Type of

Let us begin by pointing out the basic differences voltammetry

between voltammetry and the two types of electro_

chemical methods that we discussed in earlier chapters.
Voltammetry Voltammetry is based on the measurement of the cur-
rent that develops in an electrochemical cell under con- Differcntial-
ditions where concentration polarization exists. Recall pulse
vo!tammetry
from Section 22E-2 that a polarized electrode is one
to which we have applied a voltage in excess of that
predicted by the Nernst equation to cause oxidation
or reduction to occur. In contrast, potentiometric mea-
surements are made at currents that approach zero
and where polarization is absent. Voltammetry differs
from coulometry in that, with coulometry, measures are r~\

taken to minimize or compensate for the effects of con-

centration polarization. Furthermore, in voltammetry
there is minimal consumption of analyte, whereas in
coulometry essentially all of the analyte is converted to Time-----.-
another state.
FIGURE 25-1 Voltage versus time excitation signals used in voltammetry.
Voltammetry is widely used by inorganic, physical,
and biological chemists for nonanalytic:il purposes,
including fundamental studies of oxidation and re- applying polarographic methods to the determination other than the dropping mercury electrode have grown
oltammetry comprises a group of electro- duction processes in various media, adsorption pro- of a host of species, particularly those of pharma- at an astonishing pace' Furthermore, voltammetry
cesses on surfaces, and electron-transfer mechanisms and amperometry coupled with liquid chromatogra-
·analytical.methods in which information ceutical, environmental, and biological interest.' Since
at chemically modified electrode surfaces. the invention of polarography, at least 60,000 research phy have become powerful tools for the analysis of
about the a.na(rte is obtained by measur- complex mixtures. Modern voltammetry also contin-
Historically, the field of voltammetry developed papers have appeared in the literature on the subject.
ing current as ajunction of ap~lied potential under from polarography, which is a particular type of voltam- ues to be an excellent tool in diverse areas of chem-
Research activity in this field, which dominated elec-
conditions that prodlOte polarization of an indica- metry that was invented by the Czechoslovakian chem- troanalytical chemistry for more than five decades, istry, biochemistry, materials science and engineering,
ist Jaroslav Heyrovsky in the early 1920s Polarog- peaked with nearly 2,000 published journal articles In and the environmental sciences for studYing oXIdatIon,
tor, or [corking, electrode. When currentpropor-
raphy differs from other types of voltammetry in that 1973. Since that time, interest in polarographIc meth- reduction, and adsorption processes.'
tional to analyte coijcentration is monitored at fl:I:ed
the working electrode is the unique dropping mercury ods has steadily declined, at a rate nearly twice the rate
potentia~ the technique is called amperometry. electrode. At one time, polarography was an important of growth of the general chemical literature, until In
25A EXCITATION SIGNALS
Generally, to enhance polarization, working elec- tool used by chemists for the determination of inor- 2005 only about 300 papers on these methods appeared.
IN VOLTAMMETRY
trodes in voltammetryand arnperometryhave sur- ganic ions and certain organic species in aqueous so- This decline has been largely a result of concerns about
lutions. In the late 1950s and the early 19605,however, the use oflarge amounts of mercury in the laboratory as
face areas of a few square millimeters at the most In voltammetry, a variable potential excitation signal is
many of these analytical applications were replaced well as in the environment, the somewhat cumbersome
and, in SOme applications, a few square micrometers impressed on a working electrode in an electrochemIcal
by various spectroscopic methods, and polarography nature of the apparatus, and the broad availability cell. This excitation signal produces a charactenstlc
or less. became a less important method of analysis except for of faster and more convenient (mainly spectroscopIc) current response, which is the measurable quantity
certain special applications, such as the determination methods. For these reasons, we will discuss polarogra- this method. The waveforms of four of the most com-
of molecular oxygen in solutions. In the mid-1960s, phv only briefly and, instead, refer you to the many mon excitation signals used in voltammetry are shown
several major modifications of classical voltammetric so~rces that are available on the subject.' in Figure 25-1. The classical voltammetric excitation
techniques were developed that enhanced significantly Although polarography declined in importance,
the sensitivity and selectivity of the method. At about voltammetry and amperometry at working electrodes JFrom 1973 to 2005. the annual numbc:r of journal articles on \'o~tamme-
this same time, the advent of low-cost operational am- trv and amperometry grew at three times and two and on:-half tlmes, re-
plifiers made possible the commercial development of s~ectivelY, the rate of production of articles ~n all of chemistry.
Broadening Eleecrochemical Horizons: Principles and illustra-
'Some general references on voltammetry IOclu~e ~-\.,1. ~a~'i:;\~ ~~~:
relatively inexpensive instruments that incorporated faulkner Elecrrochomcal Merhods, 2nd ed., Ne\\ .lork. .' - _ '
(:. M. A. Brett and A. M. Oliveira Brett. In Encyclopedw of Electrochem-
many of these modifications and made them available S. p, Ko~naves, in Handbook of Instrumental Te~hntq~es for Analyt!cal
i~-trv A. Bard and M. Stratmann, eds .. Vol. 3. InsrrnmentatlOfI and
to all chemists. The result was a resurgence of interest in Chemistry, Frank A. Settle. ed., Upper Saddle RIVC:r. Pren~lCe-Hal~,
P. Unwin, ed., New York: WIley. 2002,
1997 . 711-28' Laboratory Techmques In ElectfOu.nalj tical ChemlSrr}.
pp. 105 -24> A. 1. Bard and L R. Faulkner, 2nd , pp K.' . d W R Heineman. eds .. "ew York: Dekker.
Throughout this chapter, this logo indicates 2nd ed .. T. Issmger an . " _ 'Jew York:
ed. New York: Wile .•..2001. Chap. 7. pp. 261-30-4; Laborator.\ .Technl~Ue5
an opportunity for online self-study at 1996; Analytual Foltammerry. \-1. R. Smyth and F G. \ o~. eds.,.
in t:leclroanalvrical Chemistry, 2nd ed., P. T Kissinger and \\'. R. Heme-
.thomsouedu.com/chemistry/skoog, linking you to Elsener, 1992
1959 Nobel Priz~ in Chc~jstry for his discO\"ery a~d development of man. -:ds.. York: Dekker. 1996, pp.
interactive tutorials, simulations, and exercises. polarograph~
716
signal is the linear scan shown in Figure 25-1a, in which ing electrode, whose potential is varied linearly with electrode pair, is then converted to a voltage and re- ~
the voltage applied to the cell increases linearly (usually time. Its dimensions are kept small to enhance its ten- corded as a function of time by the data-acquisition 0.75 em
over a 2- to 3-V range) as a function of time. The current dency to become polarized (see Section 22E-2). The system.' It is important to emphasize that the indepen-
in the cell is then recorded as a function of time, and second electrode is a reference electrode (commonly dent variable in this experiment is the potenllal of the
thus as a function of the applied voltage. In amperome- a saturated calomel or a silver-silver chloride elec- working electrode versus the reference electrode and
try, current is recorded at fixed applied voltage. trode) whose potential remains constant throughout not the potential between the working electrode and
Two pulse excitation signals are shown in Fig- the experiment. The third electrode is a counter elec- the counter electrode. The working electrode is at vir-
ure 25-1 band c. Currents are measured at various times trode, which is often a coil of platinum wire that sim- tual common potential throughout the course of the
7.5 em Hg
during the lifetime of these pulses. With the triangular ply conducts electricity from the signal source through experiment (see Section 38-3).
waveform shown in Figure 25-1d, the potential is cycled the solution to the working electrode.
between two values, first increasing linearly to a maxi- The signal source is a linear-scan voltage generator
mum and then decreasing linearly with the same slope similar to the integration circuit shown in Figure 3-16c.
to its original value. This process may be repeated nu- The output from this type of source is described by The working electrodes used in voltammetry take a
merous times as the current is recorded as a function of Equation 3-22. Thus, for a constant dc input potential variety of shapes and forms.' Often, they are small flat
time. A complete cycle may take 100 or more seconds of the output potential is given by disks of a conductor that are press filled into a rod of
or be completed in less than 1 second.
~
an inert material, such as Teflon or Kel-F, that has em- 6mm
To the right of each of the waveforms of Figure 25-1 bedded in it a wire contact (see Figure 25-3a). The con-
Eo 0 dt (a)
is listed the types of voltammetry that use the various ductor may be a noble metal, such as platinum or gold;
excitation signals. We discuss these techniques in the The output signal from the source is fed into a poten- a carbon material, such as carbon paste, carbon fiber,
sections that follow. tiostatic circuit similar to that shown in Figure 25-2 (see pyrolytic graphite, glassy carbon, dia~ond,. or carbon
also Figure 24-6c). The electrical resistante.ofthe con- nanotubes; a semiconductor, such as tm or mdlUm ox-
trol circuit containing the reference electrode is so large ide; or a metal coated with a film of mercury. As shown
10" that it draws essentially no current. Thus, the in Figure 25-4, the range of potentials that can be used
entire current from the source is carried from the with these electrodes in aqueous solutions varies and
Figure 25-2 is a schematic showing the components of counter electrode to the working electrode. Further- depends not only on electrode material but also on thc
a modern operational amplifier potentiostat (see Sec- more, the control circuit adjusts this current so that the composition of the solution in which it is immersed.
tion 24C-1) for carrying out linear-scan voltammetric potential difference between the working electrode and Generally, the positive potential limitations arc caused
measurements. The cell is made up of three electrodes the reference electrode is identical to the output volt- by the large currents that develop because of oxidation
immersed in a solution containing the analyte and also age from the linear voltage generator. The resulting of the water to give molecular oxygen. The negative
an excess of a nonreactive electrolyte called a support- current, which is directly proportional to the potential limits arise from the reduction of water to produce
ing electrolyte. One of the three electrodes is the work- difference between the working electrode-reference hydrogen. Note that relatively large negative poten-
Tutorial: Learn more about voltammetric instru- tials can be tolerated with mercury electrodes because
mentation and waveforms. of the high overvoltage of hydrogen on this metal.

