Voltammetric Techniques of Analysis: The Essentials
Voltammetric Techniques of Analysis: The Essentials
Voltammetric Techniques of Analysis: The Essentials
DOI 10.1007/s40828-015-0016-y
LECTURE TEXT
Received: 20 May 2015 / Accepted: 11 August 2015 / Published online: 9 September 2015
Springer International Publishing 2015
Abstract This text is written for a course on instrumental OHP Outer Helmholtz plane
methods of quantitative analysis. It summarizes the basic pzc Potential of zero charge
concepts of modern voltammetric techniques of analysis. RE Reference electrode
The guiding concept of this text is to demonstrate how the SHE Standard hydrogen electrode
ratio of faradaic to capacitive currents decides about the SMDE Static mercury electrode
sensitivity of the techniques, and how this ratio can be VT Voltammetric technique
increased by electronics, electrode construction and by WE Working electrode
chemical means. Finally, the advantages and disadvantages
of voltammetric techniques of analysis are briefly
described.
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such as cyclic voltammetry, chronocoulometry and impe- voltammetric techniques of analysis, simply because
dance spectroscopy. These techniques will not be discussed voltammetric techniques outnumber all other electroana-
in this text. Equally, we will not discuss electroanalytical lytical techniques. Of course, potentiometric techniques,
techniques using organic solvents. especially, pH measurements with glass electrodes, and
also other potentiometric measurements with ion-selective
(or ion-sensitive) electrodes are very frequently performed
Electroanalytical techniques based on measuring in laboratories, industry and environmental monitoring.
charge transport properties of ions
techniques
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The currents flowing in these two reactions are called What are voltammetric techniques?
faradaic currents because they follow Faradays law:
The term voltammetry is derived from voltamperometry,
‘‘The number of moles of a substance, m, produced or
and it expresses that the current is measured as a function of
consumed during an electrode process, is propor-
voltage, i.e., electrode potential. Since any electrochemical
tional to the electric charge passed through the elec-
cell needs two electrodes, it would be impossible to extract
trode, q. Assuming that there are no parallel
unambiguous analytical information, if both electrodes
processes, q ¼ nFm, where n and F are the number of
would determine the magnitude of the flowing current.
electrons appearing in the electrode reaction equa-
Therefore, one electrode is made much smaller than the
tion, and the Faraday constant, respectively’’ [9].
other, so that the flowing current is limited by this electrode
The Faraday constant is the charge of one mol electrons: only. This electrode is called the working electrode, and the
9.64853383(83) 9 104 C mol-1. The history of the dis- other (larger) electrode is called the auxiliary electrode.
covery of this law is nicely described in [10]. Although an electrochemical cell needs only two elec-
There is also another pathway of current through an trodes to operate, it is very beneficial to introduce a third
electrochemical cell: The two sides of the electrode/elec- electrode: this third electrode is a reference electrode, i.e., an
trolyte interfaces can be charged and discharged like the electrode which has a known and fixed electrode potential.
two plates of a plate condenser. Such currents are called No current should ever pass this electrode, as a current
capacitive currents or charging currents. They will be would change its potential, and possibly damage this elec-
explained in detail further down. trode. The reference electrode is used to control the potential
Electroanalytical techniques based on charge-transfer of the working electrode by measuring the voltage between
processes at electrode/electrolyte interfaces can be subdi- these two electrodes. A cell with a working electrode (WE),
vided in static and dynamic techniques. In the cases of an auxiliary electrode (AE) and a reference electrode (RE) is
static techniques, the currents are ideally zero and no net called a three-electrode cell (Fig. 2). The potential differ-
reaction occurs. In the dynamic techniques, measurable ence at the electrolyte/electrode interface of the working
currents flow and the system is dynamic in the sense that a electrode is controlled with the help of a potentiostat. Most
net reaction proceeds. potentiostats use a feedback circuit that applies such voltage
The most important static technique is potentiometry, between the auxiliary and the working electrodes, that the
where the potential of an electrode is measured relative to potential of the working electrode exactly matches the value
the potential of a reference electrode. This technique is also it should have. Usually the working electrode is grounded,
called an equilibrium technique, or I = 0 technique. In the so that in fact the potential of the solution is controlled.
case of pH glass electrodes, the potential drops at the inner Voltammetry is now the general term for all techniques in
and outer glass membrane solution interfaces are measured which the current is measured as a function of electrode
with two reference electrodes. Membrane electrodes are the potential. At the beginning of its development was Jaroslav
most important type of ion-sensitive electrodes. Heyrovský, the inventor of a voltammetric technique which he
Dynamic techniques (also called transient techniques, named POLAROGRAPHY. (The term polarography was
because they record time-dependent phenomena) to mea- meant to indicate that the polarization of an electrode was
sure processes at electrode/electrolyte interfaces can be graphically recorded as current–potential curves: current-flow
subdivided in controlled potential and controlled current means depolarization, and no-current-flow means polarization,
techniques (see the next paragraph). In controlled potential meaning that the potential increases without or only with a
techniques, devices are used (so-called potentiostats) which minor current response). Heyrovský used a dropping mercury
allow controlling the potential in a desired way, i.e., electrode (see further down) as working electrode. For some
keeping it constant at a certain value, or shifting it in a time, the terms voltammetry and polarography have been used
programmed way. The current is then measured as the as synonyms; however, now polarography is used exclusively
answer of the system to the potential. This kind of tech- for ‘‘voltammetry with a dropping mercury electrode’’.
niques is called voltammetric techniques.
