammetry

369

(7)

8.4.1 Concept of the Method

370

(1)

8.4.2 Theory

371

(3)

8.4.3 Renewal vs. Pre-Electrolysis

374

(1)

8.4.4 Residual Currents

375

(1)

8.4.5 Differential Pulse Polarography

375

(1)

8.5 Square-Wave Voltammetry

376

(7)

8.5.1 Experimental Concept and Practice

376

(1)

8.5.2 Theoretical Prediction of Response

377

(3)

8.5.3 Background Currents

380

(1)

8.5.4 Applications

381

(2)

8.6 Analysis by Pulse Voltammetry

383

(2)

8.7 References

385

(1)

8.8 Problems

386

(3)

9 Controlled-Current Techniques

389

(22)

9.1 Introduction to Chronopotentiometry

389

(2)

9.2 Theory of Controlled-Current Methods

391

(3)

9.2.1 General Treatment for Linear Diffusion

391

(1)

9.2.2 Constant-Current Electrolysis---The Sand Equation

392

(2)

9.2.3 Programmed Current Chronopotentiometry

394

(1)

9.3 Potential-Time Curves in Constant-Current Electrolysis

394

(4)

9.3.1 Reversible (Nernstian) Waves

394

(1)

9.3.2 Totally Irreversible Waves

394

(1)

9.3.3 Quasireversible Waves

395

(1)

9.3.4 Practical Issues in the Measurement of Transition Time

396

(2)

9.4 Reversal Techniques

398

(2)

9.4.1 Response Function Principle

398

(1)

9.4.2 Current Reversal

398

(2)

9.5 Multicomponent Systems and Multistep Reactions

400

(1)

9.6 The Galvanostatic Double Pulse Method

401

(2)

9.7 Charge Step (Coulostatic) Methods

403

(3)

9.7.1 Small Excursions

404

(1)

9.7.2 Large Excursions

405

(1)

9.7.3 Coulostatic Perturbation by Temperature Jump

405

(1)

9.8 References

406

(1)

9.9 Problems

407

(4)

10 Methods Involving Forced Convection---Hydrodynamic Methods

411

(32)

10.1 Theory of Convective Systems

411

(3)

10.1.1 The Convective-Diffusion Equation

412

(1)

10.1.2 Determination of the Velocity Profile

412

(2)

10.2 Rotating Disk Electrode

414

(12)

10.2.1 The Velocity Profile at a Rotating Disk

414

(2)

10.2.2 Solution of the Convective-Diffusion Equation

416

(2)

10.2.3 Concentration Profile

418

(1)

10.2.4 General i--E Curves at the RDE

419

(1)

10.2.5 The Koutecky--Levich Method

420

(3)

10.2.6 Current Distribution at the RDE

423

(3)

10.2.7 Practical Considerations for Application of the RDE

426

(1)

10.3 Rotating Ring and Ring-Disk Electrodes

426

(6)

10.3.1 Rotating Ring Electrode

427

(1)

10.3.2 The Rotating Ring-Disk Electrode

428

(4)

10.4 Transient Currents

432

(3)

10.4.1 Transients at the RDE

432

(1)

10.4.2 Transients at the RRDE

433

(2)

10.5 Modulation of the RDE

435

(1)

10.6 Electrohydrodynamic Phenomena

436

(3)

10.7 References

439

(1)

10.8 Problems

440

(3)

11 Electrochemical Impedance Spectroscopy and ac Voltammetry

443

(46)

11.1 A Simple Measurement of Cell Impedance

444

(2)

11.2 Brief Review of ac Circuits

446

(4)

11.3 Equivalent Circuits of a Cell

450

(8)

11.3.1 The Randles Equivalent Circuit

451

(1)

11.3.2 Interpretation of the Faradaic Impedance

452

(3)

11.3.3 Behavior and Uses of the Faradaic Impedance

455

(3)

11.4 Electrochemical Impedance Spectroscopy

458

(12)

11.4.1 Conditions of Measurement

458

(2)

11.4.2 A System with Simple Faradaic Kinetics

460

(5)

