Polarography

Purpose: Polarography is the measurement of the current that flows in solution as a function of an
applied voltage. The actual form of the observed "polarographic wave" depends upon the manner in
which the voltage is applied and on the characteristics of the working electrode. The working
electrode is often a Dropping Mercury Electrode (DME), and the polarographic wave thus has
oscillations imposed on it from the variations in mercury drop size. This experiment employs two
methods of applying the voltage, a linear sweep (DC) and a differential pulse. The working electrode
employed is called a Static Mercury Drop Electrode (SMDE), and provides a more sensitive
measurement of the faradaic current than the more traditional DME. The contrast between it and a
standard DME is illustrated in the figure below. The SMDE is used in this experiment to obtain DC
and differential pulse polarograms of various metal ions in solution, illustrating the abilities of
polarography for qualitative (metal species identification) and quantitative analysis.

Consult your textbook and the Student Instructions for further information on the principles of
polarography and for representative plots of polarographic (voltammetric) waves obtained through
the various voltage application methods.

Equipment: PARC model 174A polarographic analyzer and 303A SMDE.

Reagents:

• 2.0 M KCl stock solution, provided.

• 0.2 M KCl prepared from stock enough to last entire experiment, approximately 2 liters.
• Triton X-100 surfactant, 0.2%, provided
• Metal standards, the following 100 mM stock solutions are provided: Cd+2, Ni+2, Co+2, Pb+2, and
Zn+2
• Nitrogen, oxygen free

Samples: The instructor will supply the following:

• qualitative mixture
• quantiative unknown (single element)

JAROSLAV HEYROVSKY AND POLAROGRAPHY

Michael Heyrovsky
The Jaroslav Heyrovsky Institute of Physical Chemistry
Academy of Sciences of the Czech Republic
182 23 Prague 8, Czech Republic
(January, 2005, Last revision: March, 2010)

Simple principle of polarography is the study of solutions or of electrode processes by means of electrolysis with
two electrodes, one polarizable and one unpolarizable, the former formed by mercury regularly dropping from a
capillary tube. An objective document of polarographic study is the polarographic curve, that is, a curve
visualizing the processes occurring in the course of electrolytic polarization of the dropping mercury electrode. In
the case of the common voltage-controlled (or, with three-electrode systems, potential-controlled, or
"potentiostatic") electrolysis, the polarographic curve is a current-voltage (or current-potential) curve showing the
 dependence of the current, passing through the system, on the voltage applied to the electrodes, or on the
electrode potential of the dropping electrode. In the case of the current-controlled ("galvanostatic") electrolysis, it
is the time-change of potential of the dropping electrode, which is displayed by the curve. The dropping mercury
electrode keeps the interface always fresh between its constantly renewed surface and the solution, independent of
the processes that were taking place at previous drops, and thereby the measurements taken with it are perfectly
reproducible. Polarography was created in 1922 when Jaroslav Heyrovsky used dropping mercury electrode for
measuring polarization curves. Encouraged by the results, he dedicated the rest of his life to the development of
the method he thus initiated.

Once the recording of polarization curves was made automatic, the relative simplicity of the apparatus and the
rapidity of gaining results attracted attention of analytical chemists, and, especially after an exact theoretical
background was worked out, polarography has become and remains an appreciated and trusted method in
laboratories all over the world, thanks to the high reproducibility of the curves. Technical progress has continued
modifying the classical, original method to meet increasing requirements of science and technology; the latest
versions derived from the simple electrolysis with dropping mercury electrode belong to the most sensitive and
versatile methods of analysis. Jaroslav Heyrovsky received the 1959 Nobel Prize in Chemistry for his discovery
of polarography.

Electrochemistry at the beginning of the 20th century

In the course of the 19th century, electrochemistry was established as a

special branch of science and technology. Thanks to the work of
Humphry Davy and Michael Faraday, the basic theory and practice of
electrolysis became understood. Hermann Helmholtz and Walther
Nernst developed the concept of electrode potential and electrochemical
polarization; on that basis Max Le Blanc began using polarization
curves for the study of electrode processes whereby he coined the terms
"polarization voltage" and "decomposition voltage". Nernst, inspired by
the then successfully spreading spectral analysis, thought of introducing
its electrochemical analogy, and with his students and coworkers he
tried to gain polarization curves which would provide data for
qualitative and quantitative analysis of the electrolyzed species;
however, even with a variety of solid electrodes and using various ways
of polarization they were unable to achieve satisfactorily reproducible
results.

