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ANALYTICAL
ELECTROCHEMISTRY
ANALYTICAL
ELECTROCHEMISTRY
Third Edition

Joseph Wang
Copyright © 2006 by John Wiley & Sons, Inc. All rights reserved.

Published by John Wiley & Sons, Inc., Hoboken, New Jersey.

Published simultaneously in Canada.

No part of this publication may be reproduced, stored in a retrieval system, or transmitted in

any form or by any means, electronic, mechanical, photocopying, recording, scanning, or
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Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best
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visit our web site at www.wiley.com.

Library of Congress Cataloging-in-Publication Data:

Wang, Joseph, 1948–
Analytical electrochemistry / Joseph Wang.—3rd ed.
p. cm.
ISBN-13 978-0-471-67879-3 (cloth)
ISBN-10 0-471-67879-1 (cloth)
1. Electrochemical analysis. I. Title.
QD115.W33 2006
543′.4—dc22
2005028185

Printed in the United States of America.

10 9 8 7 6 5 4 3 2 1
Dedicated to the memory of my parents, Elka and Moshe Wang
CONTENTS

Preface xi
Abbreviations and Symbols xiii

1 Fundamental Concepts 1
1.1 Why Electroanalysis?, 1
1.2 Faradaic Processes, 3
1.2.1 Mass-Transport-Controlled Reactions, 4
1.2.1.1 Potential-Step Experiment, 7
1.2.1.2 Potential-Sweep Experiments, 9
1.2.2 Reactions Controlled by the Rate of Electron Transfer, 12
1.2.2.1 Activated Complex Theory, 16
1.3 Electrical Double Layer, 19
1.4 Electrocapillary Effect, 23
1.5 Supplementary Reading, 25
Problems, 27
References, 28

2 Study of Electrode Reactions and Interfacial Properties 29

2.1 Cyclic Voltammetry, 29
2.1.1 Data Interpretation, 32
2.1.1.1 Reversible Systems, 32
2.1.1.2 Irreversible and Quasi-reversible Systems, 34
2.1.2 Study of Reaction Mechanisms, 35
vii
viii CONTENTS

2.1.3 Study of Adsorption Processes, 37

2.1.4 Quantitative Applications, 41
2.2 Spectroelectrochemistry, 42
2.2.1 Experimental Arrangement, 43
2.2.2 Principles and Applications, 44
2.2.3 Electrochemiluminescence, 47
2.2.4 Optical Probing of Electrode–Solution Interfaces, 48
2.3 Scanning Probe Microscopy, 49
2.3.1 Scanning Tunneling Microscopy, 50
2.3.2 Atomic Force Microscopy, 51
2.3.3 Scanning Electrochemical Microscopy, 53
2.4 Electrochemical Quartz Crystal Microbalance, 57
2.5 Impedance Spectroscopy, 58
Examples, 61
Problems, 63
References, 64
3 Controlled-Potential Techniques 67
3.1 Chronoamperometry, 67
3.2 Polarography, 69
3.3 Pulse Voltammetry, 76
3.3.1 Normal-Pulse Voltammetry, 76
3.3.2 Differential-Pulse Voltammetry, 77
3.3.3 Square-Wave Voltammetry, 80
3.3.4 Staircase Voltammetry, 82
3.4 AC Voltammetry, 84
3.5 Stripping Analysis, 85
3.5.1 Anodic Stripping Voltammetry, 86
3.5.2 Potentiometric Stripping Analysis, 89
3.5.3 Adsorptive Stripping Voltammetry and Potentiometry, 91
3.5.4 Cathodic Stripping Voltammetry, 94
3.5.5 Abrasive Stripping Voltammetry, 94
3.5.6 Applications, 94
3.6 Flow Analysis, 98
3.6.1 Principles, 98
3.6.2 Cell Design, 100
3.6.3 Mass Transport and Current Response, 103
3.6.4 Detection Modes, 105
Examples, 108
Problems, 111
References, 112
4 Practical Considerations 115
4.1 Electrochemical Cells, 115
4.2 Solvents and Supporting Electrolytes, 117
CONTENTS ix

