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Feature Article

Eighty Years of Polarography ± History and Future

JirœÌ Barek, JirœÌ Zima
UNESCO Laboratory of Environmental Electrochemistry, Department of Analytical Chemistry, Charles University, 12843 Prague 2,
Czech Republic;
* e-mail: Barek@natur.cuni.cz

Received: June 26, 2002

Final version: August 19, 2002

Abstract
Since 1922, when Professor Jaroslav Heyrovsky¬ carried out his pioneering experiment with a dropping mercury
electrode, polarography showed remarkable ability to adjust to ever increasing demands on the sensitivity and
selectivity and up to now mercury electrodes are among the best sensors for electroanalytical measurements. The aim
of this contribution is to show both the historical development of these techniques and their presence and possible
future developments and to show that even today in certain cases polarographic and voltammetric techniques on
mercury electrodes can successfully compete with modern separation and spectrometric techniques.

Keywords: Polarography, Voltammetry, Mercury electrodes, History

Dedicated to the Memory of Professor Jaroslav Heyrovsky¬ on the Occasion of the 80th Anniversary of the
Invention of Polarography.

1. Introduction ± The method must be competitive with existing analytical

Eighty years ago, on February 10, 1922, Professor Jaroslav
Heyrovsky¬ carried out his pioneering experiment with a
dropping mercury electrode from which polarography
gradually evolved. Since then, polarography became a
mature analytical method capable to adjust to ever increas-
ing demands on the sensitivity and selectivity and we believe
that up to now mercury electrodes are among the best
sensors for electroanalytical measurements [1]. Limits of
determination gradually decreased from 10 5 M in the case
of classical polarography [2], through 10 7 M for differential
pulse polarography [3] to 10 11 M for adsorptive stripping
voltammetry [4]. History of the development of the polaro-
graphic method from the birth of Professor Jaroslav
Heyrovsky¬ in 1890 until the Nobel Prize award in 1959
was recently described in detail [5]. Nevertheless, we think it
is useful to remind the most important milestones in the
development of polarography and voltammetry on mercury
electrodes and to remind that even today in certain cases
polarographic and voltammetric techniques on mercury
electrodes can successfully compete with modern separa-
tion and spectrometric techniques in certain fields of trace
analysis.
Several conditions must be fulfilled for a practical
application of any new analytical method:
± Appropriate theory must be developed
± Reliable instrumentation must be commercially available
± Simple and reliable procedures must be developed and
validated
± An analyst must be properly informed about the techni-
que
methods in terms of cost
(both investment and running), analytical figures of merits
(e.g., limits of determination, linear dynamic range, repeat-
ability and reproducibility) and other important parameters
(e.g., selectivity, robustness, etc.).
In this article we would like to stress the role of Professor
Jaroslav Heyrovsky¬ in this process and to discuss the
position of polarography and voltammetry at mercury
electrodes from these points of view.
2. History
On February 10, 1922, Professor Heyrovsky¬ recorded the
first dependence of the current flowing through the drop-
ping mercury electrode on the applied potential and drew a
corresponding graph in his laboratory notebook which can
be considered as the first polarogram (see Fig. 1a). If we
transform the axis to the nowadays-used form (see Fig. 1b),
we can easily recognize the first and second wave of oxygen
and the decomposition of the base electrolyte. He used a
quite simple circuit with a mirror galvanometer (see Fig. 2).
However, he soon recognized that point-by-point measure-
ments and plotting of current-voltage curves were tedious
and time consuming and together with M. Shikata con-
structed a new instrument [6] (which was later called a
polarograph, see Fig. 3) that recorded photographically
such a curve in several minutes. The development of modern
polarographic and voltammetric methods on mercury
electrodes proceeded later in three parallel lines:

Electroanalysis 2003, 15, No. 5 ± 6 ¹ 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1040-0397/03/0503-0467 $ 17.50+.50/0
468
Fig. 1. The first recorded I ± E curve copied from Professor
Heyrovsky¬×s laboratory notebook (a) and transformed into the
nowadays used form (b).
± Development of mercury electrodes which proceeded
from classical dropping mercury electrode [7] through
mercury streaming electrode [8], hanging mercury drop
electrode [9], static mercury drop electrode [10], mercury
film electrode [11], mercury amalgam electrodes [12],
mercury microelectrodes, chemically modified mercury
electrodes [13], controlled growth mercury electrodes
[14 ± 18] and contractible mercury drop electrodes
[17,18]. This process initiated by Professor Heyrovsky¬
resulted in commercially available reliable mercury
electrodes suitable for nanomolar and subnanomolar
concentrations. Further progress in this field can be
documented by the above mentioned articles of Novotny
and Kowalski and by papers of Gutz on versatile
automatic mercury drop electrode [19, 20].
± Development of measuring techniques that proceeded
from classical DC polarography [2], through oscillopolar-
ography [21], Kalousek×s switcher [22], AC polarography
[23], tast polarography [24], normal pulse polarography
[25], differential pulse polarography [26], square-wave
Electroanalysis 2003, 15, No. 5 ± 6
J. Barek, J. Zima
voltammetry [27], cyclic voltammetry [28], anodic strip-
ping voltammetry [29], adsorptive stripping voltammetry
[30], convolution techniques [31, 32] and elimination
methods [33, 34]. Again, the initial impetus given by
Professor Heyrovsky¬ played a decisive role in this process
resulting in the decrease of the attainable limit of
determination from 10 5 M for DC polarography through
10 7 M for pulse techniques to 10 11 M for stripping
methods.
± Development of preconcentration techniques on the
surface of mercury electrodes enabling a substantial
increase of sensitivity which proceeded from anodic
stripping voltammetry and cathodic stripping voltamme-
try to adsorptive stripping voltammetry.
The role of Professor Heyrovsky¬ in the development of
these methods cannot be overestimated. According to
Zuman [35] the main contribution of Professor Heyrovsky¬
consists in:
± Recognition of the importance of potential and its
control;
± Recognition of analytical opportunities offered by meas-
uring the limiting currents;
± The introduction of dropping mercury electrode as an
invaluable tool of modern electroanalytical chemistry.
He also pointed out that the position of the wave on the
potential axis is characteristic of the reduced species and can
be used for qualitative analysis and last but not least he was
an enthusiastic propagator of polarography capable to
explain the method in simple terms, which helped its
acceptance as an acknowledged analytical method in
routine laboratories. He continually explained both the
theoretical and practical possibilities offered by this techni-
que and the application of polarography in practical analysis
and for solution of practical problems by lectures, parti-
cipation at meetings, visits to foreign centers of research,
invitation of guest-workers from all over the world into his
laboratories, and by publication of original papers, reviews
and monographs. Furthermore, he created in Prague a
center of polarographic research and created a scientific
school, which substantially influenced both electrochemis-
try and analytical chemistry. Professor Heyrovsky¬ person-
ally contributed to and initiated the development along all
three above-mentioned lines and played a decisive role in
fulfilling the above-mentioned conditions for practical
application of polarography. The Nobel Prize award in
1959 for polarography as an analytical method was thus very
well deserved.
3. Present State
It is necessary to admit that routine applications of polaro-
graphic and voltammetric methods on mercury electrodes
are not too frequent at present. This is caused by fast
developments of modern spectrometric and separation
techniques, by concerns about mercury toxicity, by the
Polarography
Fig. 2. Scheme of the first equipment for measuring I ± E curves at a dropping mercury electrode.
lack of properly validated methods and by a lower activity of
producers of electroanalytical instrumentation as compared
with producers of spectrometric and separation instruments.
The dwindling number of university teachers involved in
electroanalytical research plays a negative role as well as
shrinking position of electroanalytical methods in the
curriculum of most universities. Nevertheless, we strongly
Fig. 3. Scheme of the first polarograph.
469
believe that polarography and voltammetry on mercury
electrodes should be seriously considered in the process of
choice of the best method for the determination of a given
compound in a given matrix for the following reasons:
± Extremely broad linear dynamic range and low limit of
determination from 10 7 M for pulse techniques down to
10 11 M for stripping techniques;
± Diversity of determinable analytes (inorganic, organic,
metalloorganic);
± High speed;
± Easy automation;