6Earty vohammetry was performed with a two-electrode system rather

Linear than the three-electrode system shown in Figure 25-2. With a t •••. 'o-
sweep electrode syskm, the second electrode is either a large metal. electr~de (e)
generator or a reference electrode large enough to prevent its polarization dunng
an experiment. This second electrode combines the functiom of the rc- FIGURE 25-3 Some common types of commercial
ference electrode and the counter electrode in Figure 25-2. 1n the two- voltammetric electrodes: (a)a disk electrode; (b) a hang-
electrode system, we assume that the potential of this second electrode is
constant th'rouohout a scan so that the working ekctrode potential is sim-
ing mercury drop electrode (HMOE);(c) a microelectrode;
the differe~ce be~ween the applied.potentialand the potential of the (d)a sandwich-type flow electrode. (Electrodes (a], [c],
second electrode. With solutions of high electncal resistance, ho .••.e\cr, and [d]courtesy of Bioanalytical Systems, Inc., West
this assumption is not valid because the drop is significant and increases
~afayetle, IN. with permission.)
Dal3 as the current increases. Distorted voltammograms are the result. ..••• Im{)st
acquisition aU .•..
oltammetry is now performed with three-electrode systems
) Manv of the ~'orking electrodes that we dt:scribe in this chapter have -di·
mensi'ons in the millimeter range. There is nnw intense interest in studies
""ith electrodes having dinwnsions in the mi...:romet~r range and smaller Mercury working electrodes havc been widely used
We will term ~uch electrodes Such have seV- in voltammetrv for several reasons. One IS the rela-
FIGURE 25-2 An operational amplifier potentiostat. The three-electrode cell has a working eral ad\'antages ewer classical working e1ectrodes_ Vie descrihe some of the
tively largc n;gative potential range just described.
electrode (WE).reference electrode (RE),and a counter electrode (CE). uni4ue characteristics microelectfl)des in Section 25[
 tochemical, or electrochemical polymerization meth-
I M H,SO, I Pt)
ods. Immobilized enzyme biosensors, such as the am-
perometric sensors described in Section 25('-4. are a
1M NaOH (Ptl
type of modified electrode. These can be prepared by
covalent attachment, adsorption, or gel entrapment.
Another mode of attachment for electrode modifica-
OXidation tion is by self-assembled m",wlayers, or SAMs.' In the
FIGURE Potential ranges for three most common procedure, a long-ehain hydrocarbon
types of electrodes in various supporting with a thiol group at one end and an amine or carboxyl
1 M HClO,(C)
electrolytes. (Adapted from A. J. Bard and group at the other is applied to a pristine gold or mer-
10lMKCIICI
R. Faulkner, Electrochemical Methods, cury film electrode. The hydrocarbon molecules as-
2nd ed., back cover, New York:Wiley,
semble themselves into a highly ordered array with the
2001. Reprinted by permission of John
V 'S. SCE thiol group attached to the metal surface and the chosen
Wiley& Sons, Inc.)
functional group exposed. The arrays may then be fur-
ther functionalized by covalent attachment or adsorp-
Furthermore, a fresh metallic surface is readily formed tion of the desired molecular species.
perometry) in tlowing streams. The block is made of
Modified electrodes have many applications. A pri-
by simply producing a new drop. The ability to obtain a polyetheretherketone (PEEK) and is available in sev-
mary interest has been in the area of electrocatalysis.
fresh surface readily is important because the currents eral formats with different size electrodes (3 mm and or
In this application, electrodes capable of reducing oxy-
measured in voltammetry are quite sensitive to clean- 6 mm; see the blue area in the figure) and various ar-
oxidation gen to water have been sought for use in fuel cells and
liness and freedom from irregularities. An additional rays (dual 3 mm and quad 2 mm). See Figur~ 25-17 for
batteries. Another application is in the production of
advantage of mercury electrodes is that many metal a diagram showing how the electrodes are ,,!sedin tlow-
e1ectrochromic devices that change color on oxidation
ions are reversibly reduced to amalgams at the surfaee ing streams. The working electrodes may be made of
and reduction. Such devices are used in displays or
of a mercury electrode, which simplifies the chemistry. glassy carbon, carbon paste, gold, copper, nickel, plat-
smart windows and mirrors. Electrochemical devices
Mercury electrodes take several forms. The simplest of inum, or other suitable custom materials.
that could serve as molecular electronic devices, such
these is a mercury film electrode formed by electrode-
as diodes and transistors, are also under intense study.
position of the metal onto a disk electrode, such as that
Finally, the most important analytical use for such
shown in Figure 25-3a. Figure 25-3b illustrates a hang-
electrodes is as analytical sensors selective for a partic-
ing mercury drop electrode (HMDE). The electrode, An active area of research in electrochemistry is the
which is available from commercial sources, consists ular species or functional group (see Figure 1-7).
development of electrodes produced by chemical mo-
of a very fine capillary tube connected to a mercury- dification of various conductive substrates.' Such elec- PtIPtO OSi(CII')3NH(CH')2NH~ - CH, - C6H4 - FeCPz
containing reservoir. The metal is forced out of the trodes have been tailored to accomplish a broad range
capillary by a piston arrangement driven by a microm- of functions. Modifications include applying irrevers-
Figure 25-6 illustrates the appearance of a typical
eter screw. The micrometer permits formation of ibly adsorbing substances with desired functionalities.
linear-scan voltammogram for an electrolysis involving
drops having surface areas that are reproducible to 5% covalent bonding of components to the surface, and
the reduction of an analyte species A to give a product
or better: coating the electrode with polymer films or films of
graphile C-NHCH, ~ ;,:NRu(NH3
P at a mercury film electrode. Here, the working elec-
Figure 25-3e shows a typical commercial microelec- othcr substances. The covalent attachment process is
trode is assumed to be connected to the negative termi-
trode. Such electrodes consist of small-diameter metal shown in Figure 25-5 for a metallic electrode and a
nal of the linear-scan generator so that the applied
wires or fibers (5-100 ~m) sealed within tempered carbon electrode. First, the surface of the electrode
FIGURE Functional groups formed on (a) a metal or potentials are given a negative sign as shown. By con-
glass bodies. The tlattened end of the microelectrode is is oxidized to create functional groups tin the surface
(b)a carbon surface by oxidation. (Withpermission from vention, cathodic currents are taken to be positive,
polished to a mirror finish, which can be maintained as shown in Figure 25-5a and b. Then. linking agents
A J. Bard, Integrated Chemical Systems, New York:Wiley, whereas anodic currents are given a negative sign.'" In
using alumina or diamond polish or both. The electri- such as organosilanes (Figure 25-5c) or amines (Fig-
1994.) (c) A linkingagent such as the organosilane shown this hypothetical experiment, the solution is assumed
cal connection is a 0.060 in. gold-plated pin. Micro- ure 25-5d) arc attached to the surface prior to attaching
is often bonded to the functionalized surface. Reactive to be about 10 4 M in A, zero M in P, and 0.1 M in
electrodes are available in a variety of materials, in- the target group. Polymer films can be prepared from
components, such as ferrocenes, viologens, and metal
cluding carbon fiber, platinum, gold, and silver. Other dissolved polymers by dip coating. spin coating, e1ec- ,jH. O. Fmklea.1n ElecrrorlflLllvfica[ Chemistr.\'. A Series A.
bipyridine complexes, are then attached to fonmthe modi-
materials can be incorporated into microelectrodes if trodeposition, or covalent attachment. They can also be fied surfaces. A PI electrode is shown with a ferrocene Bard and l. Ruhinstt:lO, cds., Vol. 19. pp. Ne •••..York: D~kkcr,
