ELECTROCHEMISTRY FOR CHEMISTS Second Edition DONALD T. SAWYER Texas A&M University ANDRZEJ SOBKOWIAK Rzeszow University of Technology JULIAN L. ROBERTS, Jr. University of Redlands ® A Wiley-Interscience Publication JOHN WILEY & SONS, INC. New York / Chichester / Brisbane / Toronto / Singapore UNIVERSITY OF PAISLEY LIBRARYorw This text is printed on acid-free paper. Copyright © 1995 by John Wiley & Sons, Inc. All rights reserved. Published simultaneously in Canada. Reproduction or translation of any part of this work beyond that permitted by Section 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful. Requests for permission or further information should be addressed to the Permissions Department, John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012. Library of Congress Cataloging in Publication Data: Sawyer, Donald T. Electrochemistry for chemists / Donald T. Sawyer, Andrzej Sobkowiak, Julian L. Roberts, Jr.—2nd ed. Pp. cm. Rev. ed. of: Experimental electrochemistry for chemists. 1974 Includes bibliographical references. ISBN 0-471-59468-7 (cloth) 1. Electrochemistry. I. Sobkowiak, Andrzej. I. Roberts, Julian L. III. Sawyer, Donald T. Experimental electrochemistry for chemists. IV. Title QD553.832 1995 541.3'7—de20 95-2738 Printed in the United States of America 1098765432PREFACE Since the previous edition of this monograph (Experimental Electrochemistry for Chemists, 1974), the utilization of electrochemistry for chemical charac- terization has undergone a revolution. Chemists, biologists, and materials sci- entists make regular use of potentiometry and cyclic voltammetry to detect and evaluate the redox (reduction-oxidation) thermodynamics, the electron-transfer stoichiometry and kin , and the valence states of redox-active molecules. Although the basic principles and methodologies for useful electrochemical measurements remain unchanged, the currently available commercial instru- mentation, electrodes, solvents, and reagents make possible routine application of electrochemical measurements for the characterization of chemical systems and materials that were outside the realm of consideration 20 years ago. Be- cause of this, many new applications of electrochemical measurements have been perfected in recent years. These substantive changes and advances have made much of our earlier volume obsolete and seriously deficient with respect to instrumentation, solvents, reagents, and applications. The focus of this edition remains the same as that for the first, namely, to make electrochemistry an attractive, useful characterization methodology for chemists [comparable to infrared (IR), nuclear magnetic resonance (NMR) spectroscopy, and mass spectrometry (MS)]. The goal is to outline the basic principles and modern methodology of electrochemistry in such a way that the uninitiated may gain sufficient background to use electrochemical methods for the study of chemical systems. Thus chemical problems that are amenable to an electrochemical approach are introduced as representative examples. This monograph has been developed for the nonelectrochemist who is in- terested in the advantages and use of electrochemical methods for research andvi PREFACE laboratory measurements. With such a pragmatic goal, our purpose has not been to develop the theory in detail. Therefore, we have limited our presen- tation to those relations that allow the effective treatment of experimental data. Sufficient references are given for those who wish to pursue the theory. Twenty years ago the main applications of electrochemistry were trace-metal analysis (polarography and anodic stripping voltammetry) and selective-ion assay (pH, pNa, pK via potentiometry). A secondary focus was the use of voltammetry to characterize transition-metal coordination complexes (metal— ligand stoichiometry, stability constants, and oxidation-reduction thermody- namics). With the commercial development of (1) low-cost, reliable poten- tiostats; (2) pure, inert glassy-carbon electrodes; and (3) ultrapure, dry aprotic solvents, molecular characterization via electrochemical methodologies has be- come accessible to nonspecialists (analogous to carbon-13 NMR and GC/MS). The goal of this volume is to provide (1) an introduction to the basic prin- ciples of electrochemistry (Chapter 1), potentiometry (Chapter 2), voltammetry (Chapter 3), and electrochemical titrations (Chapter 4); (2) a practical, up-to- date summary of indicator electrodes (Chapter 5), electrochemical cells and instrumentation (Chapter 6), and solvents and electrolytes (Chapter 