Voltammetric Techniques of Analysis: The Essentials

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ChemTexts (2015) 1:17

DOI 10.1007/s40828-015-0016-y

LECTURE TEXT

Voltammetric techniques of analysis: the essentials


Fritz Scholz1

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.

Keywords Voltammetry  Analytical chemistry Introduction

Abbreviations In industry and research, voltammetric techniques (VTs) of


AC Alternating current analysis have certainly less importance than chromato-
ACP Alternating current polarography graphic, electrophoretic and spectroscopic techniques.
AE Auxiliary electrode However, for specific analytical tasks, they offer superior
ACV Alternating current voltammetry solutions, and hence it is important that students become
AdsSV Adsorptive stripping voltammetry acquainted with their essential features and the funda-
ASV Anodic stripping voltammetry mentals they are based on. It is not easy to give an over-
CSV Cathodic stripping voltammetry view on voltammetric techniques of analysis, because this
DC Direct current topic is very diverse and the theory behind goes deep into
DCP Direct current polarography thermodynamics and kinetics of electrochemistry, a branch
DCV Direct current voltammetry of physical chemistry which also does not find sufficient
DME Dropping mercury electrode attention in many curricula. This text is written to give a
DPP Differential pulse polarography wide overview on voltammetric techniques so that students
DPV Differential pulse voltammetry get an orientation in what cases they can and should be
EDL Electrochemical double layer used with benefit. The text is written for a general course in
IHP Inner Helmholtz plane instrumental analysis. For more detailed information the
reader is referred to monographs [1, 2], textbooks on
electrochemistry and electroanalysis [3–5], and to the
& Fritz Scholz ‘‘Electrochemical Dictionary’’ [6]. There are also electro-
[email protected]
analytical techniques which are of immense value in
1
Institute of Biochemistry, University of Greifswald, Felix- studies of the electrochemical properties of compounds and
Hausdorff-Str. 4, 17487 Greifswald, Germany systems, but of little importance for quantitative analysis,

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17 Page 2 of 24 ChemTexts (2015) 1:17

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

If one understands electroanalysis as all applications of Electroanalytical techniques based on measuring


electricity for chemical analysis, the position of voltam- charge-transfer processes at interfaces
metric analysis is that of a subdivision: an overview on
electroanalysis is given in Fig. 1. When electrodes (elec- When a current passes through an electrochemical cell, the
tron conductors, like metals, e.g. Hg, Au, Pt) or carbon following processes proceed: (a) the electrons have to be
(graphite, glassy carbon) are introduced in an electrolyte transported within the metal wires connecting a current (or
solution (or a solid electrolyte, i.e., ion conductor) it is voltage) source with the electrodes. This is guaranteed by
possible to study (a) the conduction (charge transport) in the free electrons in the metals (metal conduction).
the electrolyte, and (b) the charge transfer at the elec- (b) when the electrons reach the electrode/electrolyte
trode/electrolyte interface. Techniques based on the charge interface, a process of charge transfer has to guarantee that
transport are mainly (i) conductometry, i.e., measuring the charge can pass through the interface. In some cases, the
ionic conductivity of solutions, and (ii) electrophoresis [7, electron can be transferred to a species in solution, e.g. an
8], where the variations in charge transport are used to iron(III) ion:
separate ions. Electrophoresis is usually treated in the
Fe3þ þ e ! Fe2þ ð1Þ
framework of separation techniques, although it makes use
of migration of ions in an electric field, and thus could be In other cases, a cation may join the metal electrode
taken as an electrochemical technique. Conductometry is (e.g. a piece of lead, or a mercury droplet) and uptake
well known as a method to indicate the equivalence point electrons to be reduced:
of titrations, and also as the basic measuring principle of Pb2þ þ 2e ! Pb ð2Þ
detectors in ion chromatography.
Although electroanalytical techniques based on mea- This reaction is equivalent to the passing of electrons
suring the transport properties of ions are frequently used, through the interface, because the electrons are ‘‘neutral-
the term electroanalysis is often identified with ized’’ by the cation which joins the electrode.

