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E-raamat: Electrochemical Methods: Fundamentals and Applications

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(University of Texas at Austin, USA), (University of Texas at Austin, USA), (University of Utah, USA)
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  • Ilmumisaeg: 26-Apr-2022
  • Kirjastus: John Wiley & Sons Inc
  • Keel: eng
  • ISBN-13: 9781119334071
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Electrochemical Methods: Fundamentals and ApplicationsSuurem pilt
  • Formaat: PDF+DRM
  • Ilmumisaeg: 26-Apr-2022
  • Kirjastus: John Wiley & Sons Inc
  • Keel: eng
  • ISBN-13: 9781119334071
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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 Lebègue, 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
1(60)
1.1 Basic Ideas
2(15)
1.1.1 Electrochemical Cells and Reactions
2(2)
1.1.2 Interfacial Potential Differences and Cell Potential
4(1)
1.1.3 Reference Electrodes and Control of Potential at a Working Electrode
5(1)
1.1.4 Potential as an Expression of Electron Energy
6(1)
1.1.5 Current as an Expression of Reaction Rate
6(2)
1.1.6 Magnitudes in Electrochemical Systems
8(1)
1.1.7 Current--Potential Curves
9(7)
1.1.8 Control of Current vs. Control of Potential
16(1)
1.1.9 Faradaic and Nonfaradaic Processes
17(1)
1.2 Faradaic Processes and Factors Affecting Rates of Electrode Reactions
17(6)
1.2.1 Electrochemical Cells---Types and Definitions
17(1)
1.2.2 The Electrochemical Experiment and Variables in Electrochemical Cells
18(3)
1.2.3 Factors Affecting Electrode Reaction Rate and Current
21(2)
1.3 Mass-Transfer-Controlled Reactions
23(8)
1.3.1 Modes of Mass Transfer
24(1)
1.3.2 Semiempirical Treatment of Steady-State Mass Transfer
25(6)
1.4 Semiempirical Treatment of Nernstian Reactions with Coupled Chemical Reactions
31(3)
1.4.1 Coupled Reversible Reactions
31(1)
1.4.2 Coupled Irreversible Chemical Reactions
32(2)
1.5 Cell Resistance and the Measurement of Potential
34(7)
1.5.1 Components of the Applied Voltage When Current Flows
35(2)
1.5.2 Two-Electrode Cells
37(1)
1.5.3 Three-Electrode Cells
37(1)
1.5.4 Uncompensated Resistance
38(3)
1.6 The Electrode/Solution Interface and Charging Current
41(10)
1.6.1 The Ideally Polarizable Electrode
41(1)
1.6.2 Capacitance and Charge at an Electrode
41(1)
1.6.3 Brief Description of the Electrical Double Layer
42(2)
1.6.4 Double-Layer Capacitance and Charging Current
44(7)
1.7 Organization of this Book
51(1)
1.8 The Literature of Electrochemistry
52(2)
1.8.1 Reference Sources
52(1)
1.8.2 Sources on Laboratory Techniques
53(1)
1.8.3 Review Series
53(1)
1.9 Lab Note: Potentiostats and Cell Behavior
54(3)
1.9.1 Potentiostats
54(1)
1.9.2 Background Processes in Actual Cells
55(1)
1.9.3 Further Work with Simple RC Networks
56(1)
1.10 References
57(1)
1.11 Problems
57(4)
2 Potentials and Thermodynamics of Cells
61(60)
2.1 Basic Electrochemical Thermodynamics
61(19)
2.1.1 Reversibility
61(3)
2.1.2 Reversibility and Gibbs Free Energy
64(1)
2.1.3 Free Energy and Cell emf
64(2)
2.1.4 Half-Reactions and Standard Electrode Potentials
66(1)
2.1.5 Standard States and Activity
67(2)
2.1.6 EMF and Concentration
69(2)
2.1.7 Formal Potentials
71(1)
2.1.8 Reference Electrodes
72(4)
2.1.9 Potential-pH Diagrams and Thermodynamic Predictions
76(4)
2.2 A More Detailed View of Interfacial Potential Differences
80(11)
2.2.1 The Physics of Phase Potentials
80(2)
2.2.2 Interactions Between Conducting Phases
82(2)
2.2.3 Measurement of Potential Differences
84(1)
2.2.4 Electrochemical Potentials
85(3)
2.2.5 Fermi Energy and Absolute Potential
88(3)
2.3 Liquid Junction Potentials
91(10)
2.3.1 Potential Differences at an Electrolyte--Electrolyte Boundary
91(1)
2.3.2 Types of Liquid Junctions
91(1)
2.3.3 Conductance, Transference Numbers, and Mobility
92(4)
2.3.4 Calculation of Liquid Junction Potentials
96(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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