Alternatively, one may use devices that control the
current (so-called galvanostats) and measure the potential Faradaic versus capacitive currents
of the working electrode as the answer to the current.
Controlled potential and controlled current techniques Faradaic currents
can in principle give the same information; however, with
the development of potentiostats, controlled potential The best way to determine the concentration of compounds
techniques have won the race. is to measure faradaic currents which they generate when
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Concentration
Potentiostat Electrode
Solution
A B+e
Diffusion layer
Concentration
Solution
time
Electrode
AE
WE
RE
A B+e
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limiting the current, and if the electrode surface is planar but randomizes their position to some extent. The elec-
and the solution unstirred (and electrode not moving), the trical field acts to fix their position, but the thermal
current decay is described by the Cottrell equation: movement counteracts this fixation. The thickness of the
rffiffiffiffiffiffiffi EDL depends primarily on the number of ions per volume
DA
I ¼ nFAelectrode cA;bulk : ð4Þ of solution (i.e., their concentration), the charge of ions,
pt and on the charge density on the metal side, i.e., on the
According to this equation, the current decreases with electrode potential. The dielectric constant of the solution
t-1/2. The Cottrell equation can be derived from the fol- is a third factor. The dielectric constant varies in the
2
lowing linear differential equation:ocAotðx;tÞ ¼ DA o cox
A ðx;tÞ
with EDL, due to the non-random orientation of the dipoles.
2
At a certain potential, there is no excess charge on either
appropriate boundary conditions (see, e.g. [11]).
side of the EDL. This potential is called the ‘‘potential of
zero charge’’ (pzc). It depends on the metal, the solvent,
Capacitive currents
and the nature and concentration of the electrolyte.
Capacitive currents flow at electrodes because charge
The interface of an electron conductor and a solution
can be accumulated on the two sides of the EDL. To
forms a capacitor because charge can be accumulated on
understand the origin of capacitive currents, it is helpful to
both sides. The side of the electron conductor can be
remember the physics of a capacitor: current is the first
charged negatively by accumulating electrons and posi-
derivative of charge over time:
tively by an electron deficit. The solution side can be
charged by an excess of either anions or cations. In dQ
Ic ¼ : ð5Þ
addition to the ions, dipole molecules of the solvent can dt
be oriented on the interface and give an additional con- The accumulated charge is the product of surface area A
tribution to the accumulated charge. Because of the and charge density (charge per unit of surface area) q:
capacitive properties, the interface is also called an
dQ dðAqÞ
electrochemical double layer (EDL). Figure 5 shows a Ic ¼ ¼ : ð6Þ
simplified scheme for the case of a metal electrode in dt dt
contact with an electrolyte solution. The following fea- This gives according to the rules of mathematics:
tures are important: (a) at the very interface, there is a
dA dq
layer of adsorbed and oriented dipole solvent molecules. Ic ¼ q A : ð7Þ
dt dt
(b) Solvated cations can approach the interface only
down to a minimum fixed distance, the so-called outer Now we have to introduce a specific parameter of the
Helmholtz plane. (c) Some anions can specifically adsorb EDL, the so-called ‘‘differential double layer capacity’’
at the interface (the dark green ball in Fig. 5). The plane Cdl:
passing through the centres of the specifically adsorbed dq
anions is called the inner Helmholtz plane. (d) In the Cdl ¼ : ð8Þ
dE
diffuse layer, the excess charge compensating the charge
The differential double layer capacity takes into account
on the metal side is decaying toward the solution bulk,
that the charge density is also a function of electrode
because the numbers of cations and anions are changing
in such way that their charges compensate. (In case of potential E. Multiplication of Eq. 8 with the term dt dt leads
unit charges, this happens for equal numbers of cations to:
and anions). In reality, the structure of the EDL is more dq dt
complicated, on both sides; however, for understanding Cdl ¼ : ð9Þ
dt dE
electroanalytical methods, this is of minor importance.