By preparing the dropping mercury electrode (Figure 1), C. F. Varley

and Gabriel Lippmann gave scientists an intricate problem to study; the
Czech physicist Bohumil Kucera was the first one to treat that electrode
not as a problem but as a research tool: he used the weight of drops
Fig. 1. Dropping mercury electrode as collected from that electrode for measuring surface tension of polarized
used by Bohumil Kucera. mercury. Briefly, such was the situation in electrochemistry when the
international clan of scientific workers was joined by Jaroslav
Heyrovsky.

Jaroslav Heyrovsky (1890-1967) and his life dedicated to

polarography

The early years

Jaroslav was born on the 20th of December 1890, into the family of Leopold
Heyrovsky, professor of Roman law at Charles University in Prague, then in
Fig. 2. Jaroslav Heyrovsky as a
student at the University College,
London (1911).
the Austro-Hungarian Empire. He had three elder sisters and one younger brother. The two boys showed keen
interest in nature from their childhood, the younger one later became one of the leading Czech entomologists,
while the elder one's preferred subjects in school were biology, mathematics, and physics (chemistry was not
taught at that time). When William Ramsay was distinguished by the Nobel Prize for chemistry in 1904 for his
discovery of rare gas elements, Jaroslav, strongly impressed, decided that in the future he would like to study
physical chemistry.

After the first year of Jaroslav's study at Prague University, as physical chemistry was not an independent subject
there, father Leopold agreed to support his son's continued studies at the University College in London (Figure 2),
where William Ramsay held the chair of general chemistry. There the Czech student had the privilege to attend
the great chemist's lectures. In 1913 Ramsay retired, succeeded by the electrochemist F. G. Donnan, who affected
decisively the scientific orientation of young Heyrovsky by suggesting to him as topic for Ph.D. thesis the
electrode potential of aluminum. For the experimental measurement, in order to avoid formation of passivation
layers on the aluminum surface, Donnan advised his student to use dilute aluminum amalgam slowly flowing out
of a capillary tube thus constantly renewing its surface. This acquainted Heyrovsky with the sphere of problems
which he was later facing in his work with the dropping mercury electrode.

Back home for summer holidays in 1914, caught by the outbreak of World War I, Heyrovsky was called up to
join the Austrian army and to serve in military hospitals as dispensing chemist and x-ray technician. This position
gave him the chance, in rare moments of leisure, to work on his dissertation "On the electroaffinity of aluminum",
and so in last days of the war, in the autumn of 1918, he could present himself, in military uniform and with a
completed dissertation, for a Ph.D. examination at Prague University. His examiner in physics on that occasion
was Professor Bohumil Kucera, who asked the candidate about the method of measuring surface tension of
polarized mercury by dropping mercury electrode. Heyrovsky, knowing Kucera´s work, was prepared for such
question, and the surprised examiner suggested that the student continue, after successful examination, his own
not fully accomplished research – to solve the so-called "Kucera's anomaly" of electrocapillary curves obtained
by the dropping mercury method.