Fig. 1 A possible subdivision


of electroanalysis. ‘‘Dynamic Electroanalysis
techniques’’ are those in which
the electrochemical equilibrium
is shifted with the help of an Measuring transport properties of ion in phases Measuring of electrochemical equilibria and charge
excitation (potential changes or -Conductometry
transfer reactions and interfaces
current changes), whereas in the -Electrophoresis
‘‘static techniques’’ the
electrochemical equilibrium at
the electrode is not affected. Static methods Dynamic methods
Sometimes, dynamic techniques -Potentiometry (pH
are described as active, and the electrodes and other ion-
static techniques as passive sensitive electrodes)

techniques

Controlled potential methods Controlled current methods

Controlled potential Voltammetry Chronoamperometry Current controlled Chronopotentiometry


coulometry coulometry
(I = f(E))

Amperometry Impedance spectroscopy

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ChemTexts (2015) 1:17 Page 3 of 24 17

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

Eapplied EWE versus RE


dNernst Distance from electrode surface

Diffusion layer

Fig. 3 Diffusion layer which forms when the compound A is


oxidized to form B on an electrode surface. The (Nernst) diffusion
layer thickness dNernst is the distance from the interface to the
intercept of the two (almost) linear parts of the concentration profile

Concentration

Solution
time
Electrode

AE
WE
RE
A B+e

Distance from electrode surface

Fig. 4 Increase of diffusion layer thickness with time of experiment

Fig. 2 Scheme of a three-electrode electrochemical measurement


The diffusion profile also depends on the electrode
geometry and size. When the electrode dimension goes
down to the lm range, edge effects become important and
the diffusion layer may assume a spherical shape when the
they are oxidized or reduced at electrodes. The generation
electrode is a disc. When the solution is stirred (or the
of faradaic currents needs the molecules or ions to reach
electrode is moved, e.g. rotated, when it is a disc or wire),
the electrode surface. This can be accomplished only by
the diffusion layer shrinks because the solution is mixed.
mass transport toward the electrode surface. There are only
Since current is the first derivative of charge over time,
three possible mechanisms which can transport them:
dq
(a) diffusion in a concentration gradient, (b) migration of i.e., I ¼ dt , the current at a planar electrode (much above
ions in a potential gradient, and (c) convection. A con- lm dimension) decays with time, because of Fick’s law:
centration gradient will always build up at the elec-
ocA ðx; tÞ
trode/electrolyte interface, when the compound is oxidized JA ðx; tÞ ¼ DA ; ð3Þ
ox
or reduced at the electrode surface. Figure 3 visualizes this.
The diffusion profile depends on the diffusion coeffi- JA is the flux of species A in mol cm2 s-1, DA is the
cients of diffusing ions (or molecules), and it is a function diffusion coefficient of A in cm2 s-1, and cA is the con-
of time. The diffusion layer thickness grows with time, and centration of A in mol cm-3, as a function of distance
the concentration gradients (i.e., the steepness of concen- x from electrode surface and time t. Clearly, because the
tration versus distance function) will decrease with time. concentration gradient ocAoxðx;tÞ decreases with time, the
This is shown for the compound A only in Fig. 4. current also drops with time. If diffusion is the only process

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ChemTexts (2015) 1:17 Page 5 of 24 17

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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17 Page 6 of 24 ChemTexts (2015) 1:17

+ ‒
+ ‒
+ ‒

+ ‒
+ ‒
+ ‒
+ ‒ + ‒
+ ‒

+ ‒

+ ‒

+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒

+ ‒
+ ‒

+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒
+ ‒ + ‒
+ ‒
+ ‒
+ ‒

+ ‒

+ ‒
+ ‒

+ ‒
+ ‒
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

surface area changes with time (dA dt 6¼ 0), or (ii) the


Why do the capacitive currents limit the sensitivity
dE of voltammetric measurements?
potential changes with time ( dt 6¼ 0), or (iii) both, the
surface area and the potential change with time. Since When capacitive and faradaic currents flow at the same
voltammetry means to measure currents as a function of time, one can always only measure their sum. Often the
potential, it is clear that dE
dt can never be kept at zero, at
analytical signal is a peak-shaped faradaic current,
least not for the entire measurement. We shall later see how whereas the capacitive current is a sloping line. Further,
one can keep it at least at zero for certain short periods of all measurements involve noise, i.e., stochastic fluctua-
time. The surface area of an electrode can much easier be tions which origin in electronics, the electrode, the cell
etc. When the concentration of the analyte decreases,
kept constant (dAdt ¼ 0), as solid metal electrodes of course also the faradaic currents decrease; however, the capac-
possess a constant area. However, when a dropping mer- itive currents are unaffected by the concentration of the
cury electrode is used (see further down), it needs a valve analyte. Hence, the ratio IIcf decreases with decreasing
to stop the outflow of mercury periodically, to keep the
analyte concentration. The measurement of If will thus
surface area constant during certain periods of time.