We can rearrange Eq. 9 as follows:
The potential varies in the EDL linearly within the
compact layer and up to the outer Helmholtz plane. It dq dE
¼ Cdl ð10Þ
then decays exponentially in the diffuse layer. This is dt dt
important, because outside the EDL, there is no electric and insert this in Eq. 7:
field resulting from the charged electrode, i.e., outside the
EDL ions are not affected by the electrode potential, and dA dE
Ic ¼ q ACdl : ð11Þ
so no migration can happen. The diffuse layer results dt dt
from the thermal energy of the system, which prevents Equation 11 is of fundamental importance: It tells us
the ions to be arranged in a fixed distance from the metal, that a capacitive current will always flow when (i) the
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+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒ + ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒ + ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
OHP
IHP
+Potential
‒
+ ‒
metal + ‒
+ ‒
+ ‒
+ ‒
+ ‒ + ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒ + ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒ + ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
solution + ‒
r
OHP
IHP
compact layer diffuse layer
Fig. 5 Scheme of an electrochemical double layer. IHP inner Helmholtz plane, OHP outer Helmholtz plane. /metal and /solution are the inner
potentials in the metal and solution, respectively. On the abscissa, the distance r from the interface is plotted and on the ordinate the potential
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become less and less precise, as the overall current is set Metal Solution
by the capacitive behaviour of the EDL. This is easily
understandable when one imagines the following situa- vct vmt
tion: the mass of a captain should be measured, and
somebody has the idea to put in one measurement the charge transfer transport of educts from bulk to the electrode
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RT a quasi irreversibility) RT a
E E A/B ln ox E E A/B ln ox
nF ared interface
nF ared interface
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Fig. 11 A polarographic curve recorded with a Heyrovský polaro- from bottom to top. Reproduced from [14]. (Copied by permission
graph. On top, the voltage between the two electrodes is given. The from the ‘‘Electrochemistry Encyclopedia’’ (http://knowledge.electro
element symbols stand for the ions giving the respective waves. The chem.org/ed/dict.htm) on ‘‘March/30/2015.’’ The original material is
potential of the DME is increasingly negative going from left to right. subject to periodical changes and updates.)
There is no current scale given; the reduction currents are increasing
I I
If If
time interval
for current
measurement
Ic Ic
dropping is neglected). At positive potentials, the mercury wave shape of the reduction signal of A can be understood
(electrode) is oxidized and causes an oxidation current. At as follows: when the electrode potential is not sufficiently
rather negative potentials the protons of the solution are negative to drive the faradaic reaction, no current can flow.
reduced to hydrogen. These two currents limit the range in When the potentials reach values at which, according to the
which other signals can be measured. Fortunately, the Nernst equation
proton reduction (hydrogen evolution) is strongly retarded RT aoxðAÞ
on mercury, so that the potential window for measurements E ¼ EA=B þ ln : ð12Þ
nF aredðBÞ
is rather large (depending on the electrolyte and current
range, it can be up to 2.5 V, more realistic is a range of 1 to
1.5 V). Figure 14b shows the polarogram when a substance A needs to be converted to B, and a reduction current
A is present in the solution, and A can be reduced to B. The flows. The magnitude of this current increases with
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Fig. 15 Classification of
methods to affect the ratio of
faradaic to capacitive currents.
One arrow up (:) means that
this current is increased; two
arrows up (::) means strong
increase. Arrows down (; and
;;) mean in the same way a
decrease. A horizontal line ( )
indicates that this current is
not (or not much) affected
such combination of a Multi-Mode Electrode with Stair- essential for all ‘‘potential step techniques’’, i.e., Staircase
case Voltammetry, very low detection limits can be Voltammetry and the pulse techniques discussed further
achieved (around 10-7 mol L-1); however, this depends on down. Figure 19 depicts these dependencies. The t-1/2
a very proper functioning of the electrode and measuring dependence (see Eq. 4) is only observed for planar diffu-
instrument. It should be remarked here, that with the sion (planar electrode with dimensions much above the lm
development of digital instrumentation, all linear potential range) and for an electrochemical reversible system (see
sweeps are realized by staircase functions. further down).
We have now to understand the dependence of the far- On the right side of Fig. 19 is shown, how a proper
adaic and capacitive currents following a potential step choice for the period of current measurement minimizes
when the electrode surface area is kept constant. This is the capacitive current. This current sampling at the end of
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the step is essential to benefit from the different current diminishing of capacitive currents is due to the behaviour
transients. When staircase voltammetry (Fig. 18) is per- shown in Fig. 19. However, one can still improve the
formed with a Multi-Mode Electrode (see above) the discrimination of capacitive currents, especially, by
applying pulse techniques:
A
dA dA dA dA
Pulse techniques
0 0 0 0
dt dt dt dt
Fig. 19 Dependence of E E
faradaic and capacitive current
at an electrode with constant
surface area following a
potential step. On the right side, Estep Estep
the time tm is indicated during
which the faradaic current is
measured with minimal
contribution of capacitive
current
t t
I I
tm
1/2
if t
kt
ic e
t t
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tpulse
Epulse
Estep
staircase ramp
tstep
t t
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ΔI n , dp Phase-sensitive measurements
A + ne B
Figure 23 illustrates the phase relationship between the
E1/2 Epeak applied alternating potential and the faradaic and capaci-
tive currents. The faradaic current has a phase lead of 45
with respect to the potential, and the capacitive current has
a phase lead of 90, i.e., between the faradaic and capac-
E itive currents is a phase shift of 45. The phase shift
between capacitive current and potential is well known
from the physics of a plate capacitor, where the capacitive
current is proportional to the first derivative of potential
over time. The phase shift of faradaic current is the result
of diffusion (if no reaction rates are involved). Figure 23
shows that a current measurement at 0 is theoretically free
Fig. 22 Differential pulse polarogram (full line) in comparison with of capacitive current; however, the faradaic current is
the direct current polarogram shown in Fig. 14. The current scale pffiffi
giving DIn,dp relates only to the differential pulse voltammogram reduced by a factor of 22. This reduction of the absolute
value of faradaic current is no problem, since the ratio IIcf is
(i) phase-sensitive measurements, and (ii) measurements of strongly increased. Figure 24 shows the ac-voltammo-
higher harmonics. grams of the reduction of an experimental example (Cd2?
