Pub. Date:
Oxford University Press, USA
Broadening Electrochemical Horizons: Principles and Illustration of Voltammetric and Related Techniques

Broadening Electrochemical Horizons: Principles and Illustration of Voltammetric and Related Techniques

by Alan M. Bond, A. M. Bond


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"Electrochemistry is a well established discipline that has encompassed both applied and fundamental aspects of chemistry courses for nearly a century. In recent years, however, it has become obvious that even broader applications of this valuable technique are now available to advance knowledge and solve problems in organic, inorganic and biological chemistry. In this book, it is shown how a range of limitations that historically have restricted the use of voltammetric and related electrochemical techniques have been removed or minimised so that it is now possible to work in the gas and solid phases as well as the traditional liquid phase. Significant advances in theory, instrumentation and electrode design have also made the technique more user-friendly. The initial chapters of this book describe the basic theory and philosophy behind the modern, widespread use of voltammetric techniques. The later chapters provide examples of new areas of application and predict future possibilities for this exciting area."

Product Details

ISBN-13: 9780198504788
Publisher: Oxford University Press, USA
Publication date: 12/01/2002
Series: Oxford Science Publications
Pages: 536
Product dimensions: 9.60(w) x 6.70(h) x 1.50(d)

Table of Contents

1The fundamentals of electrochemistry1
1Introductory remarks1
2Redox reactions, electrochemical cells, and standard potentials6
3Thermodynamics versus kinetics19
4Calculation of reaction volumes and entropies from the dependence of the reversible potential on temperature and pressure21
5Voltammetry and kinetics22
6Application of the principles of electrochemistry to fuel cells, photovoltaic cells, and the lead-acid battery25
6.1Fuel cells26
6.2Dye-sensitized photovoltaic cells28
6.3Lead-acid battery29
2Principles of voltammetry, electrolysis, spectroelectrochemistry, and other techniques employed in studies involving solution phase and surface-based electrode processes33
1An overview33
2The electrochemical cell used for voltammetric experiments34
3The electrodes used in voltammetric experiments36
3.1Working electrodes36
3.2Reference electrodes38
3.3Counter/auxiliary electrodes40
4The two major classes of voltammetry41
4.1Transient voltammetry41
4.2Steady-state voltammetry42
5Evaluation of electrode reaction mechanisms43
6Factors contributing to the nature of the current-potential curve obtained in voltammetric experiments43
6.1Faradaic and non-Faradaic currents47
7Understanding the basic features of an electrode process when the redox active species are soluble in the solution phase48
7.1Mass transport48
7.2Electron transfer52
7.3Homogeneous chemical kinetics54
7.4Electrochemical and chemical reversibility55
8Cyclic voltammetry under transient conditions when the redox active species are soluble in the solution phase57
8.1Theory of cyclic voltammetry59
9Hydrodynamic voltammetry68
9.1Rotating-disc electrode voltammetry69
9.2Channel electrodes71
9.3Wall-jet electrodes74
9.4A survey of the use of the theory of hydrodynamic voltammetry75
10Voltammetric studies at microelectrodes when the redox active species are soluble in the solution phase78
10.1Principles of the theory of microelectrode voltammetry79
11Semi-integration and semi-differentiation (convolution voltammetry)83
11.1Some valuable properties of the semi-integral84
11.2Measurement of uncompensated resistance by semi-integration85
12General features associated with the modelling of voltammetric experiments88
12.1Information required to solve voltammetric theory88
12.2Methods used for solving voltammetric theory90
13A summary of the theoretical principles of voltammetry91
13.1Application of Faraday's law91
13.2A general approach to understanding a voltammetric problem92
14Comparison of voltammetric techniques when the redox active species are soluble in the solution phase95
14.1A quantitative comparison of the kinetic discrimination of homogeneous reactions at common electrode geometries under voltammetric steady-state conditions96
14.2A comparison of the homogeneous kinetic discrimination of steady-state and transient experiments98
15Bulk electrolysis100
15.1Theory of bulk electrolysis102
15.2Cells for bulk electrolysis104
16.1ESR spectroelectrochemistry108
16.2IR spectroelectrochemistry113
16.3UV-visible spectroelectrochemistry116
16.4NMR spectroelectrochemistry117
16.5Combining mass spectrometry and electrochemistry117
17Voltammetry at variable pressure and temperature123
18Voltammetric studies on solids attached to electrode surfaces in the form of thin films128
18.1General aspects128
18.2Electron transfer in ideal redox active thin films attached to electrode surfaces131
18.3Chemical reactions coupled to ideal thin-film electron-transfer process146
18.4Nuances associated with adsorption149