they are available as a wire or a fiber and form a good produced from the monomer by thermal, plasma, pho- 1996
attached. (Withpermission from J. R. Lenhard and R. W. lJThis convention. which onglOated from early polarographIC ~tudit:~. is
seal with epoxy. The electrode shown is approximatelv Murray,J. Am. Chern. Soc., 1978, 100, 7870.) In (d), a not unI\ersally accepted. Many prefer to assign a positl\~ sign to
7.5 em long and has a 4-mm outside diameter. KFur more IIlfOrmatlOll, see R. W. "~Iukcular Design of Eb:-
graphite electrode is shown with attached py-Ru(NH,)s· anodic currents. When reading the literature, it is Important to establish
trode Surfaces." Techniques Chemi.stry. Vol. 22. W found
Figure 25-3d shows a commercially available sand- (Withpermission from C. A. Kovaland C. Anson, whi•...
h cunwotion is ~ing used. Set: A. 1 Bard and L R. Faulkner. Dee
Wiky. 1992: Chemll:;t
2nd p. fl, New York: 2001
wich-type working electrode for voltammetry (or am- IlJ94. Chern., 1978, 50, 223.)
 Figure 25-7c shows a third model for the working
reference electrode potential (0.242 V with a saturated electrode in which the faradaic impedance IS repre-
Limiting current calomel electrode), the half-wave potential is closely sented as the series combination of the charge-transfer
~ A + P related to the standard potential for the half-reaction resistance Rct and the Warburg impedance The
but is usually not identical to it. Half-wave potentials charge-transfer resistance is given by where
are sometimes useful for identification of the compo- is the overpotential for the faradaic process occurnng
nents of a solution. at the working electrode (see Section 22E-2), and I IS
;: Reproducible limiting currents can be achieved the current. The Warburg impedance is a frequency-
rapidly when either the analyte solution or the work- dependent circuit analog of the resistance of the work-
ing electrode is in continuous and reproducible mo- ing electrode to mass transport of analyte molecules
tion. Linear-scan voltammetry in which the solution or across the electrode-solution interface. When expen-
the electrode is in constant motion is called hydrody- mental conditions are such that the Warburg imped-
namic voltammetry. In this chapter, we will focus much ance can be neglected, the charge-transfer resistance
of our attention on hydrodynamic voltammetry. can be easily measured, for example, at excitation fre-
quencies near zero. . .
With modern computerized frequency-analySIs In-
strumentation and software, it is possible to acquire
FIGURE 25-6 Linear-sweep voltammogram for the reduc- It is often useful and instructive to represent the elec- impedance data on cells and extract the valu,:s for all
tion of a hypothetical species A to give a product P_The trochemical cell as an electrical circuit that responds components of the circuit models of Figure 2)-7. ThIS
limitingcurrent i, is proportional to the analyte concen- to excitation in the same way as the ceiL In this discus- type of analysis, which is called electrochemical imped-
tration and is used for quantitative analysis. The half-wave sion, we focus only on the working electrode and as- ance spectroscopy, reveals the nature of the faradaiC
potential is related to the standard potential for the sume that the counter electrode is a larg~ inert elec- processes and often aids in the investigation of the
half-reaction and is often used for qualitative identification trode, that it is nonpolarizable, and that it serves only mechanisms of electron-transfer reactions.'4 In the
of species. The haif-wave potential is the applied potential to make contact with the analyte solution. Figure 25-7 section that follows, we explore the processes at the
at which the current is shows a schematic of three of a number of possible electrode-solution interface that give rise to the fara-
circuit models for the electrochemical cell. In Fig- daic impedance.
KCI, which serves as the supporting electrolyte. The ure 25-7a, we present the Randles circuit, which con-
half-reaction at the working electrode is the reversible sists of the solution resistance Rn, the double-layer
reaction capacitance Cd' and the faradaic impedance The
physical diagram of the electrode above the circuit
shows the correspondence between the circuit ele- FIGURE 25-7 Circuit model of an electrochemical cell. Rn Hydrodynamic voltammetry is performed in several
For convenience, we have neglected the charges on A ments and the characteristics of the electrode. Al- is the cell resistance, is the double-layer capacitance, ways. In one method the solution is stirred vIgorously
and P and also have assumed that the standard poten- though Rn and represent the behavior of real elec- and Z is the faradaic impedance, which may be repre- while it is in contact with a fixed working electrode. A
tial for the half-reaction is -0.26 V. trodes quite accurately over a broad frequency range, sente~ by either of the equivalent circuns shown. is the typical cell for hydrodynamic voltammetry i: pictured
Linear-scan voltammograms generally have a sig- and their values are independent of frequency, the fa- cell resistance, C, is the so-called pseudocapacitance, and in Figure 25-8. In this cell, stirring is accomplished w,th
moid shape and are called voltammetric waves. The radaic impedance does not. This is because, in general, Z is the Warburg impedance. (Adapted from A.J. Bard an ordinary magnetic stirrer. Another approach IS to
constant current beyond the steep rise is called the Z, must model any eleetron- and mass-transfer pro- a~d L R. Faulkner, Electrochemical Methods, 2nd ed., rotate the working electrode at a constant hIgh speed
diffusion-limited current, or simply the limiting current cesses that occur in the cell, and these processes are p. 376, New York:Wiley,2001. Reprinted by permission
in the solution to provide the stirring action (Fig-
because the rate at which the reactant can be brought frequency dependent. The simplest representation of of John Wiley& Sons, Inc.) ure 25-2Ia)_ Still another way of doing hydrodynamic
to the surface of the electrode by mass-transport pro- the faradaic impedance contains a series resistance voltammetry is to pass an analyte solution through a
cesscs limits the current. Limiting currents are usually and the pseudocapacitance C, (Figure 25-7b), which is tube filted with a working electrode (Figure 25-17).
directly proportional to reactant concentration. Thus, so called because of it, frequency dependence." processes. At relatively high frequencies. the capaci-
The last technique is widely used for detecting oxidiz-
tive reactance WIllbe qUite small (see
we may write In the past, clever methods were devised to deter- able or reducible analytes as they exit from a liqUId
Section 28-4), and acts essentially as a short circuit.
mine values for R and For example. suppose that chromatographic column (Section 28C-6) or a flow-
i, If we then measure the peak current in the CIrCUIt,
we apply a small-amplitude sinusoidal excitation signal injection manifold.
we find Rn This is actually a widely used
where CA is the analyte concentration and k is a con- to a cell containing the working electrode represented As described in Section 22E-3, during an electroly-
stant. Quantitative linear-scan voltammetry relies on method for determining solution conductance G
by Figure 25-7b. We further assume that the value of sis, reactant is carried to the surface of an electrode by
lfRo In a similar way, each of the circuil ele-
this relationship. the applied voltage is insufficient to initiate faradaic
The potential at which the current is equal to one ments of the model can be isolated and their valucs de- p.
111. E.
B. Randles, 1. II termined by artful application of ac circuit measure- pp.
half the limiting current is called the half-wave poten- Bard and L R. Faulkner. 2nd cd, 376, pedl1nce SpCC(roscop.l,'. New York: Wiley. 2006
tial and given the symbol After correclion for the New York: 200L ment techniques.
 reaction is rapid and reversible so that the concentra_
tions of A and P in the film of solution immediate I
adjacent to the electrode is given at any instant b t/
Nemst equation: y e