2
2 Eapp , If , Ic 0 2
Ic , If 0 2 If , Ic
2 0° 2
315° 45°
Δ 45
2 2
If , I c 270° 90° If , Ic
2 2
225° 135°
2 180° 2
Ic , If 2 Ic , If 0
2 If , Ic 0 2
2
Fig. 23 Phase shift between faradaic and capacitive currents
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Fig. 24 Phase-selective measurement of the reduction signal of Cd2? ions in 5 mol L-1 hydrochloric acid solution. cCd2þ ¼ 103 mol L1 ,
alternating potential frequency: 100 Hz, alternating potential amplitude: 10 mV. Adopted from [20]
ions) measured at different phase shifts with respect to the Many music instruments generate higher harmonics, which
applied alternating voltage. At 0, the faradaic peak is are important for the produced sound impression.
superimposed to an almost zero current background level, Since the first harmonic (f) has the form of a one peak,
which shows that the capacitive current is obviously very the second harmonic has two peaks, a maximum and a
small. At 90, the faradaic peak is superimposed to an minimum. The third harmonic has two maxima and one
appreciable background current, which is clearly the con- minimum. The higher the harmonic, the smaller are the
tribution from the capacitive current. Figure 24 also illus- currents. However, the ratio IIcf is more favourable (larger)
trates that real systems do not behave as ideally, as the higher the harmonics, because the capacitive current
predicted by theory: at 135 and 315, there should not produces only very small higher harmonics: The capacitive
appear faradaic peaks, as theoretically If should be zero, current is a much more linear function of potential (an
but the figure shows small peaks. almost linear sloping background current) and thus its
higher harmonics are exceptional small. It is also possible
Higher harmonics to perform phase-selective recording of higher harmonics,
so that the capacitive currents is reduced by both approa-
Figure 24 shows that the faradaic ac signals have the form ches. Figure 25 depicts the first to third harmonics of
of symmetric bell-shaped peaks, i.e., the relation between phase-sensitive ac-voltammograms of a solution containing
alternating current and potential is highly non-linear. In cadmium ions: the peak currents decrease with increasing
cases of non-linear current–potential relationships, there order of harmonics, and the background current reduces
are always current components also at higher frequencies: tremendously.
when the alternating potential has the frequency f (so-
called fundamental frequency), the basic ac response is at Tensammetry
the same frequency, but there are also currents at 2f, 3f, …
etc. The 2f response is called the second harmonic, the The relationships depicted in Fig. 23 can also be used to
3f response the third harmonic, etc. The shape of the cur- selectively measure capacitive currents, which is very
rent signals of the ðn þ 1Þf response ((n ? 1)th harmonic) useful in case of compounds which are strongly adsorbing
resembles the first derivative of the nf response (nth har- on the electrode surface but not undergoing faradaic
monic). Higher harmonics are well known from acoustics. transformations (oxidations or reductions). If the
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Γads
2 µA
First harmonic
‒0.5 ‒0.6 ‒0.7
Ic
Second harmonic
Fig. 25 Phase-sensitive first to third harmonics of the reduction Although this technique is suitable for some special
signal of Cd2? ions in 1 mol L-1 hydrochloric acid solution. applications, it suffers from the following drawbacks: First,
cCd2þ ¼ 104 mol L1 , alternating potential frequency: 156 Hz, alter- the peak currents are not a linear function of solution
nating potential amplitude: 10 mV. Adopted from [21] concentration, and, second, when several different
adsorbing compounds are present in the solution, there are
compound is hydrophobic (or amphiphilic) it is adsorbed strong interferences because adsorption is always a com-
strongly at potentials around the potential of zero charge petition for a limited number of adsorption sites. Thus,
(pzc), as there the coulombic interaction between the adsorption strength and concentration will affect the
electrode surface and the solution (dipoles and ions) is results.