7); and (3) illustrative examples of molecular characterization (via electrochemical mea- surements) of hydronium ion, Brgnsted acids, and H, (Chapter 8); dioxygen species (O,, 0; /HOO-, HOOH) and H,O/HO™ (Chapter 9); metals, metal compounds, and metal complexes (Chapter 10); nonmetals (Chapter 11); car- bon compounds (Chapter 12); and organometallic compounds and metallopor- phyrins (Chapter 13). The later chapters contain specific characterizations of Tepresentative molecules within a class, which we hope will reduce the ‘‘bar- riers of unfamiliarity” and encourage the reader to make use of electrochemistry for related chemical systems. This enterprise would not have been possible without the assistance, support, and encouragement of colleagues, current and former students and postdoctoral associates, and the staff of our respective universities. In particular, the dedi- cated efforts of Monica Gonzales and Lori Locke to produce the final manu- script are gratefully acknowledged. Drs. Xiu Liu and John Hage provided assistance with the graphics and equations, and Debbie Bush produced prelim- inary drafts for several chapters. Closure of what appeared to be an interminable project was made possible by a grant-in-aid from the Alcoa Foundation. A special acknowledgment to Dr. Ted Hoffman [Chemistry Editor of Wiley- Interscience for 25 years until retirement; November 1, 1994] for the encour- agement and support that made possible the first edition, and for the faith and patience that allowed the present volume to be realized. We are especially grateful for his (1) understanding of the academics’ propensity to overcommit and (2) ability to give a positive dimension to missed deadlines. The editorial staff of Wiley-Interscience have been helpful and understanding in their assis- tance to the authors.PREFACE viii Finally, a sincere and personal acknowledgment to our wives, Shirley, Krys- tyna, and Jane, for their indulgence, patience, and support in what appeared to be a never-ending project. Dona.p T. SAWYER ANDRZEJ SOBKOWIAK JuLIAN L. Roperts, JR. College Station, Texas Rzeszow, Poland Redlands, California November 1994CONTENTS 1 INTRODUCTION AND FUNDAMENTALS 1 1.1 Introduction / 1 1.2 Nomenclature and Classes of Electrochemical Methodology / 3 1.3 Sign and Graphical Conventions / 6 1.4 Utilization of Electrochemistry for Chemical Characterization / 6 1.5 The Fundamentals / 9 The Hydrated Electron / 10 Electron Transfer in Electrochemistry / 11 1.6 Nucleophile-Electrophile Electron Transfer / 16 1.7 The Dynamics of Electron Transfer (Kinetics and Thermodynamics) / 17 References / 21 POTENTIOMETRY MEASUREMENTS 24 2.1 Introduction / 24 2.2 Principles and Fundamental Relations / 25 2.3 Blectrode Systems / 30 2.4 Applications of Potentiometry / 38 References / 51CONTENTS CONTROLLED-POTENTIAL METHODS 53 3.1 Introduction / 53 Control of Potential and Measurement of Current / 53 3.2 Principles and Fundamental Relations / 55 Diffusion to a Planar Electrode / 55 3.3. Polarography / 57 Current-Sampled Polarography / 63 AC Polarography / 65 Square-Wave Polarography / 66 Pulse Polarography / 66 Stripping Analysis / 66 3.4 Linear Sweep and Cyclic Voltammetry / 68 Adsorption / 77 3.5 Microelectrode Voltammetry / 78 3.6 Ring-Disk Voltammetry / 79 3.7 Chronoamperometry and Chronocoulometry / 84 3.8 Controlled-Potential Bulk Electrolysis / 86 3.9 Methodology / 87 3.10 Application of Controlled-Potential Methods / 98 References / 135 ELECTROCHEMICAL TITRATIONS AND CONTROLLED- CURRENT METHODS 139 4.1 Introduction / 139 4.2 Endpoint Detection Methods / 139 Potentiometric Methods / 139 Amperometric Methods / 144 Conductometric Methods / 148 4.3 Autotitrators / 149 4.4 pH-Stats / 151 4.5 Coulometric Titrations / 152 4.6 Controlled-Current Methods / 159 References / 168 INDICATOR ELECTRODES 170 5.1 Measurement of Electrode Potentials / 170 Junction Potentials / 172 Cells with Liquid Junctions and Elimination of Junction Potentials / 1755.2 5.3 5.4 5.5 5.6 5. Q CONTENTS = xi Some Practical Considerations in the Use of Salt Bridges / 182 Reference Electrodes / 184 Properties of the Ideal Reference Electrode / 184 Reference Electrodes for Use in Aqueous Solutions / 185 Reference Electrodes for Use in Polar Aprotic Solvents / 199 Reference Electrodes for Use in Nonpolar Solvents / 204 Reference Electrodes for Use in Fused-Salt Systems / 204 Voltammetric Indicator Electrodes / 206 Electrode Materials and Their Electrochemical Behavior / 206 Measurement of Electrode Area / 216 Electrode Pretreatment / 219 Construction and Mass-Transport