4.3 Oxygen Removal, 118

4.4 Instrumentation, 119
4.5 Working Electrodes, 123
4.5.1 Mercury Electrodes, 123
4.5.2 Solid Electrodes, 127
4.5.2.1 Rotating Disk and Rotating Ring Disk Electrodes, 128
4.5.2.2 Carbon Electrodes, 130
4.5.2.2.1 Glassy Carbon Electrodes, 131
4.5.2.2.2 Carbon Paste Electrodes, 131
4.5.2.2.3 Carbon Fiber Electrodes, 133
4.5.2.2.4 Diamond Electrodes, 133
4.5.2.3 Metal Electrodes, 134
4.5.3 Chemically Modified Electrodes, 136
4.5.3.1 Self-Assembled Monolayers, 136
4.5.3.2 Carbon-Nanotube-Modified Electrodes, 139
4.5.3.3 Sol-gel Encapsulation of Reactive Species, 139
4.5.3.4 Electrocatalytically Modified Electrodes, 140
4.5.3.5 Preconcentrating Electrodes, 141
4.5.3.6 Permselective Coatings, 143
4.5.3.7 Conducting Polymers, 146
4.5.4 Microelectrodes, 149
4.5.4.1 Diffusion at Microelectrodes, 151
4.5.4.2 Microelectrode Configurations, 152
4.5.4.3 Composite Electrodes, 154
Examples, 158
Problems, 158
References, 159

5 Potentiometry 165
5.1 Principles of Potentiometric Measurements, 165
5.2 Ion-Selective Electrodes, 173
5.2.1 Glass Electrodes, 173
5.2.1.1 pH Electrodes, 173
5.2.1.2 Glass Electrodes for Other Cations, 177
5.2.2 Liquid Membrane Electrodes, 177
5.2.2.1 Ion Exchanger Electrodes, 179
5.2.2.2 Neutral Carrier Electrodes, 182
5.2.3 Solid-State Electrodes, 185
5.2.4 Coated-Wire Electrodes and Solid-State Electrodes Without an
Internal Filling Solution, 188
5.3 On-line, On-site, and In Vivo Potentiometric Measurements, 190
Examples, 194
Problems, 196
References, 197
x CONTENTS

6 Electrochemical Sensors 201

6.1 Electrochemical Biosensors, 202
6.1.1 Enzyme-Based Electrodes, 202
6.1.1.1 Practical and Theoretical Considerations, 202
6.1.1.2 Enzyme Electrodes of Analytical Significance, 208
6.1.1.2.1 Glucose Sensors, 208
6.1.1.2.2 Ethanol Electrodes, 212
6.1.1.2.3 Urea Electrodes, 213
6.1.1.2.4 Toxin (Enzyme Inhibition) Biosensors, 215
6.1.1.3 Tissue and Bacteria Electrodes, 215
6.1.2 Affinity Biosensors, 216
6.1.2.1 Immunosensors, 216
6.1.2.2 DNA Hybridization Biosensors, 218
6.1.2.2.1 Background and Principles, 218
6.1.2.2.2 Electrical Transduction of DNA
Hybridization, 219
6.1.2.2.3 Other Electrochemical DNA
Biosensors, 221
6.1.2.3 Receptor-Based Sensors, 222
6.1.2.4 Electrochemical Sensors Based on Molecularly
Imprinted Polymers, 224
6.2 Gas Sensors, 224
6.2.1 Carbon Dioxide Sensors, 225
6.2.2 Oxygen Electrodes, 226
6.3 Solid-State Devices, 227
6.3.1 Ion-Selective Field Effect Transistors, 227
6.3.2 Microfabrication of Solid-State Sensor Assemblies, 229
6.3.3 Microfabrication Techniques, 229
6.3.4 Micromachined Analytical Microsystems, 232
6.4 Sensor Arrays, 234
Examples, 237
Problems, 238
References, 239

Index 245
PREFACE

The goal of this textbook is to cover the full scope of modern electroanalyti-
cal techniques and devices. The main emphasis is on electroanalysis, rather
than physical electrochemistry. The objective is to provide a sound under-
standing of the fundamentals of electrode reactions and the principles of elec-
trochemical methods, and to demonstrate their potential for solving real-life
analytical problems. The high performance, small size, and low cost of elec-
trochemical devices has led to many important detection systems. Given the
impressive progress in electroanalytical chemistry and its growing impact on
analytical chemistry, this work offers also an up-to-date, easy-to-read presen-
tation of more recent advances, including new methodologies, sensors, detec-
tors, and microsystems. The book is suitable for a graduate-level course in
electroanalytical chemistry or as a supplement to a high-level undergraduate
course in instrumental analysis. It should also be very useful to those consid-
ering the use of electroanalysis in their laboratories.
The material is presented in six roughly equal chapters. The first chapter is
devoted to fundamental aspects of electrode reactions and the structure of the
interfacial region. Chapter 2 discusses the study of electrode reactions and
high-resolution surface characterization. Chapter 3 gives an overview of finite-
current-controlled potential techniques. Chapter 4 describes the electro-
chemical instrumentation and electrode materials (including new and modified
microelectrodes). Chapter 5 deals with the principles of potentiometric meas-
urements and various classes of ion-selective electrodes, while Chapter 6 is
devoted to the growing field of chemical sensors (including modern biosen-
sors, gas sensors, microchip devices, and sensor arrays). Numerous up-to-date
references, covering the latest literature, are given at the end of each chapter.
xi
xii PREFACE