11.4.3 Measurement of Resistance and Capacitance

465

(1)

11.4.4 A Confined Electroactive Domain

466

(4)

11.4.5 Other Applications

470

(1)

11.5 AC Voltammetry

470

(7)

11.5.1 Reversible Systems

470

(3)

11.5.2 Quasireversible and Irreversible Systems

473

(4)

11.5.3 Cyclic ac Voltammetry

477

(1)

11.6 Nonlinear Responses

477

(4)

11.6.1 Second Harmonic ac Voltammetry

478

(1)

11.6.2 Large Amplitude ac Voltammetry

479

(2)

11.7 Chemical Analysis by ac Voltammetry

481

(1)

11.8 Instrumentation for Electrochemical Impedance Methods

482

(3)

11.8.1 Frequency-Domain Instruments

482

(1)

11.8.2 Time-Domain Instruments

483

(2)

11.9 Analysis of Data in the Laplace Plane

485

(1)

11.10 References

485

(2)

11.11 Problems

487

(2)

12 Bulk Electrolysis

489

(50)

12.1 General Considerations

490

(5)

12.1.1 Completeness of an Electrode Process

490

(1)

12.1.2 Current Efficiency

491

(1)

12.1.3 Experimental Concerns

491

(4)

12.2 Controlled-Potential Methods

495

(6)

12.2.1 Current--Time Behavior

495

(2)

12.2.2 Practical Aspects

497

(1)

12.2.3 Coulometry

498

(2)

12.2.4 Electrogravimetry

500

(1)

12.2.5 Electroseparations

501

(1)

12.3 Controlled-Current Methods

501

(6)

12.3.1 Characteristics of Controlled-Current Electrolysis

501

(2)

12.3.2 Coulometric Titrations

503

(3)

12.3.3 Practical Aspects of Constant-Current Electrolysis

506

(1)

12.4 Electrometric End-Point Detection

507

(3)

12.4.1 Current--Potential Curves During Titration

507

(1)

12.4.2 Potentiometric Methods

508

(1)

12.4.3 Amperometric Methods

509

(1)

12.5 Flow Electrolysis

510

(11)

12.5.1 Mathematical Treatment

510

(5)

12.5.2 Dual-Electrode Flow Cells

515

(1)

12.5.3 Microfluidic Flow Cells

516

(5)

12.6 Thin-Layer Electrochemistry

521

(6)

12.6.1 Chronoamperometry and Coulometry

521

(3)

12.6.2 Potential Sweep in a Nernstian System

524

(2)

12.6.3 Dual-Electrode Thin-Layer Cells

526

(1)

12.6.4 Applications of the Thin-Layer Concept

526

(1)

12.7 Stripping Analysis

527

(4)

12.7.1 Introduction

527

(1)

12.7.2 Principles and Theory

528

(1)

12.7.3 Applications and Variations

529

(2)

12.8 References

531

(3)

12.9 Problems

534

(5)

13 Electrode Reactions with Coupled Homogeneous Chemical Reactions

539

(60)

13.1 Classification of Reactions

539

(6)

13.1.1 Reactions with One E-Step

541

(1)

13.1.2 Reactions with Two or More E-Steps

542

(3)

13.2 Impact of Coupled Reactions on Cyclic Voltammetry

545

(7)

13.2.1 Diagnostic Criteria

545

(2)

13.2.2 Characteristic Times

547

(1)

13.2.3 An Example

547

(1)

13.2.4 Including Kinetics in Theory

548

(3)

13.2.5 Comparative Simulation

551

(1)

13.3 Survey of Behavior

552

(39)

13.3.1 Following Reaction---Case ErCi

552

(4)

13.3.2 Effect of Electrode Kinetics in ECi Systems

556

(2)

13.3.3 Bidirectional Following Reaction

558

(3)

13.3.4 Catalytic Reaction---Case ErCi'

561

(3)

13.3.5 Preceding Reaction---Case CrEr

564

(5)

13.3.6 Multistep Electron Transfers

569

(7)

13.3.7 ECE/DISP Reactions

576

(8)

13.3.8 Concerted vs. Stepwise Reaction

584

(6)