the weakest. Figure 26 shows schematically the depen-
dence of surface concentration Cads of an adsorbed com- Square-wave voltammetry (SqWV)
pound on electrode potential. There are two potential
ranges (grey underlay in Fig. 26), where the change in When instead of a sinusoidal alternating potential, a
surface concentration as function of potential, i.e., dC ads
dE ,
square-wave alternating potential is superimposed to a
has maxima. In this ranges, the double layer capacity of the linear, or better to a staircase ramp, the resulting voltam-
double layer changes dramatically, and this prompts metry is called square-wave voltammetry [22]. The
capacitive currents in the form of peaks (Fig. 26, bottom). potential–time function is a train of identical pulses, and by
These peaks can be used to quantify compounds, which sampling the currents within short periods of all pulses, and
adsorb on electrodes. The most suitable electrode for this is subtraction of the currents of the negative pulse from the
a dropping mercury electrode, because (i) mercury has a following positive pulse (or vice versa), again an increase
highly hydrophobic surface at which hydrophobic com- of the IIcf ratio results. Square-wave voltammetry is very
pounds strongly adsorb, and because (ii) the electrode popular, especially also in stripping voltammetry (next
surface is constantly renewing. The ac voltammetric (po- paragraph). Like the ac-voltammetry with sinusoidal
larographic) technique aimed at measuring such adsorp- alternating potential, it suffers from the fact that irre-
tion–desorption peaks is called tensammetry, because versible systems give low currents, especially at higher
surface-active compounds (tensides) can be quantified. frequencies.
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Table 1 Elements and compounds which can be determined with the help of VTs. The limits of detection are rough estimates which can be in
special cases higher or lower than indicated here
Elements Technique Detection limit
O2, Cd, Cu, Bi, Zn, Pb, Sn, Ti, V, Mo, Fe, Ga, DCP/LSV 10-5 mol L-1
As, Se, Br, I, In, W, Tl, U, Ag, Hg, H? current sampled DCP/LSV 10-6 mol L-1
DPP/DPV, SqWP/SqWV 10-7–10-8 mol L-1
Cd, Cu, Bi, Zn, Pb, Sn, Tl, Ag, Hg Anodic stripping voltammetry down to 10-11 mol L-1
(esp. with DPV or SqWV)
S, Se, Te, Cl, Br, I, Fe, W, Mo Cathodic stripping voltammetry down to 10-11 mol L-1
(esp. with DPV or SqWV)
Mo, W, Fe, V, Ti, U, Cr, Co, Ni, Pd, Pt, H? Catalytic currents down to 10-11 mol L-1
with adsorptive preconcentration down to 10-13 mol L-1
(esp. with DPV or SqWV)
Al, Si, Fe, Cr, Ni, Co, Pd, Pt Adsorptive stripping voltammetry down to 10-11 mol L-1
with catalytic currents down to 10-13 mol L-1
(esp. with DPV or SqWV)
Tensides (generally, many organic compounds) Tensammetry 10-5–10-7 mol L-1
Electroactive organic compounds (e.g. ascorbic acid, Voltammetry/polarography 10-5–10-7 mol L-1
aldehydes, quinones, phenols, nitro compounds, thiols, with adsorptive preconcentration
ketones, sugars, etc.) much less
Stripping techniques keeping at a potential where the Cu2? ions are reduced to
copper which deposits at the electrode. If the mass trans-
Anodic stripping voltammetry (ASV) port towards the electrode is kept during reduction at a high
rate, e.g. by stirring the solution (i.e., by keeping the
The simplest way to increase the ratio IIcf is an enrichment concentration gradient steep, as shown in the paragraph
(preconcentration) of a compound on the electrode surface. ‘‘Faradaic currents’’), it is possible to accumulate a con-
Let us assume copper ions (Cu2?) are present in a solution siderable amount of copper on the electrode. If this copper
at a concentration of 10-9 mol L-1. Not any of the pre- is then anodically oxidized during a rather fast potential
viously discussed techniques is able to record a distinct scan, the current (dq =dt ) is much larger than the non-de-
signal of reduction of the copper ions, because that faradaic tectable reduction current. When metals are deposited by
current is completely obscured by the capacitive current reduction and the metal deposit is anodically dissolved, the
(and noise and other faradaic currents of impurities). The technique is called anodic stripping voltammetry. Fig-
obvious solution of the problem is to electrolyze the ure 27 shows the potential–time function and the current
solution for some minutes with the working electrode versus potential curve for the anodic stripping voltammetry
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ChemTexts (2015) 1:17 Page 19 of 24 17
of copper ions. In this figure, a simple linear scan is potential from the potential for preconcentration to poten-
depicted. Due to the enrichment of the oxidizable com- tials at which the mercury salt is reduced to mercury and
pound on the electrode, the faradaic current is much higher the chloride ions are released to the solution
than in a measurement where the diffusion of the dissolved Hg2 Cl2 þ 2e ! 2Hg þ 2Cl : ð15Þ
ions fuels a reduction current. By this simple approach, it is
already possible to decrease the detection limit to 10-8 and The sensitivity of these methods depends on the solu-
10-9 mol L-1. Even lower (10-10 and 10-11 mol L-1) can bility of the deposited salts [24]. The smaller their solu-
be reached when the dissolution reaction is recorded with bility, the lower are the concentrations which can be
