ELECTROCHEMICAL METHODS Fundamentals and Applications - Allen.J.Bard

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Major Symbols xv Symbol Meaning Usual Units Section References R RB Ret R { Rmt R s R u Ra r r c fo r\ Г2 гъ Re Re(w) AS AS 0 AS* S r (t) s T t 4 чтшх 'p Щ V V v h Vf V\ (a) gas constant (b) resistance (c) fraction of substance electrolyzed in a porous electrode (d) reflectance series equivalent resistance of a cell charge-transfer resistance feedback resistance mass-transfer resistance (a) solution resistance (b) series resistance in an equivalent circuit uncompensated resistance ohmic solution resistance radial distance from the center of an electrode radius of a capillary radius of an electrode radius of the disk in an RDE or RRDE inner radius of a ring electrode outer radius of a ring electrode Reynolds number real part of complex function w entropy change in a chemical process standard entropy change in a chemical process standard entropy of activation unit step function rising at t = т (a) Laplace plane variable, usually complementary to t (b) specific area of a porous electrode absolute temperature time transference number of species у known characteristic time in a simulation drop time at a DME pulse width in SWV mobility of ion (or charge carrier) j volume (a) linear potential scan rate (b) homogeneous reaction rate (c) heterogeneous reaction rate (d) linear velocity of solution flow, usually a function of position (a) "backward" homogeneous reaction rate (b) anodic heterogeneous reaction rate (a) "forward" homogeneous reaction rate (b) cathodic heterogeneous reaction rate component of velocity in the j direction Jmol^K" 1 ft none none ft ft a ft ft ft ft ft cm cm cm cm cm cm none kJ/K.kJmol^K" 1 kJ/K.kJmol^K" 1 kJmol^K" 1 none cm" 1 К s none s s s cn^V'V 1 cm 3 V/s mol cm" 3 s~ l mol cm" 2 s" 1 cm/s mol cm~ 3 s" 1 mol cm" 2 s -1 mol cm" 3 s" 1 mol cm" 2 s~ ] cm/s 10.1.2 11.6.2 17.1.2 10.4 1.3.3,3.4.3 15.2 1.4.2,3.4.6 1.3.4 1.2.4, 10.1.3 1.3.4, 15.6 10.1.3 5.2.2,5.3,9.3.1 7.1.3 5.2.2, 5.3 9.3.5 9.4.1 9.4.1 9.2.1 A.5 2.1.2 2.1.2 3.1.2 A. 1.7 A.I 11.6.2 2.3.3, 4.2 B.1.4 7.1.2 7.3.5 2.3.3,4.2 6.1 1.3.2,3.1 1.3.2, 3.2 1.4.1,9.2 3.1 3.2 3.1 3.2 9.2.1
xvi Major Symbols Symbol Meaning Usual Units Section References *>mt Wj(A,E) w Wj *c x > X X\ x 2 Y Y У z z Z\m ^Re 7 z Z j rate of mass transfer to a surface probability density function for species j width of a band electrode work term for reactant j in electron transfer capacitive reactance mole fraction of species j distance, often from a planar electrode distance of the IHP from the electrode surface distance of the OHP from the electrode surface admittance admittance vector distance from an RDE or RRDE (a) impedance (b) dimensionless current parameter in simulation impedance vector faradaic impedance imaginary part of impedance real part of impedance Warburg impedance (a) distance normal to the surface of a disk electrode or along a cylindrical electrode (b) charge magnitude of each ion in a z: z electrolyte charge on species j in signed units of electronic charge mol cm 2 s ' eV" 1 cm eV n none cm cm cm rr 1 ft" 1 cm n none ft ft a ft ft cm none none 1.4.1 3.6.3 5.3 3.6.2 10.1.2 13.1.2 1.2.3, 13.3.3 1.2.3, 13.3.3 10.1.2 10.1.2 9.3.1 10.1.2 B.1.6 10.1.2 10.1.3 10.1.2 10.1.2 10.1.3 5.3 13.3.2 2.3 GREEK SYMBOLS Symbol Meaning Usual Units Section References (a) transfer coefficient (b) absorption coefficient (a) distance factor for extended charge transfer (b) geometric parameter for an RRDE (c) 1 - a (a) дЕ/дС } (0, t) (b) equilibrium parameter in an adsorption isotherm for species у surface excess of species j at equilibrium relative surface excess of species у with respect to component r none 3.3 cm" 1 A" 1 none none V-cm 3 /mol none mol/cm 2 mol/cm 2 17.1.2 3.6.4 9.4.1 10.5.2 10.2.2 13.5.2 13.1.2 13.1.2
Page 1 and 2: SECOND EDITION ELECTROCHEMICAL METH
Page 3 and 4: PREFACE In the twenty years since t
Page 5 and 6: CONTENTS MAJOR SYMBOLS ix STANDARD
Page 7 and 8: Major Symbols Symbol Meaning Usual
Page 9 and 10: xii Major Symbols Symbol Meaning Us
Page 11: xiv Major Symbols Symbol Meaning Us
Page 15 and 16: xviii Major Symbols Symbol Meaning
Page 17 and 18: xx Major Symbols Abbreviation Meani
Page 19 and 20: CHAPTER 1 INTRODUCTION AND OVERVIEW
Page 21 and 22: Pt H 2 1.1 Introduction 3 Zn Ag С
Page 23 and 24: 1.1 Introduction 5 Power supply -Ag
Page 25 and 26: 1.1 Introduction 7 idation of Br~ t
Page 27 and 28: 1.1 Introduction Hg/I-Г, ВГ(1 М
Page 29 and 30: 1.2 Nonfaradaic Processes and the N
Page 37 and 38: 1.3 Faradaic Processes and Factors
Page 47 and 48: 1.4 Introduction to Mass-Transfer-C
Page 55 and 56: 1.5 Semiempirical Treatment of Nems
Page 57 and 58: 1.6 The Literature of Electrochemis
Page 59 and 60: 1.6 The Literature of Electrochemis
Page 61 and 62: 1.8 Problems 43 1.6 For the electro
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Thus the net cell reaction is 1 Zn
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2.1 Basic Electrochemical Thermodyn
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2.2 A More Detailed View of Interfa
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(a) Properties of the Electrochemic
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2.3 Liquid Junction Potentials л :
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2.3 Liquid Junction Potentials < 65
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2.3 Liquid Junction Potentials 67 T
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2.3 Liquid Junction Potentials 69 W
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2.3 Liquid Junction Potentials «I
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2.3 Liquid Junction Potentials : 73
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2.4 Selective Electrodes \ 75 Ag wi
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2.4 Selective Electrodes 77 The fir