13.3.9 Elaboration of Reaction Schemes

590

(1)

13.4 Behavior with Other Electrochemical Methods

591

(2)

13.5 References

593

(2)

13.6 Problems

595

(4)

14 Double-Layer Structure and Adsorption

599

(54)

14.1 Thermodynamics of the Double Layer

599

(3)

14.1.1 The Gibbs Adsorption Isotherm

599

(2)

14.1.2 The Electrocapillary Equation

601

(1)

14.1.3 Relative Surface Excesses

601

(1)

14.2 Experimental Evaluations

602

(4)

14.2.1 Electrocapillarity

602

(1)

14.2.2 Excess Charge and Capacitance

603

(3)

14.2.3 Relative Surface Excesses

606

(1)

14.3 Models for Double-Layer Structure

606

(13)

14.3.1 The Helmholtz Model

607

(2)

14.3.2 The Gouy--Chapman Theory

609

(5)

14.3.3 Stern's Modification

614

(3)

14.3.4 Specific Adsorption

617

(2)

14.4 Studies at Solid Electrodes

619

(8)

14.4.1 Well-Defined Single-Crystal Electrode Surfaces

620

(3)

14.4.2 The Double Layer at Solids

623

(4)

14.5 Extent and Rate of Specific Adsorption

627

(7)

14.5.1 Nature and Extent of Specific Adsorption

628

(1)

14.5.2 Electrosorption Valency

629

(1)

14.5.3 Adsorption Isotherms

630

(3)

14.5.4 Rate of Adsorption

633

(1)

14.6 Practical Aspects of Adsorption

634

(2)

14.7 Double-Layer Effects on Electrode Reaction Rates

636

(4)

14.7.1 Introduction and Principles

636

(2)

14.7.2 Double-Layer Effects Without Specific Adsorption of Electrolyte

638

(1)

14.7.3 Double-Layer Effects with Specific Adsorption

639

(1)

14.7 4 Diffuse Double-Layer Effects on Mass Transport

640

(5)

14.8 References

645

(3)

14.9 Problems

648

(5)

15 Inner-Sphere Electrode Reactions and Electrocatalysis

653

(68)

15.1 Inner-Sphere Heterogenous Electron-Transfer Reactions

653

(4)

15.1.1 The Role of the Electrode Surface

653

(1)

15.1.2 Energetics of le Electron-Transfer Reactions

654

(3)

15.1.3 Adsorption Energies

657

(1)

15.2 Electrocatalytic Reaction Mechanisms

657

(10)

15.2.1 Hydrogen Evolution Reaction

657

(3)

15.2.2 Tafel Plot Analysis of HER Kinetics

660

(7)

15.3 Additional Examples of Inner-Sphere Reactions

667

(11)

15.3.1 Oxygen Reduction Reaction

667

(3)

15.3.2 Chlorine Evolution

670

(1)

15.3.3 Methanol Oxidation

670

(3)

15.3.4 CO2 Reduction

673

(1)

15.3.5 Oxidation of NH3 to N2

674

(2)

15.3.6 Organic Halide Reduction

676

(1)

15.3.7 Hydrogen Peroxide Oxidation and Reduction

677

(1)

15.4 Computational Analyses of Inner-Sphere Electron-Transfer Reactions

678

(6)

15.4.1 Density Functional Theory Analysis of Electrocatalytic Reactions

679

(1)

15.4.2 Hydrogen Evolution Reaction

679

(2)

15.4.3 Oxygen Reduction Reaction

681

(3)

15.5 Electrocatalytic Correlations

684

(4)

15.6 Electrochemical Phase Transformations

688

(25)

15.6.1 Nucleation and Growth of a New Phase

688

(1)

15.6.2 Classical Nucleation Theory

689

(10)

15.6.3 Electrodeposition

699

(8)

15.6.4 Gas Evolution

707

(6)

15.7 References

713

(5)

15.8 Problems

718

(3)

16 Electrochemical Instrumentation

721

(34)

16.1 Operational Amplifiers

721

(4)

16.1.1 Ideal Properties

721

(2)