differential pulse voltammetry. detected. This limitation is rather severe, so that only a few
Anodic stripping voltammetry allows easy determination cathodic stripping methods are more widely applied: the
of metals which form amalgams with mercury. In these cases, determination of selenium is a good example. When a
a stationary mercury drop electrode can be used, or, even with solution contains SeO32- ions, one has to add Cu2? ions
higher sensitivity, so-called mercury film electrodes: when and can preconcentrate selenium as Cu2Se (copper(I)
mercury(II) ions are added in rather low concentration to the selenide) because at an appropriate potential the following
analyte solution, and when carbon (especially, glassy carbon) reactions proceed:
is used as working electrode, a ‘‘film’’ of micrometer size SeO2 þ 2
3 þ 6e þ 6H ! Se þ 3H2 O ð16Þ
mercury droplets is deposited, and simultaneously the analyte
metals are deposited on the surface of the mercury droplets, 2Cu2þ þ 2e ! 2Cuþ ð17Þ
where they usually dissolve and diffuse into the droplets The resulting ions Se2- and Cu? form the very sparingly
interior. Because these mercury droplets are so small, the soluble salt Cu2Se:
metals have short diffusion lengths when oxidized. This
enhances the faradaic currents and leads to very narrow peaks 2Cuþ þ Se2 ! Cu2 Se # ð18Þ
of large currents. Anodic stripping voltammetry can be
During the reductive scan, a voltammogram is recorded
applied especially for the determination of elements, which
which shows a reduction peak corresponding to the
dissolve in mercury, like Cu, Bi, Pb, Zn, Cd, Sb. However, in
reaction:
recent times, a lot of methods have been developed which use
bismuth and carbon electrodes instead of mercury. When Cu2 Se þ 2e ! 2Cu þ Se2 ð19Þ
metals are deposited in solid form on electrodes, the disso- i.e., solid Cu2Se is reduced to solid copper metal and the
lution signals are often more complicate (multi peaks) selenide ions are released to the solution.
because of the different activities of different crystallographic
surface planes. However, in recent years, it has been shown Adsorptive stripping voltammetry (AdsSV)
that bismuth film electrodes (on glassy carbon) are an
attractive alternative to mercury electrodes [23]. The fact that hydrophobic (and amphiphilic) compounds
adsorb on electrodes, can be also used for preconcentration.
Cathodic stripping voltammetry (CSV) Metal complexes with organic ligands, and also a number of
organic compounds can be preconcentrated this way. Usu-
Cathodic stripping voltammetry is a technique where a ally the adsorbed compounds do not undergo an oxidation or
material deposited on the electrode during the preconcen- reduction reaction during the preconcentration. Following
tration step is dissolved by a cathodic, i.e., reductive, the preconcentration period, a voltammetric curve is recor-
process. Ions like chloride, bromide, iodide can be pre- ded. This has to scan the potentials into positive potentials,
concentrated in the form of sparingly soluble salts, like when the adsorbed compound can be oxidized, and to neg-
Hg2Cl2, Hg2Br2, Hg2I2, when the potential of the mercury ative potentials, when the compounds can be reduced.
electrode is kept sufficiently positive to oxidize mercury to As an example, the adsorptive stripping voltammetric
Hg22? ions, which precipitate these salts: determination of Co2? and Ni2? ions is given. Every
2Hg ! Hg2þ
2 þ 2e ð14Þ chemistry student learns that dimethylglyoxime (dmg) is a
good chelating agent for these ions. The nickel complex is
Hg2þ
2 þ 2Cl ! Hg2 Cl2 # ð15Þ
very sparingly soluble in water and used for the gravimetric
(Of course, both reactions are equilibria, but the single determination of nickel. At very low concentration, the
arrow indicates the dominating direction of the reactions cobalt and nickel complexes are soluble and, due to the
during preconcentration.) hydrophobicity of the ligand dmg, strongly adsorb on a
After the preconcentration period, the cathodic reduc- mercury electrode. The metal(II) ions form a complex in
tion of these salts is recorded by scanning the electrode solution according to the reaction:
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17 Page 20 of 24 ChemTexts (2015) 1:17
MeðIIÞ þ 2dmgH2 MeðdmgHÞ2 þ 2Hþ : ð20Þ systems where the rate of electron transfer vct is smaller
than the rate of mass transfer vmt . When the rate of electron
At the mercury surface, an adsorption equilibrium is transfer is increased by means of a catalyst, this is called
established, and adsorption is used to preconcentrate the electrocatalysis. There are applications of such kind of
complex at the surface: electrocatalysis for improving the performance of voltam-
MeðdmgHÞ2 dissolved MeðdmgHÞ2 adsorbed ð21Þ metric methods of analysis. A nice example is the deter-
mination of platinum traces: a platinum complex is
The adsorbed complex is reduced during the voltam- adsorbed on a mercury electrode, the platinum ions are
metric measurement: reduced to platinum metal, which is a highly active catalyst
MeðdmgHÞ2 adsorbed þ10e þ 10Hþ Me þ 2DHAB for the reduction of protons to hydrogen. The resulting
current of hydrogen formation is a measure of platinum
ð22Þ
ions in the bulk solution and allows to analyse Pt con-
(DHAB = 2, 3-bis(hydroxylamino)butane), In this exam- centrations down to 2.5 9 10-13 mol L-1 [29]! This is a
ple [25], both the metal ions and the ligands are reduced. result of preconcentration and catalysis.