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ChemTexts (2015) 1:17 Page 7 of 24 17

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

ship with the captain, and in another measurement the


ship without the captain on a balance. Clearly, the dif- and of products from the electrode to the bulk

ference should give the captain’s mass. However, to


diffusion
measure the mass of a ship, a very large balance is migration
needed, which will have a scale in the thousand tons convection
range, but the measuring uncertainty will be so much
larger than the captain’s mass, that this experiment must
fail. The same is also true for a chemical laboratory: it Fig. 6 The rate of charge transfer vct, and the rate of mass transport
vmt of an electrode reaction
will be impossible to measure in the milligram range,
when the pot for weighing the milligram-sample has the
mass transport of product to the bulk of solution, or (iii)
mass of a kilogram (or this would need an extremely
by the rate of charge transfer. We shall discuss here only
sophisticated balance, as it is not available in chemical
case (i) and (iii), as case (ii) is less frequently found.
laboratories). From analytical point of view, current
When the equilibrium between the oxidized and reduced
measurements are not different: it will become impossi-
forms of the electroactive compound is very quickly
ble to distinguish extremely small faradaic currents from
established at the interface, i.e., when vct is faster than
large capacitive currents. Here it needs to be emphasized  
that it is not the absolute smallness of currents which vmt, the ratio aared
ox
at the interface will assume
interface
limits the quantitative determination of analytes, but it is exactly the value which follows from the Nernst equation
 
their smallness in relation to the capacitive current! The 
 aox
(E ¼ EA=B þ RT
nF ln ared ) for this potential. The
problem is getting even tougher when the base line interface
current is noisy. Noise means the stochastic fluctuation Nernst equation describes an equilibrium situation, and
 
of current which is caused by stochastic perturbations at hence a system where the ratio aared
ox
corresponds to
interface
the electrode, the cell, the electronics, etc. So-called
the potential given by the Nernst equation, is called an
white noise contains all frequencies and one may
electrochemically reversible one. However, when the
improve the signal-to-noise ratio by accumulation of
charge-transfer rate vct is smaller than the mass transport
voltammograms (like in spectroscopy), but this is another
rate vmt, the equilibrium cannot be established with a
topic.
sufficient rate and the ratio of aared
ox
at the interface will
As we have seen here, it is necessary to improve the
deviate from the ratio given by the Nernst equation for
ratio of faradaic to capacitive currents IIcf if very low analyte
this potential. Then the electrochemical system has to be
concentrations have to be determined. We shall now see regarded as more or less irreversible. One can phrase this
that all developments of voltammetric analysis techniques also as follows: the current is the observable which tells
can be seen as a long march to improve the ratio IIcf . us that an electrochemical reaction proceeds. If that cur-
rent is smaller than expected, the reaction is obviously not
proceeding at equilibrium and thus not reversible. Fig-
Electrochemical reversibility and irreversibility ure 7 illustrates this using a rate scale.
For voltammetric analysis, it is important to note that
In the following parts, we will need to refer to the the rate of charge transfer vct, and the rate of mass
reversibility or irreversibility of electrochemical reactions. transport vmt can be, in certain limits, changed by pur-
Therefore, some basic information needs to be given, pose. The transport rate can be changed by the hydro-
which relates to the kinetics of electrode reactions. (A more dynamic conditions (rate of stirring the solution, rate of
detailed discussion is given in [12] ). rotating the electrode, drop time of the DME, etc.). The
For an electrode reaction to proceed, the educt has to rate of charge transport can be only changed by changing
be transported to the interface, and the product has to be the chemistry (electrocatalysis, see later). From this fol-
transported away from the interface (cf. Figure 6). At the lows that the characterization of an electrochemical sys-
interface, the charge transfer occurs with the rate vct. The tem as reversible or irreversible, is nothing absolute, but it
overall rate of the electrode reaction can be limited (i) by depends on the experimental conditions. We will come
the mass transport of educt to the electrode, (ii) by the back to this at a later stage.