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Other Ion-Selective Electrodes 2.4
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2.4 Selective Electrodes •« 81 (
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2.5 References 83 8. M. W. Chase, J
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2.3 Devise a cell in which the foll
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3 KINETICS OF ELECTRODE REACTIONS I
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3.1 Review of Homogeneous Kinetics
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3.2 Essentials of Electrode Reactio
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3.3 Butler-Volmer Model of Electrod
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3.4 Implications of the Butler-Volm
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Г " т - ') = e f(E-E«) ( 3 A 2 7
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3.5 Multistep Mechanisms 107 -200 -
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3.5 Multistep Mechanisms 109 one-st
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3.5 Multistep Mechanisms 111 which
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3.5 Multistep Mechanisms 113 dent o
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3.6 Microscopic Theories of Charge
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3.7 References 133 17. J. A. V. But
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3.8 Problems 135 Use a spreadsheet
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CHAPTER 4 MASS TRANSFER BY MIGRATIO
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4.2 Migration 139 component at any
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4.3 Mixed Migration and Diffusion N
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4.4 Diffusion i 147 -5/ -41 -31 -21
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4.4 Diffusion 149 net mass-transfer
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4.4 Diffusion 151 X IТ i i i \ \\
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4.5 References i 153 4.4.4 Solution
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4.6 Problems 155 4.4 The mobility,
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5.1 Overview of Step Experiments 15
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5.1 Overview of Step Experiments 15
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5.2 Potential Step Under Diffusion
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and inversion produces the current-
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5.3 Diffusion-Controlled Currents a
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Responses to a Large-Amplitude Pote
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5.4 Sampled-Current Voltammetry for
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5.6 Multicomponent Systems and Mult
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5.7 Chronoamperometric Reversal Tec
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5.7 Chronoamperometric Reversal Tec
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5.8 Chronocoulometry 211 nal-to-noi
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5.8 Chronocoulometry 213 100 200 30
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5.8 Chronocoulometry «i 215 The ap
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5.9 Special Applications of Ultrami
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5.9 Special Applications of Ultrami
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5.10 References « 221 would diffus
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5.11 Problems 223 0.2, 0.5, 1, 2, 3
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5.11 Problems < 225 5.19 G. Denault
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6.1 Introduction -I 227 0 t E t E°
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6.2 Nemstian (Reversible) Systems 2
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6.2 Nemstian (Reversible) Systems <
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6.2 Nernstian (Reversible) Systems
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where Introducing E(t) from (6.2.1)
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6.4 Quasireversible Systems *4 237
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6.5 Cyclic Voltammetry 239 Figure 6
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6.5 Cyclic Voltammetry 241 0.5 -0.3
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6.7 Convolutive or Semi-Integral Te
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6.8 Cyclic Voltammetry of the Liqui
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6.9 References 255 100 I -100 I I I
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6.10 Problems 257 20 r- 15 /, цА
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6.10 Problems *« 259 -0.8 -1.0 -1.
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CHAPTER 7 POLAROGRAPHY AND PULSE VO
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7.1 Behavior at Polarographic Elect
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7.2 Polarographic Waves 273 Kouteck
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7.3 PULSE VOLTAMMETRY 7.3 Pulse Vol
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7.3 Pulse Voltammetry 277 -0.4 -0.6
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7.3 Pulse Voltammetry < 279 • Dro
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7.3 Pulse Voltammetry 281 Potential
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7.3 Pulse Voltammetry 283 duration
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7.3 Pulse Voltammetry \. 285 cant c
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7.3 Pulse Voltammetry < 287 Second
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7.3 Pulse Voltammetry 289 The shape