Properties of Voltammetric Electrodes / 220 Optically Transparent Electrodes / 234 Mercury Indicator Electrodes / 235 Solid Indicator Electrodes / 238 pH-Sensitive Solid Indicator Electrodes / 239 Selective-Ion Electrodes / 239 References / 243 ELECTROCHEMICAL CELLS AND INSTRUMENTATION 249 6.1 6.2 Electrochemical Cells: Introduction / 249 General Requirements / 249 Materials for the Construction of Cells and Electrodes / 257 Changes in Solution Composition Caused by Structural Materials / 261 The Maintenance of an Inert Atmosphere / 264 Description of General-Purpose Cells / 271 Cells for Voltammetry and Polarography / 271 Cells for Coulometric and Preparative Electrochemistry / 274 Control of Temperature and Pressure / 279 Cells for Conductimetry / 281 Microcells / 282 Flow and Circulation Cells / 283 Cells for Spectroelectrochemistry / 284CONTENTS 6.3 Instrumentation: Measurements / 286 Voltage / 286 Current / 288 Bridge Measurements of Resistance, Capacitance, and Inductance / 288 6.4 Sources / 294 References / 295 SOLVENTS AND ELECTROLYTES 7.1 Introduction / 299 The Physicochemical Properties of Solvents and Their Relevance to Electrochemistry / 299 Classification of Solvents / 311 7.2 Role of the Solvent-Supporting Electrolyte System in Electrochemistry / 313 Role of the Supporting Electrolyte / 316 Control of Cell Resistance / 316 Control of Solution Acidity / 319 Complex Formation / 322 Ion-Pairing and Double-Layer Effects / 322 Micellar Aggregates / 324 7.4 Electrochemical Properties of Water and Selected Organic Solvents / 324 Water / 324 Nonaqueous Solvents / 327 7.5 Preparation and Purification of Supporting Electrolytes / 335 7.6 Sources / 337 References / 337 a ie HYDRONIUM IONS (H,0*), BRONSTED ACIDS (HA), AND MOLECULAR HYDROGEN (H,) 8.1 Introduction / 342 8.2 Hydronium Ion (H,0*) Reduction / 343 8.3 Brfnsted Acid (HA) Reduction and Evaluation of PRasoy / 346 8.4 Oxidation of Dissolved Dihydrogen (Hz) / 350 References / 357 299 342CONTENTS xii 9 DIOXYGEN SPECIES (0,, HOO, 0; , HOOH, HOO-), OZONE (0,), AND ATOMIC OXYGEN 358 9.1 Introduction; Redox Thermodynamics / 358 Molecular Oxygen / 358 Superoxide Ion / 361 Atomic Oxygen / 362 9.2 Electrochemistry of Dioxygen / 364 Electron-Transfer Reduction of O, / 367 Aprotic Media / 370 Protic and Electrophilic Substrates / 373 Electrode Material Effects / 379 Transition-Metal Complexes (ML,); O2 Reduction Catalysts / 380 Chemical Reduction / 392 Reduction of O, by Atom Transfer / 393 Concerted One-Electron Reductions / 394 Applications / 397 9.3 Reduction of HOOH / 398 9.4 Oxidation of HOOH and HOO™ / 399 9.5 Summary / 399 References / 400 10 METALS AND METAL COMPLEXES 403 10.1 Oxidation of Metals / 403 Metal-X Bond Energies / 404 10.2 Oxidation-Reduction of Transition-Metal Complexes / 407 Metal-Ligand Bond Energies / 407 References / 419 11. NONMETALS (SULFUR, NITROGEN, AND CARBON COMPOUNDS) 420 11.1 Introduction / 420 11.2 Sulfur / 421 Elemental Sulfur (Sg) / 421 Sulfur Dioxide (SO,) / 422 Propane-1 ,3-dithiol [HS(CH);SH] / 425xiv 12 13 CONTENTS 11.3 Nitrogen / 427 Nitric Oxide (NO) / 427 Nitrous Acid (HON=O) / 428 Nitrous Oxide (N,O) / 429 Hydroxylamine (H,NOH) / 429 Hydrazines and Amines / 430 Phenazine (Phen) / 434 Carbon / 436 Carbon Dioxide (CO) / 436 Carbon Monoxide (CO) / 438 Cyanide Ion (NC~) / 438 References / 440 ORGANIC COMPOUNDS 442 12.1 12.2 Introduction / 442 Reduction of Electrophilic Substrates (Lewis Acids) / 444 Alkyl- and Aryl-Halides / 444 Quinones, Semiquinones, and Catechols / 446 Dehydroascorbic Acid and Ascorbic Acid / 451 Carbonyl Groups, Olefins, and Aromatic Hydrocarbons / 455 Brénsted Acids / 457 Viologens / 457 Oxidation of Nucleophilic Substrates and Lewis Bases / 457 Catechols and Hydroquinones / 458 Phenols / 460 Benzyl Alcohols / 461 Aromatic Hydrocarbons / 461 Dithiols / 463 References / 464 ORGANOMETALLIC COMPOUNDS AND METALLOPORPHYRINS 466 13.1 13.2 Introduction / 466 Organometallic Molecules / 467 Ferrocene / 467 Iron-Pentacarbonyl / 469 Gold-Catalyzed Oxidation of Carbon Monoxide / 469CONTENTS = XV 13.3 Metalloporphyrins / 470 Nucleophilic Character of Iron- and Cobalt-Porphyrin Anions; Evaluation of Their Metal-Carbon Bond Energies / 482 References / 492 INDEX 495CHAPTER 1 SL INTRODUCTION AND FUNDAMENTALS 1.1. INTRODUCTION The technology for the interconversion of chemical energy and electrical energy has been utilized since the midnineteenth century. This conversion is accom- plished by ionic current flow in an electrolyte solution between two electrodes connected to each other via an external circuit