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17 Page 8 of 24 ChemTexts (2015) 1:17

Fig. 7 The relation of the rate


of charge transfer vct to the rate
Metal Solution
of mass transport vmt decides
about the reversibility of an
electrochemical system. When vct vmt
the charge transfer (vct) is faster
), the
than the transport (vmt  ratio charge transfer transport of educts from bulk to the electrode
aox
of surface activities ared interface
corresponds to the electrode
potential E given by the Nernst and of products from the electrode to the bulk
equation and the system is
aox
electrochemically reversible.
When the transport is faster than ared interface
the charge transfer, the Nernst
equation is not obeyed and the
system is electrochemically
irreversible vct vct vmt

Electrochemical Reversibility Electrochemical Irreversibility


(quasi reversibility

RT a quasi irreversibility) RT a
E E A/B ln ox E E A/B ln ox
nF ared interface
nF ared interface

The early times of direct current polarography


with the dropping mercury electrode

As already mentioned, the first voltammetric technique for


20-50 µm
analytical application was polarography, invented by Jar-
oslav Heyrovský (1890–1967), who has received for this the
Nobel Prize for Chemistry in 1959. Heyrovský used a glass capillary

dropping mercury electrode (DME) as working electrode.


The DME consists of a glass capillary (about 10 cm length,
0.5 cm outer diameter, 20–50 lm inner diameter) which is
fitted to a tube connecting it to a mercury reservoir which
was placed about 50 cm above the level of the glass capil-
lary orifice, where the mercury constantly drops out (Fig. 8). mercury drop

Depending on the inner diameter of the glass capillary and


the height of the mercury reservoir (i.e., the height of the Fig. 8 The orifice of the glass capillary with a mercury drop
mercury column), the lifetime of the mercury drops (the
time they hang at the orifice) may vary between some
fractions of a second up to minutes, but normally 1–5 s. The cell as auxiliary electrode. The latter has the advantage that
mercury droplet is connected to the electrochemical circuit it has a rather constant potential when the electrolyte
by a platinum wire dipping in the mercury reservoir. This solutions contain halide ions, like chloride. The measuring
kind of free dropping mercury electrodes is now obsolete equipment was assembled from a lead–acid battery (as
and was substituted by a new generation of mercury elec- voltage source), a resistor wire, and a mirror galvanometer
trodes, which allow controlling the outflow of mercury from for current measurements. The resistor wire was coiled
the capillary [see further down the paragraph ‘‘The Multi- around an insulating cylinder that rotated driven by a
Mode electrode (static mercury drop electrode)’’]. clock-work, so that a metal contact moved along the
Heyrovský used a two-electrode cell with the DME as resistor wire as to vary the applied voltage. Coupled with
working electrode and a mercury pool on the bottom of the the cylinder holding the resistor was a cylinder holding

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ChemTexts (2015) 1:17 Page 9 of 24 17