0.0592 c~
,ppl - log E", (25-3)
A

where E,ppl is the potential between the working elec-

trode and the reference electrode and c~and c~ are the
molar concentratIOns of P and A in a thin layer of so-
lutIOn at the electrode surface only. We also assume
that because the electrode is quite small, the electroly-
SIS,over short periods, does not alter the bulk concen-
tration of .the solution appreciably. As a result, the
concentralton of A in the bulk of the solution CA is un-
changed by the electrolysis and the concentration of P Distance from surface x, rom X 103
In the bulk of the solution cp continues to be, for all
pracltcal purposes, zero 0).
FIGURE 25-10 Concentration distance profiles during the diffusion-controlled reduction of A
Profiles for Planar Electrodes in Unstirred Solutions to give P at a planar electrode. (a) 0 V.(b) point in Figure 25-6; elapsed time:
1,5, and 10 ms.
Before describing the behavior of an elecr-n~de in this
solution under hydrodynamic conditions, it is instruc- has been reduced to essentially zero and the concen-
FIGURE 25-8 A three-electrode cell for hydrodynamic all practical purposes, immediately reduced to zero
tive to consider what occurs when a potential is ap- tration of P has increased and become equal to the
voltammetry. 0). The current response to this step-cxcitation
phed to a planar electrode, such as that shown in Fig- original concentration of A; that is, c~ Moving
signal is shown in Figure 25-9b. Initially, the current
ure 25-3a, In the absence of convection - that is, in an away from the surface, the concentration of A in-
three mechanisms: migration under the influence of an rises to a peak value that is required to convert essen-
unsltrred solution. Under these conditions mass trans- creases linearly with distance and approaches c" at
elec~ric field, convection resulting from stirring or vi- tially all of A in the surface layer of solution to P. Dif-
port of the analyte to the electrode surface occurs by about 0.01 mm from the surface. A linear decrease in
bratIOn, and diffusion due to concentration differences fusion from the bulk of the solution then brings more
diffusion alone. the concentration of P occurs in this same region. As
between the film of liquid at the electrode surface and A into this surface layer where further reduction oc-
. Let us.assume that a square-wave excitation poten- shown in the figure, with time, these concentration
the bulk of the solution. In voltammetry, we attempt to curs. The current required to kecp the concentration
tial E,pp'.IS apphed to the working electrode for a pe- gradients extend farther and farther into the solution.
minimiZe the eff~ct of migration by introducing an of A at the level required by Equation 25-3 decreases
nod of time t as shown in Figure 25-9a. Let us further The current required to produce these gradients is
excess of an inactive supporting electrolyte. When the rapidly with time, however, because A must travel
assume that E,pplis large enough that the ratio c~/c~ in proportional to the slopes of the straight-line portions
concentration of supporting electrolyte exceeds that greater and greater distances to reach the surface layer
Equalton 25-3 IS1000 or greater. Under this condition of the solid lines in Figure 25-lOb. That is,
of the analyte by 50- to 100-fold, the fraction of the to- where it can be reduced. Thus, as seen in Figure 25-9b,
the concentration of A at the electrode surface is, fo;
tal current carried by the analyte approaches zero. As the current drops off rapidly after its initial surge.
a result, the rate of migration of the analyte toward the Figure 25-10 shows concentration profiles for A and
electrode of opposite charge becomes essentially inde- P after 0, 1,5, and 10 ms of electrolysis in the system
pendent of applied potential. under discussion. In this example, the concentration of where is the current in amperes, is the number of
A (solid black lines) and P (solid blue lines) are plot- moles of electrons per mole of analyte, is the faraday,
ted as a function of distance from the electrode sur- is the electrode surface area (cm'), is the diffu-
face. Figure 25-lOa shows that the solution is homoge- sion coefficient for A (cm'/s), and is the concentra-
neous before application of the stepped potential with tion of A (mol/cm J). As shown in Figure 25-lOb, these
Throughout this discussion we will consider that the the concentration of A being at the electrode sur- slopes become smaller with time, as docs the
electrode reaction shown in Equation 25-2 takes place face and in the hulk of the solution as well; the con- current. The product is called the
at an electrode in a solution of A that also contains an centration of P is zero in both of these regions. One which is the number of moles of A per unit time per
excess of a supporting electrolyte. We will assume that millisecond after application of the potential (Fig- unit area diffusing to the electrode.
the initial concentration of A is and that of the ure 25-lOb), the proliles have changed dramatically. At It is not practical to obtain limiting currents with
product P is zero. We also assume that the reduction the surface of the electrode, the concentration of A planar electrodes in unstirred solutions because the
FIGURE 25-9 Current response to a stepped potential for
Simulalion: Learn more about diffusion at currents continually decrease with time as the slopes
a planar electrode in an unstirred solution. (a) Excitation Simulation: concentration
lQJ potential. (b) Current response. of the concentration profiles become smaller.
profiles at electrodes.
 Visualizationof flow patterns in a
flowing stream. Turbulent flow,shown on the right,
becomes laminar flow as the average velocity
decreases to the left. In turbulent flow,the molecules
move in an irregular, zigzag fashion and there are
swirls and ecdies in the movement. In laminar flow,
the streamlines become steady as layers of liquid
slide by each other in a regular manner. (From An
Album of Fluid Motion, assembled by Milton Van
Dyke, no. 152, photograph by Thomas Corke and
Hassan Nagib, Stanford, CA: Parabolic Press, 1982.)

Concentration profiles at an
electrode-solution interface during the electrolysis
close to the electrode. These regions are illustrated
A ne - P from a stirred solution of A. See Fig-
Let us now consider concentration-distance profiles in Figure 25-12. In the laminar-flow region, the layers ure 25-6 for potentials corresponding to curves X,
when the reduction described in the previous section is of liquid slide by one another in a direction parallel
and Z.
performed at an electrode immerscd in a solution that to the electrode surface. Very near the electrode, at a
is stirred vigorously. To understand the effect of stir- distance centimeters from the surface, frictional
ring, wc must develop a picture of liquid flow patterns forces give rise to a region where the flo~ velocity is
in a stirred solution containing a small planar elec- essentially zero. The thin layer of solution"i.n this re-
trode. We can identify two types of flow depending on gion is a stagnant layer called the
the average flow velocity, as shown in Figure 25-11. It is only within the stagnant Nernst diffusion
flow occurs at low flow velocities and has layer that the concentrations of reactant and product
smooth and regular motion as depicted on the left in vary as a function of distance from the electrode sur-
the figure. flow, on the other hand, happens face and that there are concentration gradients. That
at high velocities and has irregular, fluctuating motion is, throughout the laminar-flow and turbulent-flow re-
as shown on the right. In a stirred electrochemical cell, gions, convection maintains the concentration of A at
we have a region of turbulent flow in the bulk of solu- its original value and the concentration of P at a very
tion far from the electrode and a rcgion of laminar flow low level.
Distance from electrode, em