The discovery of polarography

After the war, as a fresh Ph.D., Heyrovsky became assistant at the Department of Inorganic and Analytical
Chemistry at the Prague University, this time in the new Czechoslovak Republic. Following Kucera's instructions,
he started weighing drops of mercury collected in various solutions from the dropping mercury electrode under
different values of voltage applied to it with the negative pole of a voltage source, while the layer of mercury at
the bottom of the cell was connected to the positive pole. The measurements were very tedious: for each value of
applied voltage he had to count 100 drops falling into a small spoon submerged in the solution, to dry the
collected mercury, to weigh it exactly, to record the weight, to change the voltage by 10 mV, and to continue,
over the entire voltage range of 2 to 3 volts. A certain simplification was to measure drop-time, proportional to
the surface tension, under the assumption of constant rate of flow of mercury at various potentials. The drop-
weight-voltage, or drop-time-voltage curves had mostly the correct shape of the electrocapillary parabola, but
sometimes their round maximum was overlapped by a secondary sharp maximum – the Kucera's anomaly. In
some cases, Heyrovsky observed that the drop-weight, or the drop-time, remained constant over a certain voltage
range; it occurred to him that this might indicate passage of electrolytic current, and he decided from then on to
measure current, passing through the cell, in addition to the drop-weight or drop-time.
 In the afternoon of Friday, the 10th of February
1922, he connected a sensitive mirror
galvanometer, provided with a lamp irradiating
the mirror, to the electrolytic circuit with the
dropping mercury electrode dipping into 1 M
solution of sodium chloride (common salt), and
followed motions of the luminous spot, reflected
from the mirror of the galvanometer, on the
measuring scale (Figure 3). The instantaneous
current oscillated rhythmically according to the
regular growing and falling of the drops. After
the mean values of the current oscillations were
plotted as a function of the voltage applied to the
electrodes, the resulting polarization curve
showed two equally high steps of current
increase, about 0.8 V apart, and a final steep
increase of current out of scale, corresponding to
Fig. 3. Apparatus for measuring current-voltage curves in the highest value of 2.0 applied volts. In contrast
electrolysis with dropping mercury electrode. with the hitherto use of solid electrodes, this
curve turned out to be exactly reproducible. It
was the first polarization curve obtained with the dropping mercury electrode, this particular one visualized the
two-step electrolytic reduction of molecular oxygen dissolved from the air under atmospheric pressure in 1 M
solution of common salt. The height of the current steps was proportional to oxygen concentration in the solution,
and the position of the steps on the voltage scale appeared to be values characteristic of oxygen. Thanks to the
minute size of the mercury drops the amount of oxygen consumed in the electrolytic reaction was completely
negligible. Usefulness for analytical chemistry of the electrolysis with dropping mercury electrode appeared
straightforward. That day can be considered as the date of birth of the method, which later received the name
"polarography".

After the successful initial experiment, Heyrovsky continued a systematic

research of electrolysis, first with the dropping mercury cathode, as at the
beginning various reduction processes were studied, for which mercury, with
its highest hydrogen overpotential of all metals, offers the widest attainable
range of potentials in the negative direction. Later it was shown that even
oxidation processes can be followed, although limited by anodic dissolution
of metallic mercury; and in a relatively narrow positive potential range, the
dropping mercury electrode then can serve also as an anode. In April of
1922, Heyrovsky was appointed assistant professor in the newly established
Fig. 4. Masuzo Shikata and Jaroslav department of physical chemistry, and students as well as interested
Heyrovsky on the occasion of colleagues were readily joining him in his original research. His first account
Faraday Discussion in London of "Electrolysis with the dropping mercury cathode" was published in Czech
(December, 1923). in 1922, an English version appeared in the "Philosophical Magazine" in
1923. The latter article attracted the attention of a young Japanese scientist,
Dr. Masuzo Shikata, to the extent that he came to Prague in 1923 to learn the new method on the spot. In
November of the same year, Heyrovsky and Shikata attended the "General Discussion on Electrode Reactions and
Equilibria" of the Faraday Society in London, to which each contributed with communication on electrolysis with
dropping mercury electrode (Figure 4).
 The only drawback of the promising new method was the
cumbersome way of manual recording of the curves. This aspect
was discussed at length between Heyrovsky and Shikata, and on
the 30th of March 1924, a sketch was submitted to the workshop
of the physics department in Prague of an instrument for
automatic photorecording of current-voltage curves (Figure 5).
The result proved successful, and in a 1925 special issue of the
Dutch journal "Recueil des Travaux Chimiques des Pays Bas",
as part of a special series of eleven papers on "Researches with
the dropping mercury cathode", a paper was published by
Heyrovsky and his coworkers describing the new device of
Heyrovsky and Shikata. The paper was entitled "The
polarograph", meaning an instrument for recording the process
of electrolytic polarization. Although it was not specified in that
paper that the instrument should be used solely for
measurements with the dropping mercury electrode, the method
of electrolysis with that kind of electrode has gradually acquired
the name "polarography". The polarograph shortened the time of
recording polarization curves from hours to minutes and,
Fig. 5. Scheme of automatic measuring circuit moreover, it automatically provided an objective document of
with polarograph. exactly reproducible measurements. Thus, polarography brought
the fulfillment of the Nernst's idea of an electrochemical analogy
to spectroscopy (Figure 6). Moreover, polarographic analysis allowed determination of electroactive species in 10
µM concentration even in a minute volume of solution. This considerably spurred the further development and
the spreading of polarography. In 1925 Shikata left Prague for home, and in his luggage he carried one of the first
polarographs, which became the cornerstone of the Japanese polarographic school. Among other foreign scientists
who visited Prague, in order to learn polarography at the early stage and to introduce it in their own countries,
were Dr. Giovanni Semerano from Italy, then author of the very first textbook on polarography, and Dr. Wiktor
Kemula from Poland.