By discussing more recent advances, this book attempts to bridge the common
gap between research literature and standard textbooks.
This third edition of Analytical Electrochemistry is extensively revised and
updated, and reflects the rapid growth of electroanalytical chemistry since
1999. It contains a number of new topics, including DNA biosensors, imped-
ance spectroscopy, detection for capillary electrophoresis, diamond electrodes,
carbon-nanotube- and nanoparticle-based assays and devices, large-amplitude
AC voltammetry, microfluidic (“lab on a chip”) devices, or molecularly-
imprinted polymeric sensors. Other topics, such as the principles of potentio-
metric measurements, spectroelectrochemistry, electrochemiluminescence,
modified and microelectrodes, scanning electrochemical and atomic force
microscopies, electrical communication between redox enzymes and elec-
trodes, explosive detection, or enzyme and immunoelectrodes, have been
greatly expanded. The entire text has been updated to cover the very latest
(as of August 2005) developments in electroanalytical chemistry. Numerous
new illustrations, worked-out examples and end-of-chapter problems have
been added to this edition. Existing figures have been redrawn and improved.
In the 5 years since the second edition I have received numerous suggestions,
many of which have been incorporated in the second edition.
Finally, I wish to thank my wife, Ruth, and my daughter, Sharon, for their
love and patience; Vairavan Subramanian and Daphne Hui for their technical
assistance; the editorial and production staff of John Wiley & Sons, Inc. for
their help and support; Professor Erno Pretsch (ETH, Zurich) for extremely
useful suggestions; and the numerous electrochemists across the globe who led
to the advances reported in this textbook. Thank you all!

Joseph Wang
Tempe, AZ
ABBREVIATIONS AND SYMBOLS

a Activity
A Area of electrode
Ab Antibody
AC Alternating current
AdSV Adsorptive stripping voltammetry
AE Auxiliary electrode
AES Auger electron spectroscopy
AFM Atomic force microscopy
Ag Antigen
ASV Anodic stripping voltammetry
B Adsorption coefficient
BDD Boron-doped diamond
C Concentration
Cdl Differential capacitance
CE Counter electrode
CME Chemically modified electrode
CNT Carbon nanotube
CSV Cathodic stripping voltammetry
CV Cyclic voltammetry
CWE Coated-wire electrode
CZE Capillary-zone electrophoresis
D Diffusion coefficient
DME Dropping mercury electrode
DNA Deoxyribonucleic acid
DP Differential pulse
xiii
xiv ABBREVIATIONS AND SYMBOLS

DPV Differential pulse voltammetry

E Potential (V)
∆E Pulse amplitude
E° Standard electrode potential
E1/2 Half-wave potential
Ep Peak potential
Epzc Potential of zero charge
EC Electrode process involving electrochemical followed by chemical
steps
ECL Electrochemiluminescence
EQCM Electrochemical quartz crystal microbalance
ESCA Electron spectroscopy for chemical analysis
EXAFS X-ray adsorption fine structure
F Faraday constant
FET Field effect transistor
FIA Flow injection analysis
fi Activity coefficient
f0 Base resonant frequency
FTIR Fourier transform infrared
∆G‡ Free energy of activation
HMDE Hanging mercury drop electrode
i Electric current
ic Charging current
it Tunneling current
IHP Inner Helmholz plane
IRS Internal reflectance spectroscopy
ISE Ion-selective electrode
ISFET Ion-selective field effect transistor
J Flux
kijpot Potentiometric selectivity coefficient
k° Standard rate constant
Km (1) Michaelis Menten constant; (2) mass transport coefficient
LB Langmuir–Blodgett
LCEC Liquid chromatography/electrochemistry
LEED Low-energy electron diffraction
m Mercury flow rate (in polarography)
∆m Mass charge (in EQCM)
MFE Mercury film electrode
µTAS Micro–total analytical system
MIP Molecularly imprinted polymer
MLR Multiple linear regression
MWCNT Multiwall carbon nanotube
N Collection efficiency
n Number of electrons transferred
NP Normal pulse
ABBREVIATIONS AND SYMBOLS xv