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7.3 Pulse Voltammetry I 291 one ref
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7.3 Pulse Voltammetry 293 effects o
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7.3 Pulse Voltammetry 295 In genera
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7.3 Pulse Voltammetry < 297 1.0 i
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7.3 Pulse Voltammetry 299 (d) Appli
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7.4 References 301 Therefore, the b
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7.5 Problems < 303 49. L. Ramaley a
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8 CONTROLLED-CURRENT TECHNIQUES 8.1
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8.2 General Theory of Controlled-Cu
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8.2 General Theory of Controlled-Cu
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8.2.3 Programmed Current Chronopote
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8.3 Potential-Time Curves in Consta
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8.3 Potential-Time Curves in Consta
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8.4 Reversal Techniques 317 connect
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8.6 The Galvanostatic Double Pulse
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8.7 Charge Step (Coulostatic) Metho
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8.9 Problems 329 electrolysis time
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CHAPTER 9 METHODS INVOLVING FORCED
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9.2 Theoretical Treatment of Convec
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9.3 Rotating Disk Electrode 335 9.3
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9.3 Rotating Disk Electrode 337 Fig
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9.3 Rotating Disk Electrode i 339 T
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9.3 Rotating Disk Electrode 341 For
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9.3 Rotating Disk Electrode 343 1 0
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9.3 Rotating Disk Electrode 345 to
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7iim» o f j lim =l№l(i u /A)s l/
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9.4 Rotating Ring and Ring-Disk Ele
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9.4 Rotating Ring and Ring-Disk Ele
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9.5 Transients at the RDE and RRDE
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9.5.2 Transients at the RRDE 9.5 Tr
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9.6 Modulated RDE «1 357 600 400 -
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9.6 Modulated RDE < 359 Full-wave r
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9.7 Convection at Ultramicroelectro
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9.8 Electrohydrodynamics and Relate
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9.10 Problems 365 40. D. A. Saville
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9.10 Problems 367 +1.0 -0.2 Figure
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ЮЛ Introduction 369 Potentiometer
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10.1 Introduction 371 Figure 10.1.3
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10.1 Introduction 373 In this way w
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10.1 Introduction 375 *I_L -3 -2 -1
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10.2 Interpretation of the Faradaic
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10.2 Interpretation of the Faradaic
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10.3 Kinetic Parameters from Impeda
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10.4 Electrochemical Impedance Spec
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10.5 ас Voltammetry < 389 voltamm
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10.5 ас Voltammetry «I 391 exper
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10.5 ас Voltammetry 393 heterogen
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10.5 ас Voltammetry 395 This maxi
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10.5 ас Voltammetry < 397 The str
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10.5 ас Voltammetry -Щ 399 peak
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10.6 Higher Harmonics -m 401 f В R
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10.6 Higher Harmonics 403 Output H
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10.7 Chemical Analysis by ac Voltam
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10.8 Instrumentation for Electroche
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10.8 Instrumentation for Electroche
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10.9 Analysis of Data in the Laplac
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10.9 Analysis of Data in the Laplac
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10.11 Problems « 415 22. J. Vareec
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CHAPTER 11 BULK ELECTROLYSIS METHOD
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General Considerations in Bulk Elec
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General Considerations in Bulk Elec
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Controlled-Potential Methods < 423
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Controlled-Potential Methods 425 lo
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11.3.3 Electroseparations Controlle
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Controlled-Potential Methods 429 ur
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Controlled-Current Methods ^ 431 Ba
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Controlled-Current Methods i 433 Th