place by diffusion alone, just as was the case with the

Figure 25-13 shows two sets of concentration pro-
Nernst diffusion laye~ _ unstirred solution. With the stirred solutIOn, however,
files for A and P at three potentials shown as X, Y, and
diffusion is limited to a narrow layer of liquid, which
Z in Figure 25-6. In Figure 25-13a, the solution is
even with time cannot extend indefinitely into the
divided into two regions. One makes up the bulk of
solution. As a result, steady, diffusion-controlled cur-
the solution and consists of both the turbulent- and
rents appear shortly after applying a voltage. .
Flow patterns and regions laminar-flow regions shown in Figure 25-12, where
of interest near the working electrode in As is shown in Figure 25-13, at potential X, the equI-
mass transport takes place by mechanical convection
hydrodynamic voltammetry. librium concentration of A at the electrode surface has
brought about by the stirrer. The concentration of A
been reduced to about 80% of its original value and the
throughout this region is whcreas IS essentially
equilibrium concentration P has increased by an equiv-
zero. The second region is the Nernst diffUSIOnlayer,
alent amount; that is, c~ At potential Y,
which is immediately adjacent to the electrode sur-
which is the half-wave potential, the equilibrium con-
face and has a thickness of centimeters. Typically, 8
centrations of the two species at the surface arc ap-
ranges from to 10- cm, depending on the effi-
proximately the same and equal to Finally. at
ciency of the stirring and the viscosity of the lIqUid.
potential Z and beyond, the surface concentration of A
Within the static diffusion layer, mass transport takes
 approaches zero, and that of P approaches the original This derivation is based on an ovcrsimplified picture . 00592
arpl
1 og
concentration of A, Thus, at potentials more nega- of the diffusion layer in that the interface between the
tive than Z, essentially all A ions entering the surface moving and stationary layers is viewed as a sharply
Often, the ratio kA1kl' in Equation 25-11 and in Equa-
layer are instantaneously reduced to P. As is shown in defined edge where transport by convection ceases and tion 25-12 is nearly unity, so that we may wflte for the
Figure 25-13b, at potentials greater than Z the concen- transport by diffusion begins. Nevertheless, this simpli-
tration of P in the surface laver remains constant at fied model does provide a reasonable approximation of species A
c~ because of diffusion ~f P back into the stirred the relationship between current and the variables that
region. affect the current.
current- Voltage Relationships
Current-Voltage Relationships for Irreversible Reactions
for Reversible Reactions
The current at any point in the electrolysis we have just Many voltammetrie electrode processes, particularly
discussed is determined by the rate of transport of A To develop an equation for the sigmoid curve shown in those associated with organic systems, are lfreverslble,
from the outer edge of the diffusion layer to the elec- Figure 25-6, we substitute Equation 25-6 into Equa- which leads to drawn-out and less well-defined ·waves.
trode surface. Because the product of the electrolysis tion 25-5 and rearrange, which gives To describe these waves quantitatively reqUIres an ad- FIGURE 25-14 Voltammograms for two-component
P diffuses from the surface and is ultimately swept ditionalterm in Equation 25-12 involving the activa- mixtures. Half-wave potentials differ by 0.1 V in curve
i
away by convection, a continuous current is required tion energy of the reaction to account for the kmetlcs and by 0.2 V in curve
to maintain the surface concentrations demanded by of the electrode process. Although half-wave poten-
Fe2~ ~Fe3t- + e~
the Nernst equation. Convection, however, maintains a The surface concentration of P can also be ex- tials for irreversible reactions ordinarily show some de-
constant supply of A at the outer edge of the diffusion pressed in terms of the current by using a relationship pendence on concentration, diffusion currents remaIll As the potential is made more negative, a decrease in
layer. Thus, a steady-state current results that is deter- similar to Equation 25-5. That is, linearly related to concentration. Some IrreverSible the anodic current occurs; at about -0.02 Y, the cur-
mined by the applied potential. This current is a quan- nFADp , processes can, therefore, be adapted to quantltatlve rent becomes zero because the oxidation of iron(II)
titative measure of how fast A is being brought to the i c~) analysis if suitable calibration standards are available.
ion has ceased.
surface of the electrode, and this rate is given by dcAldx Curve C represents the voltammogram for a solu-
where x is the distance in centimeters from the elec- where the minus sign results from the negative slope of Voltammograms for Mixtures of Reactants tion of iron(III) in the same medium. Here, a cathodiC
trode surface. For a planar electrode, the current is the concentration proftle for P. Note that Dp is now the The reactants of a mixture generally behave inde- wave results from reduction of iron(Ill) to iron (II).
given by Equation 25-4. diffusion coefficient of P. But we have said earlier that pendently of one another at a working electrode, Thus, The half-wave potential is identical with that for the
Note that dcAldx is the slope of the initial part of throughout the electrolysis the concentration of P ap- a voltammogram for a mixture is just the sum of the anodic wave, indicating that the oxidation and reduc-
the concentration profiles shown in Figure 25-13a, proaches zero in the bulk of the solution and, there- waves for the individual components. Figure 25-14
and these slopes can be approximated by (cA - c~)IS. fore, when 0, shows the voltammograms for a pair of two-component
When this approximation is valid, Equation 25-4 re- mixtures. The half-wave potentials of the two reactants
. -nfADpc~
duces to = = differ by about 0.1 in curve A and by about 0.2 Y
. nFAD" curve B. Note that a single voltammogram may permit 2+
(25-5) where kp -nFADp/S. Rearranging gives the quantitative determination of two or more speclCs
provided there is sufficient difference between succeed-
where the constant k is equal to nFAD A/S.
ing half-wave potentials to permit evaluatIOn of md,vld-
Equation 25-5 shows that as becomes smaller
Substituting Equations 25-7 and 25-10 into Equa- ual diffusion currents. Generally, a difference of 0.1 to
as a result of a larger negative applied potential the
tion 25-3 yields, after rearrangement, 0.2 Y is required if the more easily reducible species un-
current increases until the surface concentration ap-
dergoes a two-electron reduction; a minimum of about
proaches zero, at which point the current becomes con- 0.0592 k 0.0592 i
,ppl- -~Iog-k- - -~Iog-.--. - E", 0.3 is needed if the ftrst reduction is a one-electron
stant and independent of the applied potential. Thus, n n
process.
when c~ 0, the current becomes the limiting current (25-11)
and Equation 25-5 reduces to Equation 25-6."
When the third term on the right side of this Anodic and Mixed Anodic-Cathodic
. nFAD, Voltammograms
k,c, (25-6) equation becomes equal to zero, and, by definition,
E,pplis the half-wave potential. That is, Anodic waves as well as cathodic waves arc encoun-
tered in \'oltammetry. An example of an anodic wave IS FIGURE 25-15 Voltammetricbehavior of iron(t1)and
liCarcful analysis of the unib of the variables in thIS equation leads to 0.0592 k
E,ppl - II2 - E ~--log - - iIlust~ate-d in curve of Figure 25-15, where the elec- iron(lIl)in a citrate medium. Curve anodic wave for a
' mol e ) ( C em'"J (mol ,nalyte ) n solution in which 1 x 10 Curve B: anodlc-
( trode reaction is the oxidation of iron( II) to iron( Ill)
cathodic wave for a solution which 0.5 x
Substituting this expression into Equation 25-11 gives in the presence of citrate ion. A limiting current IS
10 -, M. Curve C: cathodic wave for a solution in which
an expression for the voltammogram in Figure 25-6. observed at about +0.1 Y (versus a saturated calomel
1 x 10 M.
That is, electrode [SeED, which is due to the half-reaction
 Inlet Electrical
moved by passing an inert gas through the analyte so.
connection
lulton for several mmutes (sparging). stream of the to counter
same gas, usually mtrogen, ISpassed over the surface electrode
of the solulton during analysis to prevent reabsorption block

of oxygen. The lower curve in Figure 25-16 is a voltam_

mogram of an oxygen-free solution.

The most important uses of hydrodynamic voltamme-

try Include (1) detection and determination of chemical
species. as they exit from chromatographic columns Or
f1ow-InJeclton apparatus; (2) routine determination of
oxygen and certain species of biochemical interest. such
as gluc?se, lactose, and sucrose; (3) detection of end Electrical
POlOtS eoulometrie and volumetric titrations; and connection
FIGURE Voltammogram for the reduction of to working
oxygen in an air-saturated KCIsolution. The lower (4) fundamental studies of electrochemical processes.
electrode
curve for a KCIsolution in which the oxygen is
removed by bubbling nitrogen through the solution.

Hydrodynamic voltammetry is widely use'd.ior de tee-

tion of the two iron species are perfectly reversible at
lton and determination of oxidizable or reducible
the working electrode.
compounds or ions that have been separated by liquid
Curve B is the voltammogram of an equimolar mix-
ture of lron(II) and iron(III). The portion of the curve
below the zero-current line corresponds to the oxida-
tIOn of the iron(II); this reaction ceases at an applied
potential equal to the half-wave potential. The upper
portIOn of the curve ISdue to the reduction of iron(III).