O The oxidized species

OHP Outer Helmholz plane
OTE Optically transparent electrode
PAD Pulsed amperometric detection
PCR Principal-component regression
PLS Partial least squares
PSA Potentiometric stripping analysis
PVC Poly(vinyl chloride)
q Charge
QCM Quartz crystal microbalance
R (1) Resistance; (2) gas constant
Rp Electron transfer resistance
Rs Ohmic resistance of the electrolyte solution
RDE Rotating disk electrode
Re Reynolds number
RE Reference electrode
RRDE Rotating ring–disk electrode
RVC Reticulated vitreous carbon
S (1) Barrier width (in STM); (2) substrate
SAM Self-assembled monolayer
SECM Scanning electrochemical microscopy
SEM Scanning electron microscopy
SERS Surface enhanced Raman scattering
SPM Scanning probe microscopy
STM Scanning tunneling microscopy
SW Square wave
SWCNT Single-wall carbon nanotube
SWV Square-wave voltammetry
T Temperature
t Time
tm Transition time (in PSA)
U Flow rate
UHV Ultrahigh vacuum
v Potential scan rate
VHg Volume of mercury electrode
W Peak width (at half-height)
WE Working electrode
WJD Wall-jet detector
XPS X-ray photoelectron spectroscopy

α Transfer coefficient
Γ Surface coverage
γ Surface tension
δ Thickness of the diffusion layer
δH Thickness of the hydrodynamic boundary layer
xvi ABBREVIATIONS AND SYMBOLS

ε Dielectric constant
 Overvoltage
µ Ionic strength
 Kinematic viscosity
ω Angular velocity
1
FUNDAMENTAL CONCEPTS

1.1 WHY ELECTROANALYSIS?

Electroanalytical techniques are concerned with the interplay between

electricity and chemistry, namely, the measurements of electrical quantities,
such as current, potential, or charge and their relationship to chemical param-
eters. Such use of electrical measurements for analytical purposes has found
a vast range of applications, including environmental monitoring, industrial
quality control, or biomedical analysis. Advances since the mid-1980s, in-
cluding the development of ultramicroelectrodes, the design of tailored inter-
faces and molecular monolayers, the coupling of biological components and
electrochemical transducers, the synthesis of ionophores and receptors
containing cavities of molecular size, the development of ultratrace voltam-
metric techniques or of high-resolution scanning probe microscopies, and
the microfabrication of molecular devices or efficient flow detectors, have led
to a substantial increase in the popularity of electroanalysis and to its expan-
sion into new phases and environments. Indeed, electrochemical probes are
receiving a major share of the attention in the development of chemical
sensors.
In contrast to many chemical measurements, which involve homogeneous
bulk solutions, electrochemical processes take place at the electrode–solution
interface. The distinction between various electroanalytical techniques reflects
the type of electrical signal used for the quantitation. The two principal types

Analytical Electrochemistry, Third Edition, by Joseph Wang

Copyright © 2006 John Wiley & Sons, Inc.