± Low running and investment costs;
± Reasonable selectivity especially in combination with
preliminary separation and sample cleanup using, e.g.,
liquid-liquid extraction, solid phase extraction, thin layer
or column chromatography;
± Electroanalytical methods present an independent alter-
native to prevailing spectrometric or separation methods
which is important in those cases where the analytical
results should be ™beyond reasonable doubts∫ (speaking
in law terms) which, according to many regulations,
requires the application of several independent analytical
methods;
± Thousands of reliable polarographic or voltammetric
methods are available in scientific journals, monographs,
tables and databases and around 300 new polarographic
methods are published every year during last ten years
confirming that polarography can be a viable alternative
to other instrumental methods.
Mercury electrodes are according to our opinion the best
sensors for voltammetric measurements for the following
reasons:
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470
± Easy renewable surface eliminates or minimizes prob-
lems with electrode passivation and fouling;
± Broad potential window enables reaching negative po-
tentials up to 2.5 or even 3 V, which makes mercury
the best available material for the determination of
electrochemically reducible analytes.
Existing objections to the use of mercury in analytical
laboratories based on its toxicity are not rational because
mercury is practically innocuous at room temperature. (Toxic
organomercury compounds are not formed during polaro-
graphic and voltammetric measurements). Moreover, the
amount of mercury consumed in analytical laboratories can
be profoundly decreased by applying hanging mercury drop
semi micro- and microelectrodes. Alternatively, completely
non-toxic solid amalgam electrodes can be used [12, 36]. Solid
electrodes (noble metals, various types of carbon, etc.) are not
in general suitable for cathodic reduction and thus they
cannot compete with mercury in this region. Carbon paste
electrodes [37] offer the advantage of easy surface renewal,
however, their application in cathodic region is also limited.
Thus only bismuth film electrodes [38 ±40] seem to be a
promising alternative to mercury and other solid electrodes
for direct cathodic electrochemical detection especially of
organic compounds.
Unfortunately, electroanalytical methods are not too
frequently considered as methods of choice nowadays and
spectrometric and separation methods are quite frequently
applied notwithstanding whether they are really the best
methods for a particular case. For certain, admittedly not too
frequent cases, modern polarographic and voltammetric
techniques are really the best method and quite frequently
they are among the ™fit for the purpose methods∫. The
polarographic and voltammetric methods developed in our
UNESCO Laboratory of Environmental Electrochemistry
for the determination of sub micro and subnanomolar
concentrations of selected chemical carcinogens [41], ni-
trated pesticides or growth stimulators [42] and dyes [43] can
serve as example.
4. Future
According to our opinion mercury electrodes will be
successfully applied in the following fields:
± Mechanistic studies (especially of organic compounds)
which is important for basic research, structure-activity
relationship investigation, study of supramolecular inter-
actions etc. Thus obtained information can give us a useful
clue for the study of biological redox processes and the
transformation of investigated substances in ecosystem
and provide optimum conditions for both electroanalysis
and electrosynthesis.
± Trace metal determination and speciation where polar-
ography and voltammetry at mercury electrodes can play
a very important role in bioavailability studies and in soil
and water analysis.
Electroanalysis 2003, 15, No. 5 ± 6
J. Barek, J. Zima
± Trace determination of organic substances where modern
polarographic and voltammetric techniques can success-
fully compete with other instrumental methods in the
field of pharmaceutical analysis (both the determination
of selected drugs in pharmaceutical preparations and
their traces or metabolites in body fluids (whole blood,
plasma, urine), food analysis (determination of residues
of selected pesticides or growth stimulators), forensic
analysis (determination of traces of gun powder or
explosives), toxicology (determination of selected toxic
substances in the general or working environment and
their metabolites in body fluid, biological monitoring of
the exposition to toxic substances etc.) and environmental
analysis (determination of selected anthropogenic pollu-
tants, pesticides, genotoxic substances, chemical carcino-
gens, ecotoxic dyes etc. in rain, surface, river, sea and
drinking water and in other constituents of the environ-
ment).
± Voltammetric immuno assays in which we can use
polarographically active functional groups (e.g., nitro
group) or ions instead of radioactive markers thus
avoiding the work with radioactive isotopes and decreas-
ing the cost of the determination. Combination with
immunoassays would improve the selectivity of those