The detection limit is in the nmol L-1 range. It can be Catalytic currents can also be generated by homoge-
decreased by two orders of magnitude by a combination neous chemical reactions of the product of electrode
with catalytic currents (see further down). reaction so that the educt is recycled. A good example is a
Another example for the adsorptive stripping voltam- solution containing Mo(VI) [30]. Molybdenum(VI) is
metry is the determination of chromium using diethylene- reduced in acidic solutions first to Mo(V) and at more
triaminepentaacetic (DTPA) acid as chelating agent negative potentials to Mo(III). When the reduction is per-
(detection limit around 20 nmol L-1 [26]. This method has formed in a solution containing a high concentration of
been later modified, the sensitivity enhanced, and even chlorate ions (around 0.1 mol L-1), the following reactions
used for chromium speciation with respect to Cr(III) and proceed, when the potential range is limited to values of
Cr(VI) [27]. Mo(V) formation:
Although adsorptive stripping methods often allow to
achieve extremely low detection limits, they are also prone Mo6þ þ e ! Mo5þ ð23Þ
to severe interferences by other compounds which also
Mo 5þ
þ ClO
3
þ
þ 2H ! Mo 6þ
þ ClO2 þ H2 O ð24Þ
adsorb on the electrode.
(For simplicity, we have written here Mo6? and Mo5?,
Cathodic stripping voltammetry following an adsorptive although ions with such high charges cannot exist as aqua
preconcentration complexes, but only in complexes with oxide ions,
hydroxide ions or other ligands.). Equation 24 shows that
In this technique, metal complexes are preconcentrated on chlorate is able to oxidize Mo(V) to Mo(VI): from ther-
an electrode surface by adsorption, and the metal ions of modynamic point of view, this means that chlorate must be
the adsorbed complexes are then reduced. The latter pro- even easier reducible than Mo(VI), i.e., at even less neg-
cess may be recorded with differential pulse voltammetry ative potentials! However, this does not happen for kinetic
for an additional improvement of the current response (i.e., reasons. The reduction of chlorate is so irreversible, i.e., vct
discrimination of capacitive currents). A good example for so slow that it is absolutely not reduced at these potentials.
this strategy is the determination of copper, lead, and However, in a homogeneous chemical reaction proceeding
cadmium ions using 8-hydroxyquinoline (oxine) as com- in the diffusion layer before the electrode, reaction 24
plexing agent. This allowed to achieve detection limits of proceeds without any kinetic hindrance. Figure 28
1.2 9 10-10 mol L-1 Cd2?, 3.0 9 10-10 mol L-1 Pb2? schematically visualizes the situation in the absence and
and 2.4 9 10-10 mol L-1 Cu2? [28]. presence of chlorate ions. In the absence of chlorate, Mo5?
Adsorptive stripping voltammetry can also be used to diffuses away from the electrode surface, the diffusion
determine elements like aluminium(III)—which cannot be layer expands, and the concentration gradient of Mo6? is
reduced in aqueous solutions—when it is bond in a com- not very steep. However, in the presence of chlorate, the
plex by redox active ligands. Mo5? is reoxidized to Mo6? while diffusing away. The
result is a very thin diffusion layer, which is called in this
Catalytic currents case ‘‘diffusion and reaction layer’’ because both processes
determine its thickness. The very steep concentration pro-
Catalysis is a very important issue in electrochemistry. As file of Mo6? leads to a high current. Although this current
mentioned in the paragraph ‘‘Electrochemical reversibility originates from the reduction of Mo6? at the surface, it is in
and irreversibility’’, there are many electrochemical fact fuelled by the high concentration of chlorate ions,
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ChemTexts (2015) 1:17 Page 21 of 24 17
which are chemically reduced by Mo5?. One can formulate The combination of cathodic stripping voltammetry with
this as a catalytic cycle, where Mo6?/Mo5? is the catalyst catalytic current is also very beneficial in some cases: so it
and chlorate the substrate as shown in Fig. 29. The cat- was possible to determine iron down to 810-11 mol L-1 in
alytic current depends on the rate of the reaction given by sea water [31]. Similarly, the combination of adsorptive
Eq. 24. When chlorate is at very large excess with respect stripping voltammetry and catalytic currents can also be
to the molybdenum concentration, the currents are directly used to decrease the limit of detection: thus, in the presence
proportional to the molybdenum concentration. This way it of the oxidant nitrite (NO2-), the adsorptive stripping
is possible to reach detection limits down to 10-10 mol L-1 determination of Co2? (see the paragraph ‘‘Adsorptive
(and lower). Such catalytic currents are observed especially stripping voltammetry’’) has a detection limit in the 10-12
with transition metal ions, which easily undergo redox mol L-1 range [32].