photographic paper (containing light-sensitive silver E


halides), so that the light beam of the galvanometer could
‘‘write’’ the measuring curve by passing through a long slit
of the housing. The entire instrument, called polarograph,
Eend dE
was the first self-recording analytical instrument. Figure 9
const.
shows a schematic drawing of the instrument. The linear dt
function of electrode potential versus time used in this kind
of polarography (voltammetry) is shown in Fig. 10. This
technique was called direct current polarography (DCP) [or
now, more generally, linear scan (or sweep) voltammetry
(LSV)].
The curves recorded with such polarograph showed
characteristic current oscillations due to the dropping out of
the mercury: during each drop life the current grows, and Estart
abruptly decreases when the drop falls down, because the
next drop at the orifice is substantially smaller. This hap-
t
pens both with the capacitive and the faradaic currents.
When ions or molecules are present in the solution, which Fig. 10 Potential versus time dependence for direct current polarog-
can be reduced or oxidized, wave-like current signals are raphy (voltammetry)
recorded. Figure 11 shows a historical curve with the
waves of several metal ions. For a better understanding of
polarographic curves, we shall use the modern notation,
i.e., drawing the potential axis from negative potentials on
the left side to positive potentials of the right side, and
giving reduction currents with a negative sign, and oxida-
tion currents with a positive sign.
At a DME, the surface area of the mercury drop grows
proportional to t2/3 (t is time). This follows because the
outflow of mercury is constant and the drop has the shape
of an almost perfect sphere. The faradaic current at a
growing drop is proportional to t1/6, when it is limited by
diffusion only (cf. Fig. 12). This proportionality was
derived by Dionýz Ilkovič, a coworker of Heyrovský. The
capacitive current at a growing mercury drop is propor-
tional to t-1/3, i.e., the capacitive current drops during the
life of a drop, whereas the faradaic current grows (see
Fig. 12). When the current is continuously measured dur-
ing the entire life time of the drop, it is obvious that the
sum of both currents has a large capacitive contribution in
the early period of drop life, and a relative small capacitive
contribution at the end of the life time. This sparked the
idea to measure the current only during a relative short
time period at the end of the drop life (Fig. 13): the result is
that the measured current will then have a more favourable
Fig. 9 Scheme of a Heyrovský polarograph: AB is the resistor wire ratio of IIcf . This was the first instrumental approach to
coiled around a cylinder. C is the sliding contact, F is the housing of discriminate the capacitive current in a voltammetric
the cylinder with the photographic paper, G is the mirror of the
galvanometer, L is the light source, N is the nitrogen inlet for
measurement. The technique is called ‘‘current sampled
deaerating the solution (because oxygen must be removed as it is polarography’’. Normally, the average current measured
reducible and would produce undesirable currents), K the glass during those time intervals at the end of each drop will
capillary, R is the circuit to connect the galvanometer, S is the slit produce one data point, so that the entire polarogram
through which the light beam of the galvanometer passes to the
consists of a series of data points.
photographic paper. As illustrated, the glass capillary was connected
via a tube with the mercury reservoir. Reproduced with permission Figure 14a shows schematically the polarogram of an
from [13] acidic solution when using a DME (the oscillation due to the

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17 Page 10 of 24 ChemTexts (2015) 1:17

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

drop life time t drop life time t


Fig. 12 Dependence of the faradaic and capacitive currents on time Fig. 13 Current sampling at a growing mercury drop for discrimi-
during the life time of a growing mercury drop nating the capacitive current

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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ChemTexts (2015) 1:17 Page 11 of 24 17

(a) I The long march to improve the ratio of faradaic


2Hg Hg 22 + 2e
to capacitive currents

The introduction of the current sampling technique to


polarography with the DME allowed to decrease the
detection limit from about 10-5 mol L-1 to around 5 9
10-6 mol L-1. The next important steps in decreasing the
E
Potential window for measurements
detection limits have been achieved (i) thanks to instru-
mental developments of the measuring techniques, (ii)
thanks to electrode developments, and (iii) thanks to inge-
nious chemical ideas. Without caring for the historical
pathways, we will briefly discuss the various approaches
2H + 2e H2 here. Figure 15 shows a classification of the different
approaches.