19Techniques for obtaining molecular level information on reactions associated with the voltammetry of surface-attached species152
19.1The use of scanning probe microscopies in electrochemistry155
19.2The electrochemical quartz crystal microbalance162
3Illustrating the basics of voltammetry for solution-soluble redox active species involving reversible electron transfer and reversible coupled chemical reactions: the reduction of electrochemically rich polyoxometalate compounds177
2Structural features of polyoxometalates177
3Coupled electron- and proton-transfer reactions associated with the reduction of [alpha]-[P subscript 2]W[subscript 18]O[subscript 62 superscript 6-] and [alpha]-[H subscript 2]W[subscript 12]O[subscript 40 superscript 6-]: comparison of simulated and experimental cyclic voltammograms obtained in aqueous media as a function of pH179
3.1Reduction of [alpha]-[P subscript 2]W[subscript 18]O[subscript 62 superscript 6-]180
3.2Reduction of [alpha]-[H subscript 2]W[subscript 12]O[subscript 40 superscript 6-]190
3.3Discussion of results obtained from the simulation of the reduction of [alpha]-[P subscript 2]W[subscript 18]O[subscript 62 superscript 6-] and [alpha]-[H subscript 2]W[subscript 12]O[subscript 40 superscript 6-]192
4Studies of the electrochemical reduction of [alpha]-[S subscript 2]Mo[subscript 18]O[subscript 62 superscript 4-] in aprotic and protic media[superscript 3]195
4.1Voltammetry of [alpha]-[S subscript 2]Mo[subscript 18]O[subscript 62 superscript 4-] in aprotic acetonitrile media197
4.2Spectroelectrochemistry in acetonitrile207
4.3Electrochemical synthesis of one- and two-electron reduced forms of [S subscript 2]Mo[subscript 18]O[subscript 62 superscript 4-]211
4.4A systematic approach to chemical synthesis of a two-electron reduced form of [S subscript 2]Mo[subscript 18]O[subscript 62 superscript 4-]212
4.5Voltammetry of [S subscript 2]Mo[subscript 18]O[subscript 62 superscript 4-] in acidic (95/5) acetonitrile/water media215
4.6Photoelectrochemical studies of [S subscript 2]Mo[subscript 18]O[subscript 62 superscript 4-] using a hydrodynamic channel electrode230
5Use of voltammetric techniques to identify the products formed when [S subscript 2]Mo[subscript 18]O[subscript 62 superscript 4-] reacts with Ph[subscript 3]P and Bu[subscript 3]P in (95/5) CH[subscript 3]CN/H[subscript 2]O234
5.1Reaction of [S subscript 2]Mo[subscript 18]O[subscript 62 superscript 4-] with Ph[subscript 3]P in (95/5) CH[subscript 3]CN/H[subscript 2]O236
5.2Reaction of [S subscript 2]Mo[subscript 18]O[subscript 62 superscript 4-] with Ph[subscript 3]P under irradiative conditions239
5.3Reaction of [S subscript 2]Mo[subscript 18]O[subscript 62 superscript 4-] with "Bu[subscript 3]P in (95/5) CH[subscript 3]CN/H[subscript 2]O: an explanation of differences relative to reaction with PPh[subscript 3]241
6An overview of results obtained by application of voltammetric, simulation, and spectroelectrochemical techniques to polyoxometalate reduction studies243
6.1Cyclic voltammetry244
6.2Rotated-disc electrode voltammetry244
6.3Channel-electrode voltammetry244
6.4Microdisc-electrode voltammetry244
6.6Bulk clcctrolysis245
6.7Combinations of techniques245
4Electrode processes that illustrate the influence of irreversible homogeneous reactions and the competition between reactions that occur in the solution phase and on the electrode surface: fundamental studies, photovoltaic dye-sensitizers, stripping voltammetry and glucose biosensors248
2Elucidation of the homogeneous reaction pathways that accompany the electrochemical oxidation of cis,mer-Mn(CO)[subscript 2]([eta superscript 1]-dpm)([eta superscript 2]-dpm) Br(dpm = Ph[subscript 2]PCH[subscript 2]PPh[subscript 2]) in dichloromethane250
2.1Voltammetric studies in dichloromethane251
2.2Bulk electrolysis and spectroelectrochemical experiments253
2.3Simulation of the voltammetry260
2.4Conclusions derived from electrochemical studies on cis,mer-Mn(CO)[subscript 2]([eta superscript 1]-dpm)([eta superscript 2]-dpm)Br261
3Electrochemical studies on the [V(CO) subscript 6 superscript -/0] process in aqueous media262
3.1Voltammetric oxidation of [V(CO) subscript 6 superscript -] in acetone solutions containing water262
3.2Voltammetric, EQCM, and chronocoulometric studies on the oxidation of [V(CO) subscript 6 superscript -] in water264
3.3Conclusions derived from voltammetric studies on [V(CO) subscript 6 superscript -] in aqueous media267
4Voltammetric studies on the oxidation of the highly surface-active polypyridyl ruthenium photovoltaic sensitizer cis-Ru(II)(dcbpy)[subscript 2] (NCS)[subscript 2](dcbpy = 2,2'-bipyridine-4,4'-dicarboxylic acid268
4.1Reference studies on model mass-transport-controlled processes269
4.2Electrochemical studies on cis-Ru(dcbpy)[subscript 2](NCS)[subscript 2] in acetone272
4.3Voltammetry of cis-Ru(dcbpy)[subscript 2](NCS)[subscript 2] in tetrahydrofuran, acetonitrile, and dimethylformamide280
4.4Conclusions related to the voltammetry of surface-active cis-Ru(dcbpy)[subscript 2](NCS)[subscript 2]281
5Stripping voltammetry282
5.1Anodic stripping voltammetry with thin-film mercury electrodes283