The first decade

In 1926 Heyrovsky became full professor, and polarography was

going to be the primary subject of research in his department of
physical chemistry. At that time, Heyrovsky and his friend, x-
ray spectroscopist Dr. Vaclav Dolejsek, were preoccupied with
the search for the new chemical element No 75; it appeared that
polarographic curves of certain manganese ores provided results
which could be ascribed to reduction of one of the oxidation
states of this new element. However, Heyrovsky has proven
with further polarographic experiments that, contrary to his
previous belief, the manganese ores did not contain element No.
75, and he conceded the discovery of the new element to W. and
I. Noddack, who called it "rhenium".

The problem of Kucera's anomaly was not forgotten: with

Fig. 6. "Polarographic spectrum" – curve of Kucera´s assistant, Dr. Rudolf Simunek, Heyrovsky showed that
polarographic reduction of seven different the pointed maxima on electrocapillary curves appeared with
cations. solutions with which similar maxima appeared also on
polarographic curves – commonly it occurred when oxygen
contained in the solution was reduced at the electrode. Later it was explained that both maxima were caused by
the streaming of the solution around the mercury drops when electrolytic processes, accompanied by changes of
 adsorption of the electroactive species, were taking place at the electrode – the streaming was rinsing the mercury
surface, seemingly increasing the surface tension on the electrocapillary curves, and it increased transport of the
electroactive substance to the electrode increasing the electrolytic current on the polarographic curves. Professor
Kucera, unfortunately, did not witness these results – he had passed away untimely in early 1921.

In the course of the first decade of polarography, the Prague group gathered a wealth of experimental experience
providing sufficient material for the development of a basic theory underlying various types of polarographic
current-voltage curves. The first impulse came from Kemula, who studied the most common type of
polarographic currents where the electroactive species arrives to the electrode by diffusion. He found that, in the
same solution, two polarographic capillaries provide about the same current when the rate of flow of mercury
through them (in milligram/second) is equal. Further he observed that the "diffusion current" increased with the
square root of mercury pressure given by the height of the level of mercury in the reservoir above the tip of the
capillary. Theoretical explanation of these experimental facts was soon provided by Heyrovsky's assistant, Slovak
physicist Dionyz Ilkovic, who in 1934 derived the equation of electrolytic current, controlled by the rate of
diffusion of the electroactive species to surface of the dropping mercury electrode. The equation was derived
under the simplifying assumption of linear diffusion, and agreed well with experimental results. Almost twenty
years later, the equation was precisely recalculated for spherical diffusion by another theoretician of the Prague
group, Jaroslav Koutecky. According to his results, the currents should be about 10% higher than predicted by the
Ilkovic equation. That was later confirmed by rigorous measurements with exclusion of the partial transfer of
exhaustion of the electroactive species around the tip of the currently used vertically positioned cylindrical
capillary. The good agreement of the original Ilkovic equation with experiment was thus explained by a
compensation of the experimental error and the error introduced by the theoretical simplification.

Ilkovic further completed the basic theory of polarography by deriving and

verifying an equation for the double-layer charging current at the dropping
mercury electrode. That made polarographers aware of the capacity of the
electrode double layer and allowed them to follow adsorption of the solution
components at the mercury surface. The charging current, which is basically
inherent in polarographic measurements, has an average value of the order of
diffusion currents corresponding to about 10 µM concentration of an electroactive
substance. Thus, it limits to this concentration the sensitivity of simple
polarographic measurements, at lower concentrations the diffusion current is
overlapped by higher charging current. As the mean charging current, unlike the
diffusion current, increases linearly with applied voltage, Ilkovic with Semerano
suggested sending through the galvanometer an empirically selected artificial
counter-current decreasing with applied voltage, which would thus compensate to
some extent the unwanted charging current. Since then, the Ilkovic-Semerano
circuit is included in commercially produced polarographs.

