Laboratory Techniques in Electroanalytical Chemistry

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Laboratory Techniques in Electroanalytical Chemistry Second Edition, Revised and Expanded edited by Peter I Kissinger Purdue University and

1 Laboratory Techniques in Electroanalytical Chemistry Second Edition, Revised and Expanded edited by Peter I Kissinger Purdue University and Bioanalytical Systems, Inc. West Lafayette, Indiana William R. Heineman University of Cincinnati Cincinnati, Ohio m M A R C E L MARCEL»SHE«DEKKER, INC. NEW YORK BASEL

2 Contents Preface Contributors An Overview Peter T. Kissinger I. Some Philosophy II. III. Progress and Prognosis So Much Nomenclature, So Much Jargon Bibliography Fundamental Concepts of Analytical Electrochemistry Peter T. Kissinger, Carl R. Preddy, Ronald E. Shoup, and William R. Heineman II. Mass Transport: Linear Diffusion III. The Charged Interphase IV. The Nernst Equation and Electrochemical Reversibility V. Coupled Chemical Reactions and Chemical Reversibility VI. VII. Liquid-Solid Adsorption Conclusion Large-Amplitude Controlled-Potential Techniques William R. Heineman and Peter T. Kissinger II. Potential-Step Techniques in Stationary Solution III. IV. Potential-Scan Techniques in Stationary Solution Controlled-Potential Techniques in Flowing Solution in xv И vii

Contents 4 Large-Amplitude Controlled-Current Techniques 127 William R. Heineman and Peter T. Kissinger I. Controlled-Current Techniques in Stationary Solution 127 II.

3 Contents 4 Large-Amplitude Controlled-Current Techniques 127 William R. Heineman and Peter T. Kissinger I. Controlled-Current Techniques in Stationary Solution 127 II. Controlled-Current Techniques in Flowing Solution Small-Amplitude Controlled-Potential Techniques 141 Peter T. Kissinger and Thomas H. Ridgway 141 II. Faradaic Impedance 148 III. Sinusoidal Alternating-Current Voltammetry 150 IV. Cyclic Alternating-Current Voltammetry 152 V. Tensammetry 153 VI. Step-Based Methods 154 VII. Staircase Voltammetry 155 VIII. Differential Pulse Methods 156 IX. Square-Wave Methods 158 X. Differential "Normal Pulse" Voltammetry 159 XI. Conclusion Introduction to Analog Instrumentation 165 Peter T. Kissinger I. Classical Controlled-Potential Instrumentation 165 II. Controlled-Potential Instrumentation Based on Operational Amplifiers 172 III. Classical Controlled-Current Instrumentation 187 IV. Controlled-Current Instrumentation Based on Operational Amplifiers 188 V. Microprocessor-Based Electrochemical Instrumentation 189 VI. Conclusion 194 Reference Overcoming Solution Resistance with Stability and Grace in Potentiostatic Circuits 195 David K. Roe 195 II. Input-Output Relations of Cells and Potentiostats 199 III. Stability of Potentiostat-Cell Circuits and the Role of R u 205 IV. Compensation for ir u by Positive Feedback 217 V. Achieving Stability Through Gain-Frequency Shaping 222 VI. Real Systems 231 Appendix 232 Bibliography 234

Contents 8 Conductivity and Conductometry F. James Holler and Christie G. Enke I. Some Basic Relationships II. DC Contact Measurement of Conductance III.

4 Contents 8 Conductivity and Conductometry F. James Holler and Christie G. Enke I. Some Basic Relationships II. DC Contact Measurement of Conductance III. Capacitive Contact Measurement of Conductance 9 Electrochemical Cells Fred M. Hawkridge I. Design Concepts II. Stationary-Solution Experiments III. Convected-Solution Experiments IV. Thin-Layer Cell Design V. Cells for Spectroelectrochemistry 10 Carbon Electrodes Richard L. McCreery and Kristin K. Cline II. Performance Criteria III. Carbon Electrode Materials Properties IV. Common Carbon Electrode Materials V. Selection of Carbon Electrodes for Analytical Applications 11 Film Electrodes James L. Anderson and Nicholas Winograd II. Applications of Thin-Film Electrodes III. Properties of Film Electrodes IV. Metal Film Electrodes V. Carbon Film Electrodes VI. Semiconductor Film Electrodes VII. Techniques of Cell Design Based on Film Electrodes VIII. Prospects for Disposable, Integrated Sensor Systems 12 Microelectrodes Adrian C. Michael and R. Mark Wightman II. Construction of Microelectrodes III. Diffusion at Microelectrodes IV. High-Speed Cyclic Voltammetry V. Ohmic Drop at Microelectrodes Z ллз one

X Contents VI. Very Small Electrodes 396 VII. Conclusions 398 399 13 Chemically Modified Electrodes 403 Charles R. Martin and Colby A. Foss, Jr. 404 II.