16.1.2 Nonidealities

723

(2)

16.2 Current Feedback

725

(3)

16.2.1 Current Follower

725

(1)

16.2.2 Sealer/Inverter

726

(1)

16.2.3 Adders

726

(1)

16.2.4 Integrators

727

(1)

16.3 Voltage Feedback

728

(2)

16.3.1 Voltage Follower

728

(1)

16.3.2 Control Functions

729

(1)

16.4 Potentiostats

730

(4)

16.4.1 Basic Considerations

730

(1)

16.4.2 The Adder Potentiostat

731

(1)

16.4.3 Refinements to the Adder Potentiostat

732

(1)

16.4.4 Bipotentiostats

733

(1)

16.4.5 Four-Electrode Potentiostats

734

(1)

16.5 Galvanostats

734

(2)

16.6 Integrated Electrochemical Instrumentation

736

(1)

16.7 Difficulties with Potential Control

737

(7)

16.7.1 Types of Control Problems

737

(3)

16.7.2 Cell Properties and Electrode Placement

740

(1)

16.7.3 Electronic Compensation of Resistance

740

(4)

16.8 Measurement of Low Currents

744

(4)

16.8.1 Fundamental Limits

744

(2)

16.8.2 Practical Considerations

746

(1)

16.8.3 Current Amplifier

746

(1)

16.8.4 Simplified Instruments and Cells

746

(2)

16.9 Instruments for Short Time Scales

748

(1)

16.10 Lab Note: Practical Use of Electrochemical Instruments

749

(2)

16.10.1 Caution Regarding Electrochemical Workstations

749

(1)

16.10.2 Troubleshooting Electrochemical Systems

749

(2)

16.11 References

751

(1)

16.12 Problems

752

(3)

17 Electroactive Layers and Modified Electrodes

755

(64)

17.1 Monolayers and Submonolayers on Electrodes

756

(1)

17.2 Cyclic Voltammetry of Adsorbed Layers

757

(18)

17.2.1 Fundamentals

757

(1)

17.2.2 Reversible Adsorbate Couples

758

(5)

17.2.3 Irreversible Adsorbate Couples

763

(3)

17.2.4 Nernstian Processes Involving Adsorbates and Solutes

766

(4)

17.2.5 More Complex Systems

770

(1)

17.2.6 Electric-Field-Driven Acid--Base Chemistry in Adsorbate Layers

771

(4)

17.3 Other Useful Methods for Adsorbed Monolayers

775

(5)

17.3.1 Chronocoulometry

775

(2)

17.3.2 Coulometry in Thin-Layer Cells

777

(1)

17.3.3 Impedance Measurements

778

(1)

17.3.4 Chronopotentiometry

779

(1)

17.4 Thick Modification Layers on Electrodes

780

(2)

17.5 Dynamics in Modification Layers

782

(9)

17.5.1 Steady State at a Rotating Disk

783

(1)

17.5.2 Principal Dynamic Processes in Modifying Films

784

(5)

17.5.3 Interplay of Dynamical Elements

789

(2)

17.6 Blocking Layers

791

(7)

17.6.1 Permeation Through Pores and Pinholes

792

(4)

17.6.2 Tunneling Through Blocking Films

796

(2)

17.7 Other Methods for Characterizing Layers on Electrodes

798

(1)

17.8 Electrochemical Methods Based on Electroactive Layers or Electrode Modification

798

(14)

17.8.1 Electrocatalysis

799

(1)

17.8.2 Bioelectrocatalysis Based on Enzyme-Modified Electrodes

799

(4)

17.8.3 Electrochemical Sensors

803

(6)

17.8.4 Faradaic Electrochemical Measurements in vivo

809

(3)

17.9 References

812

(5)

17.10 Problems

817

(2)

18 Scanning Electrochemical Microscopy

819

(32)

18.1 Principles

819

(2)

18.2 Approach Curves

821

(4)

18.3 Imaging Surface Topography and Reactivity

825

(3)

18.3.1 Imaging Based on Conductivity of the Substrate

825

(1)

18.3.2 Imaging Based on Heterogeneous Electron-Transfer Reactivity

826

(1)