The Multi-Mode electrode (static mercury drop


(b) I
electrode)
2Hg Hg 22 + 2e

An important idea was to exchange the continuously dropping


mercury electrode (DME), where the surface area continu-
E1/2 ously changes (dAdt ¼
6 0) and prompts rather large capacitive
currents, by an electrode with an intermitting dropping. This
E
electrode operates with a valve that controls the outflow of
Ilim mercury in such way that a drop is quickly formed and then
hangs for a fixed time, until it is dislodged and a new drop is
A + ne B formed. Figure 17 shows the dependence of surface area on
time for a train of drops. Such electrodes are sold under the
2H + 2e H2 name Multi-Mode Electrode (Metrohm) (see Fig. 16), Static
Mercury Drop Electrode (Princeton Applied Res.), Controlled
Fig. 14 a Schematic drawing of a polarogram showing the base Growth Mercury Electrode (BASi).
currents in a acidic solution using a DME. b Polarogram of the same
solution, when a reducible compound A is present in the solution The basic idea of this electrode has been published by
Gokhshtein [17], a Russian scientist, already in 1961, but it
needed some decades and electronic progress to make a
decreasing electrode potential because the potential accel- commercial system. As Fig. 17 shows, each drop is hang-
erates the reduction. The potential acts like an increasing ing for a certain period of time having a constant surface
activation energy. However, the current grows only up to a area. If a measurement is made during that time span, it has
limiting value (Ilim) because each mercury drop is exposed no contribution of dA dt to the capacitive current, as this
to fresh solution with the bulk concentration of A, and the differential is zero. However, if a linear function of elec-
diffusion layer (see Fig. 4) grows during each drop life to trode potential versus time (Fig. 10) is still used, there is
the same thickness. The two effects (i) increasing of cur-
also still the capacitive current caused by dE dt , as this is not
rent magnitude with decreasing potential, and (ii) diffusion
zero. If one likes to reduce that capacitive current, a
limitation result in a current wave. This is typical for
staircase potential ramp (Fig. 18) has to be used. This kind
electrodes with a continuous mass transport towards the
of voltammetry (polarography) is called staircase voltam-
electrode surface, and the resulting voltammograms are
called steady-state voltammograms (polarograms). At half- metry (polarography). When potential steps where dE dt ¼ 0
height of the wave, there is a turning point that is called the are synchronized with the periods of drop life where
half-wave potential. This is the qualitative parameter dA ¼ 0, in principle both sources of capacitive currents are
depending on what compound is reduced (or oxidized). In dt
suppressed. This is only true to some (although large)
case of electrochemical reversible systems, it is directly
extent, because the stepwise growth of potential also means
related to the standard potential (respectively, formal
potential [15, 16] ) of the compound. In rare cases, it can be that dE
dt is very large from one step to the other (the
almost equal to the standard potential. potential rise happens with a rate around 1 MV s-1). With

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17 Page 12 of 24 ChemTexts (2015) 1:17

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

Fig. 16 The Multi-Mode


electrode of the Metrohm
company. a photo, b cut. This
figure has been made using
figures provided by Deutsche
Metrohm GmbH & Co. KG

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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ChemTexts (2015) 1:17 Page 13 of 24 17

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

Many different pulse techniques have been developed.


Among them differential pulse voltammetry (DPV) is the
most important and the most widely applied [18, 19].
The main idea realized in DPV is to subtract from the
current measured at the end of a potential step (cf.
drop life time t Figure 20) the current measured before the step. For this,
potential pulses are superimposed to a staircase ramp
Fig. 17 The surface area as function of time for a Multi-Mode
electrode (static mercury drop electrode) (Fig. 20)
The potential–time function shown in Fig. 20 (right
side) offers the possibility to subtract the current shortly
E
before the pulses from the current sampled at the end of the
pulse. This is depicted in Fig. 21. Each pulse will produce
Eend one measuring point according to the equation
dE
const. In2  In1 ¼ DIn;dp ð13Þ
dt

with n being the number of the individual pulse. The dif-


Estep
ferential pulse voltammogram consists of discrete DIn,dp
data plotted as a function of potential. This curve resembles
tstep the first derivative of the direct current voltammogram
(polarogram), but it should be emphasized that it is NOT
simply the mathematical first derivative. Figure 22 shows a
Estart
schematic differential pulse voltammogram. The peak
potential Epeak of the signal is almost equal to the half-
t wave potential E1/2 in DCP (deviates only due to the pulse
Fig. 18 Staircase potential ramp for staircase voltammetry
amplitude Epulse).

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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17 Page 14 of 24 ChemTexts (2015) 1:17

Fig. 20 Left side: superposition


E pulses
E
of a staircase ramp with
potential pulses. Right side: the
potential–time function
resulting from this
superposition. Typical
parameters are: pulse duration
tpulse = 200 ms, pulse height:
Epulse = 20 mV, staircase ramp:
tstep = 500 ms, Estep = 5 mV

tpulse

Epulse
Estep
staircase ramp
tstep

t t

Fig. 21 Potential–time function E


in differential pulse
voltammetry. On the right side,
the time periods Dt1 and Dt2 for
current measurements are
shown and also the faradaic and
capacitive currents before the If
pulse (dashed lines) and at the
end of the pulse (full lines).
Note that they have opposite
signs because the potential
foregoing potential steps go in Ic
opposite directions Ic
If
Δt1 Δt2