with an electrical load or current source, Batteries, fuel cells, and corrosion processes convert the energy of chemical reactions into electrical energy. Electrolysis, electroplating, and some forms of electroanalysis reverse the direction of conversion, using electrical energy to produce a net chemical change. The basic principles and quantitative relationships (voltage, current, charge conductance, capacitance, and concen- tration) for electrochemical phenomena were empirically elucidated by Michael Faraday and other European scientists before the discovery of the electron (J. J. Thompson, 1893) and the development of chemical thermodynamics (G. N. Lewis, 1923). Building on this foundation, the utilization of electrochemical phenomena for thermodynamic characterization and analysis of molecules and ions (electroanalytical chemistry) began at the beginning of this century [po- tentiometry (1920) and polarography (1930)]. Relationships that describe the techniques of potentiometry and polarography derive directly from solution thermodynamics. In the case of polarography, there is a further dependence on the diffusion of ionic species in solution. The latter is the basis of conductivity measurements, another area that traces its origin to the nineteenth century. These quantitative relationships make it possible to apply electrochemistry to2 INTRODUCTION AND FUNDAMENTALS. the detailed characterization of chemical species and processes in the solution phase. During the past four decades the dynamics and mechanisms of electron- transfer processes have been studied via the application of transition-state theory to the kinetics for electrochemical processes. As a result, both the kinetics of the electron-transfer processes (from solid electrode to the solution species) as well as of pre- and post-electron-transfer homogeneous processes can be char- acterized quantitatively. By the use of various transient methods, electrochemistry has found exten- sive new applications for the study of chemical reactions and adsorption phe- nomena. Thus a combination of thermodynamic and kinetic measurements can be utilized to characterize the chemistry of heterogeneous electron-transfer re- actions. Furthermore, heterogeneous adsorption processes (liquid-solid) have been the subject of intense investigations. The mechanisms of metal ion com- plexation reactions also have been ascertained through the use of various elec- trochemical impulse techniques. The so-called renaissance of electrochemistry has come about through a combination of modern electronic instrumentation and the development of a more pragmatic theory implemented with the data-processing and computa- tional power of computers. Within the area of physical chemistry, numerous thermodynamic studies of unstable reaction intermediates have made use of moder electrochemistry. In addition, extensive studies of the kinetics of elec- tron-transfer processes in aqueous and nonaqueous media have been accom- plished. The electrochemical characterization of adsorption phenomena has been of immense benefit to the understanding of catalytic processes. Some of the most exciting applications of electrochemistry have occurred in the areas of organic and inorganic chemistry, and biochemistry. The applica- tions have ranged from mechanistic studies to the synthesis of unstable or exotic species. The control of an oxidation or reduction process through electrochem- istry is much more precise than is possible with chemical reactants. Within the area of inorganic chemistry, electrochemistry has been especially useful for the determination of formulas of coordination complexes and the electron-transfer stoichiometry of new organometallic compounds. Electrochemical synthesis is increasingly important to the field of organometallic chemistry. During the past 40 years there have been numerous exciting extensions of electrochemistry to the field of analytical chemistry. A series of selective-ion potentiometric electrodes have been developed, such that most of the common ionic species can be quantitatively monitored in aqueous solution. A highly effective electrolytic moisture analyzer provides continuous online assays for water in gases. Another practical development has been the voltammetric mem- brane electrode for dioxygen (O,), which responds linearly to the partial pres- sure of QO), either in the gas phase or in solution. The use of an immobilized enzyme (glucose oxidase) on an electrode sensor to assay glucose in blood is another extension of electrochemistry to practical analysis.