18.3.3 Simultaneous Imaging of Topography and Reactivity

827

(1)

18.4 Measurements of Kinetics

828

(7)

18.4.1 Heterogeneous Electron-Transfer Reactions

828

(3)

18.4.2 Homogeneous Reactions

831

(4)

18.5 Surface Interrogation

835

(4)

18.6 Potentiometric Tips

839

(1)

18.7 Other Applications

839

(2)

18.7.1 Detection of Species Released from Surfaces, Films, or Pores

839

(1)

18.7.2 Biological Systems

840

(1)

18.7.3 Probing the Interior of a Layer on a Substrate

841

(1)

18.8 Scanning Electrochemical Cell Microscopy

841

(5)

18.9 References

846

(3)

18.10 Problems

849

(2)

19 Single-Particle Electrochemistry

851

(34)

19.1 General Considerations in Single-Particle Electrochemistry

851

(1)

19.2 Particle Collision Experiments

852

(2)

19.3 Particle Collision Rate at a Disk-Shaped UME

854

(3)

19.3.1 Collision Frequency

854

(1)

19.3.2 Variance in the Number of Particle Collisions

855

(1)

19.3.3 Time of First Arrival

856

(1)

19.4 Nanoparticle Collision Behavior

857

(13)

19.4.1 Blocking Collisions

857

(4)

19.4.2 Electrocatalytic Amplification Collisions

861

(3)

19.4.3 Electrolysis Collisions

864

(6)

19.5 Electrochemistry at Single Atoms and Atomic Clusters

870

(5)

19.6 Single-Molecule Electrochemistry

875

(4)

19.7 References

879

(2)

19.8 Problems

881

(4)

20 Photoelectrochemistry and Electrogenerated Chemiluminescence

885

(46)

20.1 Solid Materials

885

(7)

20.1.1 The Band Model

885

(1)

20.1.2 Categories of Pure Crystalline Solids

886

(3)

20.1.3 Doped Semiconductors

889

(1)

20.1.4 Fermi Energy

890

(1)

20.1.5 Highly Conducting Oxides

891

(1)

20.2 Semiconductor Electrodes

892

(9)

20.2.1 Interface at a Semiconducting Electrode in the Dark

892

(4)

20.2.2 Current--Potential Curves at Semiconductor Electrodes

896

(3)

20.2.3 Conducting Polymer Electrodes

899

(2)

20.3 Photoelectrochemistry at Semiconductors

901

(7)

20.3.1 Photoeffects at Semiconductor Electrodes

901

(2)

20.3.2 Photoelectrochemical Systems

903

(2)

20.3.3 Dye Sensitization

905

(1)

20.3.4 Surface Photocatalytic Processes at Semiconductor Particles

906

(2)

20.4 Radiolytic Products in Solution

908

(2)

20.4.1 Photoemission of Electrons from an Electrode

908

(1)

20.4.2 Detection and Use of Radiolytic Products in Solution

909

(1)

20.4.3 Photogalvanic Cells

909

(1)

20.5 Electrogenerated Chemiluminescence

910

(12)

20.5.1 Chemical Fundamentals

910

(2)

20.5.2 Fundamental Studies of Radical-Ion Annihilation

912

(4)

20.5.3 Single-Potential Generation Based on a Coreactant

916

(1)

20.5.4 ECL Based on Quantum Dots

917

(1)

20.5.5 Analytical Applications of ECL

918

(4)

20.5.6 ECL Beyond the Solution Phase

922

(1)

20.6 References

922

(5)

20.7 Problems

927

(4)

21 In situ Characterization of Electrochemical Systems

931

(36)

21.1 Microscopy

931

(9)

21.1.1 Scanning Tunneling Microscopy

932

(2)

21.1.2 Atomic Force Microscopy

934

(3)

21.1.3 Optical Microscopy

937

(1)

21.1.4 Transmission Electron Microscopy

938

(2)

21.2 Quartz Crystal Microbalance

940

(2)

21.2.1 Basic Method

940

(2)

21.2.2 QCM with Dissipation Monitoring

942

(1)