Differential pulse voltammetry is so popular because it Alternating current voltammetry (ACV)


is possible to determine electroactive compounds down to
10-7–10-8 mol L-1. Here it is appropriate to explain that Alternating current techniques are attractive because one
in voltammetric methods of analysis, detection limits are can measure selectively only the capacitive or only the
usually given in mol L-1 because the currents depend on faradaic currents. When an alternating voltage, e.g. a
molar concentrations due to diffusion. Therefore, the sinusoidal voltage, is superimposed to a linear voltage
nature of the electroactive compounds is less important ramp (or a staircase ramp), the voltage oscillations give rise
(the different numbers n of electrons involved in the to an alternating current component. This alternating cur-
electrode reaction have only a marginal effect on detec- rent can be separated from the direct current, which results
tion limits). from the linear voltage ramp. Measuring the complete
Despite differential pulse voltammetry, so-called normal alternating current (after rectification) is of no benefit for
pulse voltammetry and reverse-pulse voltammetry are the detection of faradaic signals, because the ratio IIcf is even
other pulse techniques [18, 19]. The latter techniques are worse (smaller) than in direct current measurements.
very suitable for studies of electrode mechanisms, but less However, there are two possibilities to increase Ic;ac
If;ac
, i.e.
for analytical purposes.

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ChemTexts (2015) 1:17 Page 15 of 24 17

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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17 Page 16 of 24 ChemTexts (2015) 1:17

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

123
ChemTexts (2015) 1:17 Page 17 of 24 17

Γads

2 µA

First harmonic
‒0.5 ‒0.6 ‒0.7

0 Potential vs. Epzc


0.2 µA

Ic
Second harmonic

0 Potential vs. Epzc


Third harmonic
Fig. 26 Top: dependence of surface concentration Cads of an
0.02 µA adsorbed compound on electrode potential. Bottom: capacitive
currents resulting from adsorption–desorption at potentials where
dCads
dE has maxima

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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17 Page 18 of 24 ChemTexts (2015) 1:17

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

Fig. 27 Scheme of the


potential–time function and the
current versus potential curve
for the anodic stripping
voltammetry of copper ions

123
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:

123
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

Conclusions: the advantages and disadvantages


Mo 6 Solution of voltammetric techniques of analysis
Electrode
This lecture text aimed at demonstrating that voltammetric
techniques (VTs) of analysis have one central challenge,
i.e., the discrimination of capacitive currents to achieve
most favourable ratios of the faradaic to capacitive cur-
Mo5 rents. Only rarely, capacitive currents are used for analyt-
ical determinations, in which cases the faradaic currents
Distance from electrode surface have to be discriminated.
Combinations of techniques, each discriminating
Diffusion layer
capacitive currents, are especially effective to achieve low
detection limits. Examples of such combinations are:
Concentration
(a) Preconcentration techniques (electrochemical or
6
Mo Solution
adsorptive) ? differential pulse (or square-wave, or
phase-sensitive ac techniques) ? static mercury
Electrode electrode (or mercury film electrode).
(b) Preconcentration techniques (electrochemical or
adsorptive) ? catalytic currents ? differential pulse
(or square-wave, or phase-sensitive ac tech-
niques) ? static mercury electrode (or mercury film
Mo5 electrode) [33].

Distance from electrode surface


Table 2 shows examples of applications of VTs for the
determination of elements and compounds.
Diffusion and reaction layer
Speaking about the advantages and disadvantages of
Fig. 28 Concentration profile of Mo6? and Mo5? at an electrode in VTs, one has to compare them with spectroscopic, chro-
the absence of chlorate ions (top graph), and in its presence (bottom matographic, electrophoretic, and radiochemical methods,
graph) to name just the most important. Then, the following fea-
tures of VTs should be noted:
(i) VTs can be applied for the quantitative
determination of inorganic and organic spe-
cies (ions and molecules). They are best
suited for species which can be either oxi-
dized or reduced on electrodes.
(ii) There are also possibilities (e.g. tensammetry)
to determine species, which—under the
experimental conditions—do not undergo
Fig. 29 Catalytic cycle showing the regeneration of Mo6? by electron transfer reactions.
oxidation of Mo5? with chlorate ions

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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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