1
2 FUNDAMENTAL CONCEPTS

of electroanalytical measurements are potentiometric and potentiostatic. Both

types require at least two electrodes (conductors) and a contacting sample
(electrolyte) solution, which constitute the electrochemical cell. The electrode
surface is thus a junction between an ionic conductor and an electronic con-
ductor. One of the two electrodes responds to the target analyte(s) and is thus
termed the indicator (or working) electrode. The second one, termed the ref-
erence electrode, is of constant potential (i.e., independent of the properties
of the solution). Electrochemical cells can be classified as electrolytic (when
they consume electricity from an external source) or galvanic (if they are used
to produce electrical energy).
Potentiometry (discussed in Chapter 5), which is of great practical impor-
tance, is a static (zero-current) technique in which the information about the
sample composition is obtained from measurement of the potential estab-
lished across a membrane. Different types of membrane materials, possessing
different ion recognition processes, have been developed to impart high selec-
tivity. The resulting potentiometric probes have thus been widely used for
several decades for direct monitoring of ionic species such as protons or
calcium, fluoride, and potassium ions in complex samples.
Controlled-potential (potentiostatic) techniques deal with the study of
charge transfer processes at the electrode–solution interface, and are based on
dynamic (non-zero-current) situations. Here, the electrode potential is being
used to derive an electron transfer reaction and the resultant current is meas-
ured. The role of the potential is analogous to that of the wavelength in optical
measurements. Such a controllable parameter can be viewed as “electron pres-
sure,” which forces the chemical species to gain or lose an electron (reduction
or oxidation, respectively). Accordingly, the resulting current reflects the rate
at which electrons move across the electrode–solution interface. Potentiosta-
tic techniques can thus measure any chemical species that is electroactive, that
is, that can be made to reduce or oxidize. Knowledge of the reactivity of func-
tional group in a given compound can be used to predict its electroactivity.
Nonelectroactive compounds may also be detected in connection with indi-
rect or derivatization procedures.
The advantages of controlled-potential techniques include high sensitivity,
selectivity toward electroactive species, a wide linear range, portable and
low-cost instrumentation, speciation capability, and a wide range of electrodes
that allow assays of unusual environments. Several properties of these
techniques are summarized in Table 1.1. Extremely low (nanomolar)
detection limits can be achieved with very small (5–20-µL) sample volumes,
thus allowing the determination of analyte amounts ranging from 10−13 to
10−15 mol on a routine basis. Improved selectivity may be achieved via the
coupling of controlled-potential schemes with chromatographic or optical
procedures.
This chapter attempts to give an overview of electrode processes, together
with discussion of electron transfer kinetics, mass transport, and the
electrode–solution interface.
FARADAIC PROCESSES 3

TABLE 1.1 Properties of Controlled-Potential Techniquesa

Speed
Working Detection (Time per Response
Technique Electrode Limit (M) Cycle) (min) Shape
DC polarography DME 10−5 3 Wave
NP polarography DME 5 × 10−7 3 Wave
DP polarography DME 10−8 3 Peak
DP voltammetry Solid 5 × 10−7 3 Peak
SW polarography DME 10−8 0.1 Peak
AC polarography DME 5 × 10−7 1 Peak
Chronoamperometry Stationary 10−5 0.1 Transient
Cyclic voltammetry Stationary 10−5 0.1–2 Peak
Stripping voltammetry HMDE, MFE 10−10 3–6 Peak
Adsorptive stripping HMDE 10−10 2–5 Peak
voltammetry
Adsorptive stripping Solid 10−9 4–5 Peak
voltammetry
Adsorptive catalytic HMDE 10−12 2–5 Peak
stripping voltammetry
a
All acronyms used here are included in the “Abbreviations and Symbols” list following the
Preface.

1.2 FARADAIC PROCESSES

The objective of controlled-potential electroanalytical experiments is to

obtain a current response that is related to the concentration of the target
analyte. Such an objective is accomplished by monitoring the transfer of elec-
tron(s) during the redox process of the analyte:

O + ne − ∫ R (1.1)

where O and R are the oxidized and reduced forms, respectively, of the redox
couple. Such a reaction will occur in a potential region that makes the elec-
tron transfer thermodynamically or kinetically favorable. For systems con-
trolled by the laws of thermodynamics, the potential of the electrode can be
used to establish the concentration of the electroactive species at the surface
[CO(0,t) and CR(0,t)] according to the Nernst equation

2.3RT C O ( 0, t )
E = E° + log (1.2)
nF C R ( 0, t )

where E° is the standard potential for the redox reaction, R is the universal
gas constant (8.314 J K−1 mol−1), T is the Kelvin temperature, n is the number
of electrons transferred in the reaction, and F is the Faraday constant [96,487 C
4 FUNDAMENTAL CONCEPTS

(coulombs)]. On the negative side of E°, the oxidized form thus tends to be
reduced, and the forward reaction (i.e., reduction) is more favorable. The
current resulting from a change in oxidation state of the electroactive species
is termed the faradaic current because it obeys Faraday’s law (i.e., the reaction
of 1 mol of substance involves a change of n × 96,487 C). The faradaic current
is a direct measure of the rate of the redox reaction. The resulting
current–potential plot, known as the voltammogram, is a display of current
signal [vertical axis (ordinate)] versus the excitation potential [horizontal axis
(abscissa)]. The exact shape and magnitude of the voltammetric response is
governed by the processes involved in the electrode reaction. The total current
is the summation of the faradaic currents for the sample and blank solutions,
as well as the nonfaradaic charging background current (discussed in Section
1.3).
The pathway of the electrode reaction can be quite complicated, and
takes place in a sequence that involves several steps. The rate of such
reactions is determined by the slowest step in the sequence. Simple reactions
involve only mass transport of the electroactive species to the electrode
surface, electron transfer across the interface, and transport of the product
back to the bulk solution. More complex reactions include additional chemi-
cal and surface processes that either precede or follow the actual electron
transfer. The net rate of the reaction, and hence the measured current, may
be limited by either mass transport of the reactant or the rate of electron
transfer. The more sluggish process will be the rate-determining step. Whether
a given reaction is controlled by mass transport or electron transfer is
usually determined by the type of compound being measured and by various
experimental conditions (electrode material, media, operating potential,
mode of mass transport, time scale, etc.). For a given system, the rate-deter-
mining step may thus depend on the potential range under investigation.
When the overall reaction is controlled solely by the rate at which the
electroactive species reach the surface (i.e., a facile electron transfer), the
current is said to be mass-transport-limited. Such reactions are called nernst-
ian or reversible, because they obey thermodynamic relationships. Several
important techniques (discussed in Chapter 4) rely on such mass-transport-
limited conditions.