voltammetric determinations.
± Metal speciation where mercury electrodes can be a
useful tool providing information about the oxidation
state of the metal and the possibility to determine the free
metal and metal ion in different individual complexes.
± Combination of mercury electrodes (hanging mercury
drop or mercury film) with flow injection analysis or
HPLC which can substantially increase either the
throughput or the selectivity of these determinations.
HPLC with electrochemical detection increases the
selectivity as compared, e.g., with UV detection because
not all UV absorbing substances are polarographically
active.
± Screening methods that can represent a cost effective
alternative. The absence of a polarographic or voltam-
metric wave or peak and its appearance after a standard
addition can be a sufficient proof of the absence of the
analyte in the test sample at the corresponding concen-
tration level. However, in the presence of the signal the
presence of the analyte should be confirmed by some
other, more sophisticated but obviously more expensive
technique (HPLC-MS etc.). Taking into consideration the
fact that substantial proportion of samples does not
contain the sought analyte, this approach can substan-
tially decrease the cost of monitoring projects.
Mercury electrodes can play a useful role in the nucleic acid
research [44 ± 51]. AC voltammetry at hanging mercury
drop electrode can be used to detect small damage of DNA
[49] in solution or the electrode modified with intact
supercoiled DNA can be used as a sensor to detect the
DNA damaging agent (e.g., hydroxyl radical) in the
environment. The amount of DNA required for the analysis
is below 10 ng and the method is faster than the currently
Polarography
applied gel electrophoresis. Both conventional and adsorp-
tive transfer stripping voltammetry can detect sensitively
small damages to the DNA double helix induced by
relatively low doses of ionizing radiation [50]. Recently
reported [48] application of adsorptive stripping potenti-
ometry to the reductive detection of nucleic acids at mercury
electrodes allows the quantitation of ss DNA or t RNA in
the presence of ds DNA, and offers new possibilities for
electrochemical studies of DNA structure and interactions.
Mercury film plated on a glassy carbon electrode can be also
used for the analysis of nucleic acids and nucleic acid-
modified mercury electrodes appears suitable for various
applications [47]. A new technology in which DNA is
hybridized at a hybridization surface and the hybridization
is detected at the detection electrode has been proposed
[51]. This technology significantly extends the choice of
hybridization surfaces and detection electrodes and enables
specific detection of the hybridization of polyribonucleo-
tides, m RNA, oligodeoxynucleotides, and a DNA PCR
product. This aproach opens new possibilities in the devel-
opment of the DNA hybridization sensors, including
utilization of catalytic signals in nucleic acid determination
at mercury electrodes. A great progress in the development
of electrochemical sensors for DNA hybridization and
DNA damage achieved in recent years suggests that these
sensors may soon become important tools in medicine and
other areas of practical life of the 21st century [46].
Modern polarographic and voltammetric methods are
undeservedly perceived as less selective, but they offer
certain degree of selectivity because not all constituents of
most samples are polarographically active. This can be
demonstrated by simple determination of nitrated polycy-
clic aromatic hydrocarbons in the presence of parent
polycyclic aromatic hydrocarbons, which do not interfere,
by the determination of drugs in tablets, injection liquids, or
body fluids, by metal speciation etc. Polarographic deter-
minations can be carried out in certain cases in the presence
of colloid particles, solids and surface-active substances.
Moreover, the selectivity of modern polarographic and
voltammetric methods can be further increased by their
combination with a preliminary separation using liquid-
liquid extraction, solid phase extraction, and thin layer or
column chromatography.
The improvements in electronics, computers and instru-
mentation, the availability of increasingly sophisticated and
user friendly software together with the increasing reliabil-
ity of commercially available mercury electrodes of various
types and with advancement in theory and the development
of new types of potential programs and new types of the
treatment of the current responses could result in a
renaissance of polarographic methods in coming years
because of increasing importance of economic considera-
tion. However, the most important impetus for further
development and more frequent practical applications
would be the enthusiasm of innovative electrochemists.
471
5. Acknowledgements
J. B. thanks the Grant Agency of the Charles University for
financial support (Grant no. 253/2001/B-CH/PrF) and J. Z.
thanks the Czech Ministry of Education, Youth and Sports
for financial support (Research project 113100002).
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