Fig. 7. Polarographic curves When an electroactive substance is present in the solution, it manifests itself on the
showing constancy of "half- polarographic curve as a stepwise increase of current, the shape of which can be
wave potential" of Cd2+ ion regarded as a wave. The height of the step, or of the wave, is the limiting current, a
reduction at different measure of concentration of the substance in the solution. For quantitative
concentrations of CdCl2. analytical measurements it is not necessary to record the whole curve, it is
sufficient to apply to the electrode a constant potential, within the range of the
limiting current, and to measure the change of the limiting current as function of concentration in the course of a
titration. Such titrations, originally called "polarometric", have later become known as "amperometric" titrations.

In order to derive an equation for the whole polarographic wave, Heyrovsky and Ilkovic considered the simple
common case of an electroactive substance transported in the solution towards the electrode by diffusion, and
undergoing a fast and reversible exchange of electrons with the electrode. Then, by combination of the Nernst and
the Ilkovic equations one arrives at the Heyrovsky-Ilkovic equation of the diffusion-controlled polarographic
 wave. The potential, at which the current reaches one half of the total waveheight, has been called the half-wave
potential. For a reversible redox-system the half-wave potential, denoted as "E½", is constant, independent of
concentration (Figure 7). Values of "E½" of various electroactive substances have been since listed in many
textbooks and manuals; "E½"has become an important symbol in electrode kinetics.

Apart from diffusion currents, also a different type of

polarographic current was observed: as a rule, this current is
much higher than the diffusion current, it appears in the negative
range of potentials, it strongly depends on pH of the supporting
solution, and it occurs with compounds which are not
necessarily electroactive, like proteins or alkaloids. This current
was explained as due to catalytic evolution of hydrogen at the
mercury electrode: the high hydrogen overpotential of mercury
becomes lowered when an apt substance, the catalyst, mediates
Fig. 8. Polarographic "Brdicka reaction" of transfer of hydrogen ions from solution to close contact with
blood sera of different patients with following negatively polarized mercury surface, where they undergo
diagnoses: 1) status febrilis 2) tumor hepatis reduction to gaseous hydrogen. A great number of
susp 3) ca. ventriculi susp 4) normal serum 5) electroinactive substances can thus be followed
cirrhosis hepatic 6) atherosclerosis. polarographically. Heyrovsks's second assistant, Dr. Rudolf
Brdicka, discovered a sensitive catalytic hydrogen-evolution
reaction of proteins: in buffer solutions of pH about 9, containing ions of cobalt, proteins yield a prominent
catalytic "double-wave"; this polarographic reaction was used in many countries over several decades as a
diagnostic tool in treatment of cancer (Figure 8).

Polarography becomes a standard technique

After the success of the first polarographs made in the

mechanical workshop of Department of Physics at the Faculty of
Science (Figure 9), a commercial production of the
photorecording instruments was started in Prague in 1929; in the
following years various foreign-made polarographs were
appearing on the world market, indicating growing interest in the
method. With the intention of making the results of
Czechoslovak chemists known abroad, Heyrovsky and his senior
friend, Professor Emil Votocek from the Prague Technical
University, started in 1929 the monthly journal "Collection of
Czechoslovak Chemical Communications", which accepted
papers in English and French; the "Collection" kept publishing
all important results of the Prague polarographic school.
Dissemination of polarography in USA was initiated in 1933 by
Heyrovsky, who, as Carnegie Visiting Professor, lectured for
five months at universities in California and in the middle and
eastern States. In German speaking countries, polarography
became first known from a chapter by Heyrovsky, included in
1936 in the second volume of the well known series
Fig. 9. The first polarograph built at the "Physikalische Methoden der analytischen Chemie", edited by
University, which became a model for W. Bottger from Leipzig University. The interest in
commercial instruments. polarography in Soviet Union was spurred by the Russian
geochemist A. P. Vernadskii, who sent his coworkers to learn the
method in Prague, he also had Heyrovsky's Czech textbook from 1933 translated into Russian, and he invited
Heyrovsky to lecture on polarography on the occasion of Mendeleev's 1934 centenary celebrations in Russia. The
main pioneer and teacher of polarography in the USA over several decades was Professor Isaak Maurits Kolthoff,
an analytical chemist at the University of Minneapolis, Minnesota, he visited Heyrovsky's laboratory several
times in the nineteen-thirties, he became interested in the method and wrote a well known textbook on
polarography which appeared in two editions and was translated into other languages. The French chemist Dr.
Edgar Verdier spent several months in Prague before the outbreak of World War II doing research in
polarography; after returning home he wrote the first French textbook on the subject. Thus the knowledge and use
of polarography in the world was spreading – while by the end of 1930 the polarographic bibliography contained
a total number of 125 publications, after ten years it was already at 900.