reactions, e.g. Mo, W. Ti, Fe, Ni, Pt, etc.
Concentration
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17 Page 22 of 24 ChemTexts (2015) 1:17
(iii) VTs are much better suited to determine Capacitive current Current due to the charging (or
inorganic species than organic compounds, discharging) of the
because in the analysis of organic compounds electrochemical double layer
only very rarely a single compound is present, Charge transfer The crossing of an interface by
and in case of mixtures, the interferences charge (electrons or ions)
usually circumvent the use of VTs (or need Charge transport The transport of charges (electrons
combinations with separation techniques). or ions) inside a phase
(iv) For the determination of inorganic species in Charging current =capacitive current
aqueous solutions, organic compounds present Chronoamperometry Measuring the current at an
in the sample have to be completely destroyed electrode as function of time
(e.g. digested by hydrogen peroxide and UV (usually at a constant potential)
irradiation). This is especially important in Chronocoulometry Measuring the charge flowing
trace analysis using stripping techniques. through an electrode as function of
(v) It is a great advantage of VTs that they probe time (usually at a constant
the species really existing in solutions. (This is potential)
not the case for atomic spectroscopy, where the Chronopotentiometry Measuring the potential of an
species present in solution are transferred to a electrode as function of time
plasma where they are present as atoms.) VTs (either at constant current or zero
are therefore suitable for speciation analysis. current)
Speciation analysis determines not only con- Conductometry Measurement of the conductivity
centration, but also qualitatively identifies of a phase
different species (different complexes, or dif- Coulometry Measurement of the conductivity
ferent oxidation species); VTs can do that at of a phase
trace concentrations, e.g. well below 10-6 mol Cyclic voltammetry Measurement of current through
L-1. This is something which only some an electrode when the electrode
spectroscopic techniques can achieve in rare potential is periodically cycled
cases. between two potentials (usually
(vi) VTs are primarily used to analyse solutions. with constant potential scan rate)
Applications to solid samples are possible, but Electrode The term ‘‘electrode’’ has different
this affords much more sophisticated strate- meaning; (a)The electronic
gies, and then it is only applicable to main conductor at which
components [34]. electrochemical reactions take
(vii) The instrumentation for VTs is rather inex- place (e.g. a platinum
pensive (compared with atomic spectroscopy wire) (b)The half-cell consisting
techniques). of an electron and an ion
(viii) Instrumentation for VTs can be made so small conductor having a common
and lightweight that it can be used in field interphase (e.g. a silver wire and
analysis (portable instruments with batteries) its adjacent electrolyte solution
containing silver ions)
Electrochemical cell An electrochemical cells consist of
Glossary at least two electron conductors
(usually metals) in contact with
Amperometry Measurement of current (usually
ionic conductors
at a constant electrode potential)
Electrochemical Capacitor formed at the interphase
Analyte Compound to be determined in an
double layer (EDL) of two phases, esp. of that formed
analysis
at the interface of an electron
Auxiliary electrode In an electrochemical cell with a
conductor and ion conductor
working electrode and an auxiliary
(electrode)
electrode (and possibly a reference
electrode), the latter only serves to
Electrode of second Metal electrode (Menþ =Me) where
close the electric circuit. The
kind the activity of Menþ is fixed by the
auxiliary electrode does not limit solubility of a sparingly soluble
the overall current salt of Menþ
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ChemTexts (2015) 1:17 Page 23 of 24 17
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17 Page 24 of 24 ChemTexts (2015) 1:17
30. Pelzer J, Scholz F, Henrion G, Heininger P (1989) Fresenius Z 34. Scholz F, Schröder U, Gulaboski R, Doménech-Carbó A (2015)
Anal Chem 334:331–334 Electrochemistry of immobilized particles and droplets, 2nd edn.
31. van den Berg CMG, Aldrich AP (1998) Electroanalysis 369–373 Springer, Berlin
32. Vega M, van den Berg CMG (1997) Anal Chem 69:874–881
33. Czae M-Z, Wang J (1999) Talanta 921–928
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