Dissolved oxygen is easily reduced at many working

elect~odes. Thus, as shown in Figure 25-16, an aqueous FIGURE (continued) (b) Detail of a commercial flow cell assembly. (c) Configurations of
solulton saturated with air exhibits two distinct oxygen working electrode blocks. Arrows show the direction of flow in the cell. ([b]and [c] courtesy of
waves. The first results from the reduction of oxygen to Bioanalytical Systems, Inc., West Lafayelle, IN.)
hydrogen peroxide:
from a counter electrode by a thin spacer as shown.
02(g) + 2H' + 2e' ~ H 0, chromatography or that are produced by flow-injec-
The volume of such a cell is typically 0.1 to I ilL. A
The second wave corresponds to the further reduction tion methods. 16 thin-layer cell such as the one shown
voltage corresponding to the limiting-current region
of the hydrogen peroxide: schematically in Figure 25-17a is used in these applica-
for analytes is applied between the working electrode
tions. The working electrode in these cells is usually
H 0, + 2H' + 2e- ~2H20 and a silver-silvcr chloride reference electrode that
embeddcd in the wall of an insulating block separated
is located downstream from the detector. We present
Because both reactions are two-electron reductions
an exploded view of a commercial flow cell in Fig-
the two waves are of equal height. ' 16Voitammetric detectors are a particular type of transducer called /imiJ-
transducers. In this dIScussion and subsequent discussions in- ure 25-17b, which shows clearly how the sandwiched
Voltammetric measurements offer a convenient
volving voltammetric transducers. we use the more common tcrm cell is assembled and held in place by the quick -release
and widely used method for determining dissolved metric de/ector. When a voltammetric transducer is inherently selective mechanism. locking collar in the counter electrode
oxygen In solutions. However, the presence of oxygen for a particular speCies by virtue of control of various experimental vari-
FIGURE (a)A schematic of a voltammetric system ables or ""hen it is co\ereu with a chemically selective layer of polymer or block, which is electrically connected to the poten-
often Interferes with the accurate determination of for detecting eiectroactive species as they elute from a other membranous material. we rder to It as a voltammecric sensor. For tiostat, retains the reference electrode. Five different
other species. Thus. oxygen removal is usuallv the first coiumn. The cell volume is determined by the thickness of a discussion of transducc:rs. detectors. sensors. and their definitions, see
configurations of working electrode are shown in
step in amperometrie procedures. Oxygen c~n be re- the gasket.
 Figure 25-l7c. These configurations pcrmit optimiza-
tIon of dctector sensitivity under a variety of experi- is an immobilized enzyme (see Section 23F-2). glucose used as labels in immunoassays, but tbese have largely
mental conditions. Working electrode blocks and elec- oxidase in this example. The inner layer is a cellulose been replaced by more convenient lahels such as fluo-
trode materials are described in Section 25B-1. This acetate membrane. which is permeable to small mole- rescent molecules and enzymes. Thus, immunosensors
type of application of voltammetry (or amperometry) cules, such as hydrogen peroxide. When this device is can use a variety of detection methods, such as optical
has detection limits as low as 10-' to M. We dis- immersed in a glucose-containing solution, glucose dif- and electrochemical techniqucs. More recently. label-
cuss. voltammetric detection for liquid chromatogra- fuses through the outer membrane into the immobi- free immunosensors have been developed based on
phy rn more detail in Section 28C-6. lized enzyme, where the following catalytic reaction piezoelectric (Section lC-4). surface plasmon reso-
occurs: nance (Section 2IE-I), and other detection strategies.
Figure 25-19 shows a scheme and an amperometric
glucose gllll:Ose oxida~e ) H20Z + gluconic acid
biosensor for determining specific proteins using a
In Section 23F-2, we described how the specificity of
The hydrogen peroxide then diffuses through the inner sandwich assay." In thisscheme (Figure 25-19a), an an-
potentIometriC sensors could he enhanced by applying
layer of membrane and to the electrode surface. where tibody appropriate for the desired analyte is immobi-
molecular recognition layers to the electrode surfaces.
it is oxidized to give oxygen. That is, lized on the surface of an electrode (A). In this example,
There has been much research in recent years in ap- Ring-Shaped" Pt disk
Ag anode " the antibody is immobilized by physical adsorption."
plyrng the same concepts to voltammetric electrodes," H,o, + OH - a, + H,G + 2e
When the electrode is in contact with a solution con-
A number of voltammetric systems are available com-
The resulting current is directly proportional to the taining the analyte, which is represented as blue trian-
mercially for the determination of specific species in .---------
glucose concentration of the analyte solution. A var- gles in the figure, it binds preferentially with the anti-
rndustrlal, biomedical, environmentaL and research Layernf KCI R<:p(aceahl~ membrane
solutIon -10 pm iation on this type of sensor is often found in home body (B). The electrode is then rinsed and brought into
applications. These devices are sometimes called elec- -10 pm thick. permeahlt'
glucose monitors widely used by diabetic patients. contact with a second antibody that has been tagged, or
trodes or detectors but are, in fact, complete voltam-
This device is one of the largest-selling chemical in- labeled, which is indicated by the stars in the figure
metric cells and are better referred to as sensors. In the FIGURE 25-18 The Clark voltammetric oxyger ~ensor.
struments in the world." In this example, the antibody is tagged with the enzyme
sections that follow, we describe two commercially Cathodic reaction: + 4H- 4e ~ 2H,6.~odic
Several other sensors are available that are based alkaline phosphatase, which catalyzes the conversion
avaIlable sensors and one that is under development in reaction: Ag CI- ~ AgCI(s) eo.
on the voltammetrie measurement of hydrogen perox- of hydroquinone diphosphate to hydroquinone. When
this rapidly expanding field.
ide produced by enzymatic oxidations of other species a voltage of 320 m V versus Ag-AgCl is applied to the
When the oxygen sensor is immersed in a flowing or of clinical interest. These analytes include sucrose, lac- working electrode, hydroquinone undergoes a two-
Oxygen Sensors. The determination of dissolved oxy- stirred solution of the analyte, oxygen diffuses through tose, ethanol, and L-Iactate. A different enzyme is. of electron oxidation to quinone (D). The resulting cur-
gen rn a variety of aqueous environments, such as sea- the membrane into the thin layer of electrolyte imme- course, required for each species. In some cases. en- rent is directly proportional to the original concentra-
water, blood, sewage, effluents from chemical plants, diately adjacent to the disk cathode, where it diffuses zyme electrodes can be based on measuring oxygen or tion of the analyte.
and soils, is of tremendous importance to industry, bio- to the electrode and is immediately reduced to water. on measuring pH as discussed in Section 23F-2. Figure 25-19b is a photo of the biosensor array used
medIcal and environmental research, and clinical med- In contrast with a normal hydrodynamic electrode, to carry out the immunoassay described in the previ-
icine. One of the most common and convenient meth- two diffusion processes are involved - one through Immunosensors. Sensor specificity is often achieved ous paragraph. The biosensor consists of an array of
ods for making such measurements is with the Clark the membrane and the other through the solution be- by using molecular recognition elements that react ex- electrodes, with each electrode being an independent
oxygen sensor, which was patented by C. Clark Jr in tween the membrane and the electrode surface. For clusively with the analyte. Antibodies are proteins that immunoscnsor. This arrangement permits multiple
18
1956. A schematic of the Clark oxyg~n sensor is sho~n a steady-state condition to be reached in a reasonable have exceptional specificity toward analytes and arc proteins to be determined simultaneously. The array
in Figure 25-18. The cell consists of a cathodic platinum- period (10 to 20 s), the thickness of the membrane and the recognition clements most commonly used in im- was fabricated on glass using photolithographic techni-
disk working electrode embedded in a centrally locatcd the electrolyte film must be 20 or less. Under these munosensors.") Immunosensors arc typically fabri- ques that are common in the semiconductor industry.
cylindrical insulator. Surrounding the lower e~d of this conditions, it is the rate of equilibration of the transfer cated hy immobilizing antibodies on the sensor surface In this procedure, the glass substrate was patterned
insulator is a ring-shape silver anode. The tubular insu- of oxygen across the membrane that determines the either through adsorption, covalent attachment, poly- with a polymer (photoresist) that is easily removed by
lator and electrodes are mounted inside a second cylin- steady-state current that is reached. mer entrapment. or other methods. solvent. The pattern of the polymer was the negative
der that contains a buffered solution of potassium chlo- A variety of assay formats are used with immuno- of the pattern of the electrodes. Iridium (-100 nm)
ride. A thin (- 20 replaceable, oxygen-permeable Enzyme-Based Sensors. A number of enzyme.based sensors. One of the most common methods uses two an- was then deposited over the entire substrate using
membrane of Teflon or polyethylene is held in place at voltammetric sensors are available comme~ciallv. An tihodies. one that is immobilized on the sensor surface sputtering. The polymer was then removed to leave the
the bottom end of the tube by an a-ring. The thickness example is a glucose sensor that is widelv used it; clin- and is used to capture the target analyte, and one that iridium working and counter electrodes on the sub-