5 X Contents VI. Very Small Electrodes 396 VII. Conclusions Chemically Modified Electrodes 403 Charles R. Martin and Colby A. Foss, Jr. 404 II. Methods for Preparing Chemically Modified Electrodes 404 III. Electrochemistry at Chemically Modified Electrodes 412 IV. Characterization and Analysis of Chemically Modified Electrodes 419 V. Applications of Chemically Modified Electrodes 431 VI. Conclusions Mercury Electrodes 443 Zbigniew Galus 443 II. Dropping Mercury Electrode 444 III. Hanging Mercury Drop Electrode 452 IV. Static Mercury Drop Electrode 456 V. Streaming Mercury Electrodes 457 VI. Mercury Film and Other Types of Mercury Electrodes Solvents and Supporting Electrolytes 469 Albert J. Fry 469 II. Recommended Solvents and Electrolytes 473 III. Some Other Solvents 474 IV. Solvent- and Electrolyte-Dependent Phenomena 476 V. Experimental Procedures 478 Appendix: Other Literature Electrochemical Studies at Reduced Temperature 487 Dennis H. Evans and Susan A. Lerke 487 II. Motivations for Variation of the Temperature in Electrochemical Studies 488 III. Examples of the Study of the Rates of Coupled Chemical Reactions 492 IV. Practical Aspects of Electrochemical Studies at Low Temperatures

6 Contents xi 17 Electroanalytical Chemistry in Molten Salts 511 Charles L. Hussey 511 II. Molten Salt Systems 513 III. Apparatus and Techniques Vacuum-Line Techniques 543 Vladimir Katovic, Michael A. May, and Csaba P. Keszthelyi 543 II. Vacuum Line 544 III. Electrochemical Glassware for the Vacuum Line Electrochemistry in the Dry Box 569 Steven N. Frank and Su-Moon Park 569 II. Choosing an Inert-Atmosphere System 570 III. Experimental Procedures 572 Appendix Digital Simulation of Electrochemical Problems 583 J. T. Malay 583 II. The Finite Difference Representation of Fick's Laws 584 III. The Model Diffusion Coefficient: Defining At and Ax 586 IV. Establishing Initial and Boundary Conditions 588 V. Dimensionless Parameters 591 VI. A Sample BASIC Program 593 VII. Chronocoulometry 595 VIII. Other Nernstian Electrode Boundary Conditions 599 IX. Homogeneous Kinetics 601 X. Parametric Substitutions 606 XI. Electrogenerated Chemiluminescence 608 XII. Chronopotentiometry 609 XIII. Linear Sweep and Cyclic Voltammetry 611 XIV. Simulation of Rotating Disk Hydrodynamics 613 XV. Simulation of Rotating Ring Disk Behavior 614 XVI. The Steady-State Assumption 616 XVII. Beyond the Basics

xh Contents 21 Evaluation of Mechanisms of Organic Reactions 623 M. Dale Hawley 623 II. Reduction of p-chlorobenzonitrile 624 III. Oxidation of Adrenaline 629 IV. Oxidation of a-tocopherol 633 V.

7 xh Contents 21 Evaluation of Mechanisms of Organic Reactions 623 M. Dale Hawley 623 II. Reduction of p-chlorobenzonitrile 624 III. Oxidation of Adrenaline 629 IV. Oxidation of a-tocopherol 633 V. Concluding Remarks Electroorganic Synthesis 641 Eberhard Steckhan I. What Is Electroorganic Synthesis? 641 II. Advantages and Disadvantages of Electroorganic Reactions 641 III. Technically Interesting Processes 643 IV. Classification of Electroorganic Reactions 647 V. Experimental Factors and Techniques Instructional Examples of Electrode Mechanisms of Transition Metal Complexes 683 William E. Geiger I. Electrode Mechanisms 683 II. Obtaining High-Quality Data 686 III. Mechanistic Studies 693 IV. Examples of Selected Mechanisms 694 V. Comments on Second-Order Homogeneous Reactions Electrochemical Preconcentration 719 Joseph Wang I. Why Preconcentration? 719 II. Stripping Analysis 719 III. Electrochemical Preconcentration for Spectroscopic Analysis Controlled-Current Coulometry 739 David J. Curran 739 II. Coulometric Generation of Reagents 740 III. Coulometric Titrations

8 Contents xüi 26 Electrochemistry in Pharmaceutical Analysis 769 Marvin A. Brooks and Eric W. Tsai 769 II. Coulometric Methods 774 III. Voltammetric Methods Electrochemical Detection in Liquid Chromatography and Capillary Electrophoresis 813 Susan M. Lunte, Craig E. Lunte, and Peter T. Kissinger 813 II. Transducer Design 816 III. Waveforms 832 IV. Applications Review 840 V. Capillary Electrophoresis/Electrochemistry 847 VI. Conclusions 850 VII. Performance Criteria for Electrochemical Detectors Photonic Electrochemistry 855 Andrew B. Bocarsly, Hiroyasu Tachikawa, and Larry R. Faulkner 855 II. Photoelectrochemistry Semiconductor/Electrolyte Interfaces 856 III. Photoemission from Metal Electrodes 882 IV. Electrochemical Monitoring of Photolytic Intermediates 884 V. Electrochemiluminescence 887 Appendix: Structures of Cited Molecules Principles and Techniques of Electrochemical-Electron Paramagnetic Resonance Experiments 901 Ira B. Goldberg and Ted M. McKinney I. Magnetic Resonance in Electrochemical Studies 901 II. Molecular Orbitals in Electrochemistry and EPR 903 III. Principles of EPR 907 IV. EPR Instrumentation 920 V. Experimental Methods of EPR-Electrochemical Studies 927 VI. Selected Applications of EPR and Electrochemical Measurements 943 Appendix I: Selected Bibliography 954 Appendix II: Units Index 961

FUNDAMENTALS OF ELECTRO- ANALYTICAL CHEMISTRY

FUNDAMENTALS OF ELECTRO- ANALYTICAL CHEMISTRY Paul Monk Manchester Metropolitan University, Manchester, UK JOHN WILEY & SONS LTD Chichester New York Weinheim Brisbane Toronto Singapore Contents Series