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Electrometric End-Point Detection 4
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Electrometric End-Point Detection i
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Electrometric End-Point Detection <
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Flow Electrolysis 441 11.6 FLOW ELE
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Flow Electrolysis ) = nFv dC o (x)
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Flow Electrolysis 445 This allows t
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Flow Electrolysis ^ 447 I Solution
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Flow Electrolysis 449 Spacer Auxili
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Flow Electrolysis 451 are much high
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Thin-Layer Electrochemistry 453 Mic
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Thin-Layer Electrochemistry 455 thr
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Thin-Layer Electrochemistry 457 -0.
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Stripping Analysis 459 Deposition (
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Stripping Analysis 461 -0.6 Figure
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Stripping Analysis 463 0 -0.2 1 1 1
Page 483 and 484:
References 465 7. N. Tanaka, op. ci
Page 485 and 486:
Problems 467 1.0 +0.8 +0.6 +0.4 +0.
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Problems 469 are equal and (b) thos
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CHAPTER 12 ELECTRODE REACTIONS WITH
Page 491 and 492:
12.1 Classification of Reactions i
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12.1 Classification of Reactions 47
Page 495 and 496:
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Page 499 and 500:
12.2 Fundamentals of Theory for Vol
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(as above) дС т д2 С т С О2
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12.2 Fundamentals of Theory for Vol
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12.3 Theory for Transient Voltammet
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Catalytic Reaction—E r Cj 12.3 Th
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Icurr< 12.3 Theory for Transient Vo
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12.4 Rotating Disk and Ring-Disk Me
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12.7 Controlled-Potential Coulometr
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12.8 References « 529 12.8 REFEREN
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12.9 Problems =4 531 92. G. Denuaul
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12.9 Problems 533 12.11 Consider cu
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13.1 Thermodynamics of the Double L
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13.1 Thermodynamics of the Double L
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13.2 Experimental Evaluation of Sur
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13.2 Experimental Evaluation of Sur
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13.2.3 Relative Surface Excesses 13
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13.3 Models for Double-Layer Struct
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The total charge per unit volume in
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13.4 Studies at Solid Electrodes 55
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13.5 Extent and Rate of Specific Ad
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13.6 Effect of Adsorption of Electr
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13.7 Double-Layer Effects on Electr
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13.7.2 Double-Layer Effects in the
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13.8 Referencess 575 / / / 4 —% -
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13.9 Problems 577 64. D. M. Mohilne
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13.9 Problems 579 13.13 Aramata and
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14.2 Types, Preparation, and Proper
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14.3 Electrochemical Responses of A
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14.4 Overview of Processes at Modif
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where the permeation current, ip, i
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14.5 Blocking Layers 619 One can al
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14.5 Blocking Layers 621 current at
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14.5 Blocking Layers 623 The parame
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14.5 Blocking Layers 625 at the ele
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14.6 Other Methods of Characterizat
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14.7 References . 629 (b) H. S. Whi
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14.8 Problems 631 15 20 25 [ВГ],
Page 651 and 652:
15.1 Operational Amplifiers 633 +15
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15.2 Current Feedback 635 (f) Other
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15.2 Current Feedback < 637 i Figur
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15.3 Voltage Feedback * 639 This ki
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15.4 Potentiostats 641 Counter Work
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15.4 Potentiostats -4 643 I Potenti
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15.6 Difficulties with Potential Co
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15.7 Measurement of Low Currents
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15.8 Computer-Controlled Instrument
Page 673 and 674:
15.9 Troubleshooting Electrochemica
Page 675 and 676:
15.11 Problems 657 25. P. He, J. P.
Page 677 and 678:
CHAPTER 16 SCANNING PROBE TECHNIQUE
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16.2 Scanning Tunneling Microscopy
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16.3 Atomic Force Microscopy 667 no
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16.4 Scanning Electrochemical Micro
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16.6 Problems 679 tip and the subst
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17.1 Ultraviolet and Visible Spectr
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17.2 Vibrational Spectroscopy 701 R
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17.2 Vibrational Spectroscopy ; 703
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17.2 Vibrational Spectroscopy 705 h
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17.2 Vibrational Spectroscopy 707 0
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17.3 Electron and Ion Spectrometry
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17.4 Magnetic Resonance Methods 723
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17.5 Quartz Crystal Microbalance 72
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17.5 Quartz Crystal Microbalance ;
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17.6 X-Ray Methods 729 few millimet
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17.7 References 731 17.7 REFERENCES
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17.7 References =- 733 87. D. M. Ko
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17.8 Problems 735 17.2 Given D = 6.
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18.1 ElectrogeneratedChemiluminesce
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18.2 Photoelectrochemistry at Semic
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18.3 Electrochemical Detection of P
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18.3 Electrochemical Detection of P
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18.4 References ! 765 41. L. L. Shu
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18.5 Problems 767 18.4 The transien
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А Р Р #Й D IX А MATHEMATICAL M
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АЛ Solving Differential Equations
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А. 1 Solving Differential Equation
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А. 1 Solving Differential Equation
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А.2 Taylor Expansions 777 10 Figur
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А.З The Error Function and the Ga
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А.5 Complex Notation «i 781 A val
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А.8 Problems 783 In most applicati
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APPENDIX В DIGITAL SIMULATIONS OF
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ut the definition of a derivative a
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B.I Setting Up the Model 789 1. C*
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B.I Setting Up the Model 791 could
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В.2 An Example < 793 and imax « 6
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В.2 An Example « 795 mensionless
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В.З Incorporating Homogeneous Kin
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В.4 Boundary Conditions for Variou
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В.4 Boundary Conditions for Variou
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В.6 Miscellaneous Digital Simulati
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В.6 Miscellaneous Digital Simulati
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В.8 Problems 807 / B vs. x f° r t
Page 827 and 828:
TABLE C.I (continued) Reaction 2H +
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Reference Tables 811 TABLE C.3 Esti
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Referem TABLE C.4 Selected Diffusio
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816 • Index Blocking polymers, 58
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818 Index Convective-diffusion equa
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820 Index Dropping mercury electrod
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822 ; Index Ellipsometry, described
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824 Index Instrumentation (continue
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826 Index Multicomponent systems: m
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828 Index Potential step methods (c
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830 • Index Sampled-current volta
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832 Index Thin-layer electrochemist
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ELECTROCHEMICAL METHODS Fundamentals and Applications - Allen.J.Bard

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