Mthe electrolyte solution between the cathode and the ical laboratories for the routine determi~ation of glu- is labeled and is used to detect the captured analyte strate. The refcrence electrode was prepared using a
membrane is approximately 1 m. Cose In blood "~crum. This de\'ice is similar in construc- (a sandwich Traditionally, radionuclides were similar procedure and depositing silver. The reference
tion to the oxygen sensor shnv.'o in Figure 25-1 X. The
I'For a rec~n( review of ekctrochemic<:Il ."'-L'r.: L ,md membrane in this caSe is more comrl~ex and cunsists .'1.\1 Wit'ion and W Nl<\ Anal. Chem" 2006, 7R. 2507,
Om. Anal. 2006. 7R. 3965 . of three layers. The outer lavcr IS a polvcarbonate him 'See FIgure 33-1Y lor photo of a home glucose and ." f'Jf a disLUssion of the t<.:rmsand dt'tinitions..d~S()<:iated with <.:hcmi..:all)
I~Fur a detailed discussion of the CI;uk oxvgen sen"(lT, see M. L. Hitchman tHin :'3[)·1 for a of discr~re clinical analyzers
that is permeable to glucose but impe~meable to pro-
Mcasurrment Dissolved Chaps. 3-5, New York~ \Vile). Fur of the prinCIples and applications of lmmunmcnsors. S(;C'P.B C Pure and Applied Chrmistry,
tems and other constituents (If blood. The middle laver Luppa. 1. Sokoll. and D \\'. Chao. Clinica ChimiL'1l Acta, 2001. I http:,''''wwwlupac.org/puhlicationslp,t<.:iI997ipdf!o90flxI31 7,pdf
 to titrations in which a precipitate or a stablc complex
electrode was then completed by electrochemical de-
is the product. Precipitating reagents include silver
posItIon of AgO from a solution containing KCl d
nitrate for halide ions, lead nitrate for sulfate ion, and
added Ag+. The array was coated with an insula~~
several organic reagents, such as 8-hydroxyquinoline,
polymer film leaving the electrode and contact area~
dimethylglyoxime, and cupferron, for various metallic
exposed, and finally, a cylindrical polycarbonate well
ions that are reducible at working electrodes. Scveral
(not shown) was attached over the electrodes to con-
metal ions have also been determined by titration with
tam the analyte solution.
Volume of standard solutions of ethylenediaminetetraacetic acid
The 0.785-mm 2 Ir working electrodes were then Volume of
reagent, mL reagent. mL (EDTA). The exception just noted involves titrations
* electrochemically activated to build up a layer of irid-
Ium oXIde on each. The porous oxide was grown to in-
(aJ of organic compounds, such as certain phenols, aro-
HO matic amines, and olefins; hydrazine; and arsenic(lfI)
crease the surface area available for antibody immobi-
and antimony(IIl) with bromine. The bromine is often
hzatlOn on the electrode. Drops of solution containing
generated coulometrically. It has also been formed by
the appropnate antIbodies were then applied over the
adding a standard solution of potassium bromate to an
working electrodes, and the array was incubated at 4"C
acidic solution of the analyte that also contains an ex-
to complete the immobilization.
cess of potassium bromide. Bromine is formed in the
Analyses were performed on serum samples con-
o acidic medium by the reaction
taining a mixture of goat IgG, mouse IgG, human IgG,
and chIcken IgY antibodies (0-125 ng/mL). In this as- reagent, mL
say, the target analytes were also antibodies (IgG and
IgY),.and so the capture and detection antibodies were This type of titration has becn carried out with a ro-
FIGURE 25-20 Typical amperometric titration curves:
antibodies toward antibodies (anti-IgG aqd·anti-IgY). tating platinum electrode or twin platinum electrodes.
(a)analyte is reduced, reagent is not; (b) reagent is
Analy1e solutions were added to the sen~or well, fol- reduced, analyte is not; (c) both reagent and analyte There is no current prior to the equivalence point; after
lowed by a mixture of detection antibodies. To perform are reduced. thc equivalence point, there is a rapid increase in cur-
the electrochemical measurements, the biosensor was rent because of the electrochemical reduction of the ex-
connected to a multichannel computer-controlled po- cess bromine.
or of time if the reagent is generated by a constant-
tentiostat via the edge contacts of the array, and cur- There are two advantages in using a pair of iden-
current coulometric process. Plots of the data on either
rent measurements were made on all eight working tical metallic electrodes to establish the equivalence
side of the equivalence point arc straight lines with dif-
electrodes. point in amperometric titrations: simplicity of equip-
ferent slopes; the end point is established by extrapo-
The precision of the measurements ranged from ment and not having to purchase or prepare and main-
1.9% to 8.2% relative standard deviation, and the de- lation to the intersection of the lines."
tain a reference electrode. This type of system has
Amperometric titration curves typically take one of
tection limit was 3 ng/mL for all analytes. The results been incorporated in instruments designed for routine
the forms shown in Figure 25-20. Figure 25-20a repre-
compare quite favorably (2.4%-6.5% difference) with automatic determination of a singlc species, usually
sents a titration in which the analyte reacts at the elec-
results from commercial single-analyte assays using with a coulometrically generated reagent. An instru-
trode but the reagent does not. Figure 25-20b is typical
(b) spectroscopic enzyme-linked immunosorbent assays ment of this type is often used for the automatic deter-
of a titration in which the reagent reacts at the work-
FIGURE 25-19 (a) A: electrode containing immobilized (ELISAs). In this application, four analytes were de- mination of chloride in samples of serum, sweat, tissuc
ing electrode and the analyte does not. Figure 25-20c
antibody B: binding of target analyte (") to electrode- termined in duplicate, but any combination of up to cxtracts, pesticides, and food products. The reagent in
corresponds to a titration in which both the analyte
bound antibody; C: binding of alkaline phosphatase-labeled e'ghtanalytes may be determined simultaneously. It is this system is silver ion coulometrically gcneratcd from
and the titrant react at the working electrode.
antibody to electrode-bound analyte; D: application of 320 antiCipated that when the array biosensor is coupled a silvcr anode. About 0.1 is applied between a pair
There are two types of amperometric electrode sys-
mVto the electrode and addition of hydroquinone diphos- wIth a mlcrotluidics system (Section 33C) for solution of twin silver electrodes that serve as thc indicator sys-
phate (HODP).Electrochemical oxidation of AP-generated tems. One uses a single polarizable electrode coupled
handling, the combined device will become a powerful tem. Short of the equivalence point in the titration of
hydroquinone (HO)generates a current at the electrode to a reference electrode; the other uses a pair of iden-
tool for the routine determination of this important chloride ion, thcre is essentially no current because no
that is proportional to the amount of analyte bound to the tical solid-state electrodes immersed in a stirred solu-
class of biochemical analytes. electroactive species is present in the solution. Be-
electrode. (b) Photograph of the biosensor showing the tion. For the first, the working electrode is often a ro-
cause of this, there is no electron transfer at the cath-
arrangement of IrOx 1-mm-diameter working electrodes, tating platinum electrode constructed by sealing a
ode, and the electrode is completely polarized. Note
4-mm-d,ameter counter electrode, 7-mm-outside-diameter platinum wire into the sid" of a glass tube that is con-
Ag-AgCIreference electrode, and electrical contacts on the Hydrodynamic voltammetry can be used to estimate that the anode is not polarized because the reaction
the equivalence point of titrations if at least onc of the nected to a stirring motor.
substrate (28 x 35 x 1 mm). For clarity,the sample well is Amperometric tit rations with one indicator elec-
not shown. (Adapted from M. S. Wilson and W. Nie, Ana/. participants or products of the reaction involved is
trodc have. with onc notable exccption, becn confmcd
Chern., 2006, 78, 2507, with permission of the American oxidized or reduced at a working electrode. Here, the
occurs in the presence of a suitable cathodic reactant
Chemical Society.) Image reprinted with permission from current at some fixed potential in the limiting-current 23S. R. Crouch and F 1. Hollc:r. Applications of J,ficrosoft" Excel
AnaJ. Chern. Copyright 2006 American Chemical Society. lylical
or depolarizer.
region is measured as a function of the rcagent volume
 Past the equivalence point, the cathode becomes
depolarized because silver ions are present; these ions
react to give silver. That is,
Ag- +e-~Ag
Disk
This half-reaction and the corresponding oxidation of
silver at the anode produce a current whose magnitude
is, as in other amperometric methods, directly pro-
portional to the concentration of the excess reagent. (aJ (b)
Thus, the titration curve is similar to that shown in Fig-
25-22 Disk (a) and ring (b) current for reduction of oxygen at the rotating-ring-disk
ure 25-20b. In the automatic titrator just mentioned, electrode. (From Laboratory Techniques in Electmanalytical Chemistry, 2nd ed., P. Kissinger
an electronic circuit senses the amperometric detec- and W. R. Heineman, eds., p. 117, New York:Dekker, 1996. With permission.)
tion current signal and shuts off the coulometric gener-
ator current. The chloride concentration is then com-
puted from the magnitude of the titration current and reactions have been performed with ROEs. A common
the generation time. The instrument has a range of 1 to experiment with an ROE is to study the dependence of
on A plot of versus is known as a Levich plot, In cyclic voltammetry (CV),26 the current response of
999.9 mM C1- perliter, a precision of 0.1 %, and an ac-
and deviations from the linear relationship often indi- a small stationary electrode in an unstirred solution is
curacy of 0.5%. Typical titration times are about 20 s.
cate kinetic limitations on the electron-transfer pro- excited by a triangular voltage waveform, such as that
The most common end-point detection method
cess. For example, if becomes independent of w at shown in Figure 25-23. In this example, the potential is
for the Karl Fischer titration for determining water