5.2Theory for a reversible process288
5.3Comparison of experimental results and theory293
5.4Mechanism associated with the adsorptive stripping voltammetry of cobalt (and nickel) dimethylglyoxime complexes at mercury electrodes301
6Glucose biosensors319
6.1The ferrocene-based glucose sensor322
6.2Optimization of the performance of a solution-phase electrochemical glucose biosensor325
6.3Fabrication of a glucose bioelectrochemical sensor employing glucose oxidase immobilized onto an electrode surface329
6.4Glucose analysis of whole blood with a commercially available glucose bioelectrochemical sensor329
5Illustration of the principles of voltammetry at solid-electrode-solvent (electrolyte) interfaces when redox active microparticles are adhered to an electrode surface334
2Strategies to detect factors that may be important in the voltammetry of redox active microparticles adhered to an electrode surface336
3Mechanistic aspects of the electron and ion-transport processes across the electrode-solid-solvent (electrolyte) interface when arrays of non-conducting microparticles are attached to an electrode337
3.1The oxidation of decamethylferrocene337
3.2Electrochemistry of microparticles of trans-Cr(CO)[subscript 2](dpe)[subscript 2], trans-[Cr(CO) subscript 2](dpe)[subscript 2 X] salts, and cis-Cr(CO)[subscript 2](dpe)[subscript 2], (dpe = bidentate Ph[subscript 2]PCH[subscript 2]CH[subscript 2]PPh[subscript 2], X[superscript -] = anion) attached to an electrode surface345
3.3Overview of factors that influence the voltammetry of decamethylferrocene and trans-Cr(CO)[subscript 2](dpe)[subscript 2] attached to an electrode surface361
3.4Problems with a theoretical description of the voltammetry of non-conducting microcrystals365
4Voltammetry of TCNQ adhered to an electrode surface: detection of solid-state transformation, redistribution, and dissolution processes by application of X-ray diffraction, electron scanning microscopy, atomic force microscopy and electron spin resonance techniques367
4.1Solution-phase voltammetry of TCNQ368
4.2Voltammetric studies on microcrystals of TCNQ adhered to electrode surfaces in contact with Na[superscript +], K[superscript +], Rb[superscript +], and Cs[superscript +] containing electrolytes369
4.3Electrochemically driven transformation of microcrystalline TCNQ to tetraalkylammonium [TCNQ superscript -] salts392
4.4Dissolution of solid TCNQ and [TCNQ superscript -] salts from electrode surfaces395
4.5Comparison of electrochemical data with microcrystals and other forms of surface-confined TCNQ415
4.6Conclusions related to the electrochemistry of TCNQ adhered to electrode surfaces423
5Voltammetric studies on systems where coupled electron and ion transport within an adhered microparticle are rate determining424
6Voltammetric studies on adhered microparticles where 'thin-film' behaviour is exhibited428
7An overview of the techniques used in electrochemical studies of microparticles adhered to electrode surfaces436
6Use of metalloprotein voltammetry to illustrate the nuances of electrochemistry related to blocked electrodes, chemically modified electrodes, electrode functionality, and microscopic aspects of electrode behaviour441
2Structural features of metalloproteins that may give rise to features that are different to those encountered in the voltammetry of small molecules442
3Studies on protein-surface attachment to a gold electrode by in situ scanning probe microscopy443
4The influence of surface attachment of metalloproteins on voltammetric studies447
4.1General features of voltammetry of metalloproteins at bare (unmodified) gold electrodes447
4.2The transient nature of the voltammetry of cytochrome c at 'bare' gold electrodes: an explanation based on a self-blocking mechanism450
5Voltammetry of metalloproteins at chemically modified gold electrodes459
6Voltammetry of metalloproteins at naturally and deliberately functionalized carbon electrodes464
6.1Cytochrome c471
6.4General conclusions concerning the voltammetry of metalloproteins at carbon electrodes476
7Quantitative use of a microscopic model to explain the unusual features of metalloprotein voltammetry at carbon electrodes476
7.1Cytochrome c voltammetry at carbon macrodisc electrodes477
7.2Cytochrome c voltammetry at carbon microdisc electrodes480
7.3Conclusions derived from modelling the voltammetry of cytochrome c at carbon electrodes485
8Evidence that chemical modification of the electrode surface can alter the reversible potential486
8.1The thermodynamic effects of chemical modification of graphite electrodes on rubredoxin electrochemistry487
8.2Thermodynamic effects of chemical modification of graphite electrodes on ferredoxin electrochemistry488
8.3Conclusions concerning the dependence of the reversible potential on the presence of a surface modifier490
9Long-range electron-transfer effects encountered in cytochrome c voltammetry at long-chain alkane thiolate modified electrodes492
10Voltammetry of metalloproteins in surfactant environments494
11Conclusions related to the voltammetry of metalloproteins497

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