21.3 UV--Visible Spectrometry

942

(5)

21.3.1 Absorption Spectroscopy with Thin-Layer Cells

942

(3)

21.3.2 Ellipsometry

945

(1)

21.3.3 Surface Plasmon Resonance

946

(1)

21.4 Vibrational Spectroscopy

947

(6)

21.4.1 Infrared Spectroscopy

947

(3)

21.4.2 Raman Spectroscopy

950

(3)

21.5 X-Ray Methods

953

(1)

21.6 Mass Spectrometry

954

(1)

21.7 Magnetic Resonance Spectroscopy

955

(2)

21.7.1 ESR

955

(1)

21.7.2 NMR

956

(1)

21.8 Ex-situ Techniques

957

(3)

21.8.1 Electron Microscopy

957

(1)

21.8.2 Electron and Ion Spectrometry

958

(2)

21.9 References

960

(7)

Appendix A Mathematical Methods

967

(18)

A.1 Solving Differential Equations by the Laplace Transform Technique

967

(9)

A.1.1 Partial Differential Equations

967

(1)

A.1.2 Introduction to the Laplace Transformation

968

(1)

A.1.3 Fundamental Properties of the Transform

969

(1)

A.1.4 Solving Ordinary Differential Equations by Laplace Transformation

970

(2)

A.1.5 Simultaneous Linear Ordinary Differential Equations

972

(1)

A.1.6 Mass-Transfer Problems Based on Partial Differential Equations

973

(2)

A.1.7 The Zero-Shift Theorem

975

(1)

A.2 Taylor Expansions

976

(1)

A.2.1 Expansion of a Function of Several Variables

976

(1)

A.2.2 Expansion of a Function of a Single Variable

977

(1)

A.2.3 Maclaurin Series

977

(1)

A.3 The Error Function and the Gaussian Distribution

977

(2)

A.4 Leibnitz Rule

979

(1)

A.5 Complex Notation

979

(2)

A.6 Fourier Series and Fourier Transformation

981

(1)

A.7 References

982

(1)

A.8 Problems

983

(2)

Appendix B Basic Concepts of Simulation

985

(22)

B.1 Setting Up the Model

985

(8)

B.1.1 A Discrete System

985

(1)

B.1.2 Diffusion

986

(1)

B.1.3 Dimensionless Parameters

987

(3)

B.1.4 Time

990

(1)

B.1.5 Distance

990

(1)

B.1.6 Current

991

(1)

B.1.7 Thickness of the Diffusion Layer

992

(1)

B.1.8 Diffusion Coefficients

993

(1)

B.2 An Example

993

(6)

B.2.1 Organization of the Spreadsheet

993

(3)

B.2.2 Concentration Arrays

996

(1)

B.2.3 Results and Error Detection

996

(1)

B.2.4 Performance

997

(2)

B.3 Incorporating Homogeneous Kinetics

999

(2)

B.3.1 Unimolecular Reactions

999

(1)

B.3.2 Bimolecular Reactions

1000

(1)

B.4 Boundary Conditions for Various Techniques

1001

(3)

B.4.1 Potential Steps in Nernstian Systems

1001

(1)

B.4.2 Heterogeneous Kinetics

1002

(1)

B.4.3 Potential Sweeps

1003

(1)

B.4.4 Controlled Current

1003

(1)

B.5 More Complex Systems

1004

(1)

B.6 References

1005

(1)

B.7 Problems

1005

(2)

Appendix C Reference Tables

1007

(8)

References

1013

(2)

Index

1015

Allen J. Bard is Professor and Hackerman-Welch Regents Chair in Chemistry at the University of Texas at Austin in the United States. His research is focused on the application of electrochemical methods to the study of chemical problems.

Larry R. Faulkner is President Emeritus of the University of Texas at Austin in the United States. He has served on the chemistry faculties of Harvard University, the University of Illinois, and the University of Texas.

Henry S. White is Distinguished Professor and John A. Widstoe Presidential Chair in the Department of Chemistry at the University of Utah in the United States. His research is focused on experimental and theoretical aspects of electrochemistry.

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