large values of w' the current is not limited by mass first varied linearly from +0.8 V to -0.15 V versus an
(see Section 240-1) is the amperometric method with
transport of the electroactive species to the electrode SCE. When the extreme of -0.15 V is reached, the scan
dual polarized electrodes. Several manufacturers of-
surface, but instead, the rate of the reaction is the limit- direction is reversed, and the potential is returned to
fer fully automated instruments for use in performing
ing factor. ROEs, such as the versatile commercial its original value of +0.8 V. The scan rate in either di-
these titrations. A closely related end-point detection
model shown in Figure 25-21c, have attracted renewed rection is 50 m This excitation cycle is often re-
method for Karl Fischer titrations measures the po-
_ interest in recent years for both fundamental and quan- peated several times. The voltage extrema at which
tential difference between two identical electrodes ~ Disk
through which a small constant current is passed. titative analytical studies as enthusiasm for the drop-
ping mercury electrode (polarography) has faded. 26For brief reviews, see P. 1'. Kissinger and W. R. Heineman. 1. Chern.
Educ., 60, 702~ D. H. Evans, K. M. O'Connell, T A. Petersen, and
ROE detection with a mercury film electrode is some-
M.1. Kelly, 1. Chern. Educ., 1983,60,290.
To carry out theoretical studies of oxidation-reduction times referred to as pseudopolarography.
reactions, it is often of interest to know how in The rotating-ring-disk electrode is a modified ROE
Equation 25-6 is affected by the hydrodynamics of the that is useful for studying electrode reactions; it has
system. A common method for obtaining a rigorous little use in analysis. Figure 25-21d shows that a ring-
description of the hydrodynamic flow of stirred solu- disk electrode contains a second ring-shape electrode
tion is based on measurements made with a rotating that is electrically isolated from the center disk. After
disk electrode (ROE), such as the one illustrated in an electroactive species is generated at the disk, it is
Figure 25-21a and b. When the disk electrode is ro- 25-21 (a) Side view of an showing solution then swept past the ring where it undergoes a second +0.2
tated rapidly, the flow pattern shown by the arrows in flow pattern. (b) Bottom view of a disk electrode. (c) Photo electrochemical reaction. Figure 25-22 shows voltam-
the figure is set up. At the surface of the disk, the liq- of a commercial (Courtesy of BioanalyticalSystems, mograms from a typical ring-disk experiment. The
Inc., West Lafayette, IN.)(d) Bottom viewof a ring-disk curve on the left is the voltammogram for the reduc-
uid moves out horizontally from the center of the de-
electrode. tion of oxygen to hydrogen peroxide at the disk elec-
vice, which produces an upward axial flow to replenish
the displaced liquid. A rigorous treatment of the hy- trode. The curve on the right is the anodic voltammo-
drodynamics is possible in this case 24 and leads to the The terms F, A, and D in this equation have the same gram for the oxidation of the hydrogen peroxide as it
Levich equation2; meaning as in Equation 25-5, w is the angular velocity flows past the ring electrode. Note that when the po-
of the disk in radians per second, and" is the kinematic tential of the disk electrode becomes sufficiently nega-
viscosity in centimeters squared per second, which is tive so that the reduction product is hydroxide rather
the ratio of the viscosity of the solution to its density. than hydrogen peroxide, the current in the ring elec-
Voltammograms for reversible systems generally have trode decreases to zero. Studies of this type provide
24A. Bard and L R. Faulkner. Electrochemical i'ttemods, 2nd ed., New
the ideal shape shown in Figure 25-6. Numerous studies much useful information about mechanisms and intcr-
York:: Wiley, 2001, pp. 335 -39
!5V. G. Le\lch, Acta Physicochimica CRSS, 1942, /7, 257. of the kinetics and the mechanisms of electrochemical mediates in electrochemical reactions.
reversal takes place (in this case, -0.15 and +0.8 V) are Important variables in a cyclic voltammogram are
called switching potentials. The range of switching po- the cathodic peak potential the anodic peak poten-
tentIals chosen for a given experiment is one in which a tial the cathodic peak current and the anodic
diffusion·controlled oxidation or reduction of one or peak current p,' The definitions and measurements of
more analytes occurs. The direction of the initial scan these parameters are illustrated in Figure 25-24. For a
may be either negative, as shown, or positive, depending reversible electrode reaction, anodic and cathodic peak
on the composition of the sample (a scan in the direc- currents are approximately equal in absolute value but
tion of more negative potentials is termed a forward opposite in sign. For a reversible electrode reaction at
scall, and one in the opposite direction is called a reverse 25°C, the difference in peak potentials, j.E is expected
scan). Generally, cycle times range from I ms or less to tobe
100 s or more. In this example, the cvcle time is 40 s.
Figure 25-24b shows the current response when a
solution that is 6 mM in K]Fe(CN)6 and 1 M in KNO, where is the number of electrons involved in the
is subjected to the cyclic excitation signal shown in Fig- half-reaction. Irreversibility because of slow electron-
ures 25-23 and 25·24a. The working electrode was a transfer kinetics results in exceeding the expected
carefully polished stationary platinum electrode and b value. Although an electron-transfer reaction may
20
the reference electrode was an SCE. At the initial appear reversible at a slow sweep rate, increasing the
potential of +0.8 V, a tiny anodic current is observed, sweep rate may lead to increasing values of j.E a sure
which immediately decreases to zero as the scan is con- sign of irreversibility. Hence, to detect slow electron-
tinued. This initial negative current arises from the transfer kinetics and to obtain rate constants, p is
oxidation of water to give oxygen (at more positive po- measured for different sweep rates.
10 Potential, V vs. Agl
tentials, this current rapidly increases and becomes Quantitative information is obtained from the
quite large at about +0.9 V). No current is observed FIGURE 25-25 Cyclic voltammogram of the insecticide
Randles·Sevcik equation, which at 25°C is
between a potential of +0.7 and +0.4 V because no re- parathion in 0.5 M pH 5 sodium acetate buffer in 50% eth-
ducible or oxidizable species is present in this potential anol. Hanging mercury drop electrode. Scan rate: 200 m
range. When the potential becomes less positive than Vis. (From W. R. Heineman and P. Kissinger, Arner. Lab.,
0 1982, no. 11,34. Copyright 1982 by International
approximately +0.4 V, a cathodic current begins to de- where p is the peak current (A), A is the electrode area
(cm'), is the diffusion coefficient (cm'/s), c is the con- Scientific Communications, Inc.)
velop (point B) because of the reduction of the hexa-
cyanoferrate(llI) ion to hexacyanoferrate(ll) ion. The centration (mollcm3), and v is the scan rate (Vis). CV
reaction at the cathode is then offers a way of determining diffusion coefficients if the
concentration, electrode area, and scan rate are known. The anodic peak at B arises from the oxidation of the
hydroxylamine to a nitroso derivative during the re-
verse scan. The electrode reaction is
A rapid increase in the current occurs in the region of
R-C6H,NHOH R-C6H4NO + 2H+ + 2e~
B to D as the surface concentration of Fe(CN)6'- be-
The primary use of CV is as a tool forfundamental and (25-19)
comes smaller and smaller. The current at the peak is diagnostic studies that provides qualitative informa-
made up of two components. One is the initial current tion about electrochemical processes under various The cathodic peak at C results from the reduction of
surge required to adjust the surface concentration of conditions. As an example, consider the cyclic voltam- the nitroso compound to the hydroxylamine as shown
the reactant to its equilibrium concentration as given mogram for the agricultural insecticide parathion that by the equation
by the Nernst equation. The second is the normal FIGURE 25-24 (a) Potential versus time waveform and
is shown in Figure Here, the switching poten- R-C6H,NO + 2e + 2H· R-C6H,NHOH
ditfusion-controlled current. The first current then de- (b)cyclic voltarnmograrn for a solution that is 6.0 mM in
tials were about -1.2 V and +0.3 V The initial forward (25-20)
cays rapidly (points to as the diffusion layer is ex- K Fe(CN)6and 1.0 M in KN0 (From P Kissinger and
W.H. Heineman, Chern. EduG.. 1983, 60, 702. Copy- scan was, however, started at 0.0 V and not +0.3 V
tended farther and farther away from the electrode sur- Cyclic voltammograms for authentic samples of the
right 1983; Divisionof Chemical Education, Inc.) Three peaks are observed. The first cathodic peak (A)
face (see also Figure 25-lOb). At point -0.15 V), the results from a four-electron reduction of the parathion two intermediates conlirmed the identities of the com-
sean direction is switched. The current, however, con- pounds responsible for peaks Band C.
ally reduction of Fe(CNk' no longer occurs and the to give a hydroxylamine derivative
tinues to be cathodic even though the scan is toward CV is widely used in organic and inorganic chem-
current goes to zero and then becomes anodic. The an-
more positive potentials because the potentials are still R-C6H,N02 + 4e~ + 4H+ R-C6H,NHOH + H20 istry. It is often the first technique selected for investi-
odic current results from the reoxidation of Fe( CN),'-
negative enough to cause reduction of Fe(CN)6 As (25·18) gation of a system with electroactive species. For ex-
that has accumulated near the surface during the for·
the potential sweeps in the positive direction, eventu- ample, CV was used to investigate the behavior of the
ward scan. This anodic current peaks and then de-
modified electrodes described in Section 25B-2 and
creases as the accumulated Fe( is uscd up by the ~7This discussion and the \oltammogram arc from R Heineman and
P. T Kissinger, .4mer. Lab .. 1982 (11). 29
shown in Figure 25-5. The resulting cyclic voltammo-
~ Sirnu[atinn: Learn more about cyclic \'oltammetr~·.