1.2.1 Mass-Transport-Controlled Reactions

Mass transport occurs by three different modes:

• Diffusion—the spontaneous movement under the influence of concen-

tration gradient, from regions of high concentrations to regions of lower
ones, aimed at minimizing concentration differences.
• Convection—transport to the electrode by a gross physical movement; the
major driving force for convection is an external mechanical energy asso-
ciated with stirring or flowing the solution or rotating or vibrating the
FARADAIC PROCESSES 5

electrode (i.e., forced convection). Convection can also occur naturally

as a result of density gradients.
• Migration—movement of charged particles along an electrical field (i.e.,
where the charge is carried through the solution by ions according to their
transference number).
These modes of mass transport are illustrated in Figure 1.1.

The flux (J), a common measure of the rate of mass transport at a fixed
point, is defined as the number of molecules penetrating a unit area of an imag-
inary plane in a unit of time and is expressed in units of mol cm−2 s−1. The flux
to the electrode is described mathematically by a differential equation, known
as the Nernst–Planck equation, given here for one dimension

∂C( x,t ) zFDC ∂φ( x, t )

J ( x, t ) = − D − + C ( x, t )V ( x, t ) (1.3)
∂x RT ∂x

Diffusion

– Migration –
+ –
–
+
– –
–
+
–
+ +
– – –
Convection

Figure 1.1 The three modes of mass transport. (Reproduced with permission from
Ref. 1.)
6 FUNDAMENTAL CONCEPTS

where D is the diffusion coefficient (cm2/s); [∂C(x,t)]/∂x is the concentration

gradient (at distance x and time t); [∂φ(x,t)]/∂x is the potential gradient; z and
C are the charge and concentration, respectively, of the electroactive species;
and V(x,t) is the hydrodynamic velocity (in the x direction). In aqueous media,
D usually ranges between 10−5 and 10−6 cm2/s. The current (i) is directly pro-
portional to the flux and the surface area (A):

i = − nFAJ (1.4)

As indicated by Eq. (1.3), the situation is quite complex when the three
modes of mass transport occur simultaneously. This complication makes it dif-
ficult to relate the current to the analyte concentration. The situation can be
greatly simplified by suppressing the electromigration through the addition of
excess inert salt. This addition of a high concentration of the supporting elec-
trolyte (compared to the concentration of electroactive ions) helps reduce the
electrical field by increasing the solution conductivity. Convection effects can
be eliminated by using a quiescent solution. In the absence of migration and
convection effects, movement of the electroactive species is limited by diffu-
sion. The reaction occurring at the surface of the electrode generates a con-
centration gradient adjacent to the surface, which in turn gives rise to a
diffusional flux. Equations governing diffusion processes are thus relevant to
many electroanalytical procedures.
According to Fick’s first law, the rate of diffusion (i.e., the flux) is directly
proportional to the slope of the concentration gradient:

∂C( x,t )
J ( x, t ) = − D (1.5)
∂x

Combination of Eqs. (1.4) and (1.5) yields a general expression for the current
response:

∂C( x,t )
i = nFAD (1.6)
∂x

Hence, the current (at any time) is proportional to the concentration gradient
of the electroactive species. As indicated by the equations above, the diffu-
sional flux is time-dependent. Such dependence is described by Fick’s second
law (for linear diffusion):

∂C( x,t ) ∂ 2C( x,t )

=D (1.7)
∂t ∂x 2

This equation reflects the rate of change with time of the concentration
between parallel planes at points x and (x + dx) (which is equal to the differ-
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