Ilkovic's work in building the polarographic theory was continued by Rudolf Brdicka. He provided a general
treatment of a two-stage reversible polarographic reduction with formation of semiquinones and their dimers, he
introduced the concept of polarographic currents controlled by adsorption of the electroactive species, and, with
his junior coworker Karel Wiesner, he opened the wide field of polarographic currents controlled by chemical
reactions. The dropping mercury electrode was thus supplying new topics for general electrode kinetics.

During World War II, polarography, as a modern analytical technique, was applied in various branches of the war
industry including the development of the atomic bomb – in the "Manhattan Project" the transuranium elements
were determined by several polarographs. Czechoslovakia was occupied by the German army, and the Czech
universities were taken over by Germans. Thanks to the help of his anti-nazi colleague, German physical chemist
Professor Johann Bohm, Heyrovsky was able to continue working in his laboratory. He used this time, free of
teaching duties, to finish his major textbook on polarography, which appeared in German published by Springer
in Vienna, and he began to use cathode-ray oscilloscope in polarographic research. Complying with the
possibilities of electronic technology at that time, and intending to try another type of electrolytic polarization, he
introduced what he called "oscillographic polarography". The dropping mercury electrode was polarized by
alternating current and the corresponding rapid changes of electrode potential were followed on the screen of an
oscilloscope. That method allowed the study of fast electrode processes; for that purpose, Heyrovsky, with his
coworker Dr. Jindrich Forejt, was using a mercury jet electrode, with which the contact between the electrode
surface and the solution lasted only fractions of a second. For analytical purposes the potential dependence of the
first derivative of electrode potential by time was used – it formed a closed, oval-shaped curve, with cathodic and
anodic branches opposite each other; on such a curve, the electrolytic processes appeared as indentations. That
technique clearly displayed reversibility of the processes involved, and accelerated polarographic analysis from
minutes to seconds.

In the years after the war, polarography was among the five most often used methods of chemical analysis. As a
guest of the British Council in 1946, Heyrovsky visited several universities in the UK, lecturing on polarography.
The next year he was invited by Svenska Institutet to lecture in Sweden and in Denmark. The first international
congress on polarography was organized in Prague in February of 1951. By that time, Czechoslovakia had
become part of the Soviet bloc and potential participants from abroad were not admitted to the country; however,
most of them submitted their contributions to the congress proceedings, which appeared in three volumes. The
organizer of the congress was the "Institute of Polarography", one of eight new institutes founded in 1950 by the
communist government in order to boost research in science and technology. Heyrovsky was appointed director
of the institute, nevertheless, as he was not politically trusted by the regime, his further invitations to conferences
and to lecture tours abroad were being turned down without official reason. When the new Academy of Sciences,
according to Soviet example, was established in the country in 1953, the Institute of Polarography was included in
it, and Heyrovsky, as institute director, was nominated for membership in the Academy. His teaching duties at the
University were reduced, and the directorship of the Department of Physical Chemistry was taken over by
Brdicka, who had in the meantime become full professor.

The task of the newly established academic Institute was to carry out basic research in all fields of polarography,
to introduce and supervise its practical applications in the country, to collect and publish polarographic
bibliography, and to control the state-organized production of polarographs. This sounded very good, however,
the world situation was not very favorable for such a project. Because of political division of the world, and due
to forced isolation of Czech experts from their western colleagues, the progress of technology in the entire eastern
 bloc, especially in the field of electronics, was lagging behind. The technical progress of the post-war world
required highly sensitive, specific, and rapid methods of analysis. The original, simple form of polarography
needed further modifications to meet these requirements. From the nineteen-fifties on, the innovations and
improvements of polarographic instrumentation were steadily moving to western countries together with the
advanced theoretical studies brought about by the new techniques. In this way, the Prague polarographic school
was gradually losing its exclusive position in instrumental and theoretical polarography.

Members of the Heyrovsky's group tried to keep pace with the international development. Another Heyrovsky's
pre-war assistant at the University, Dr. Mirko Kalousek, introduced the "commuter polarography", in which, in
course of recording the curve, the potential of the dropping electrode could be commuted with variable frequency
to a certain selected constant potential; the resulting curve could then indicate reversibility of the studied
electrode reaction, and electroactivity and other properties of its prospective intermediates. Shortly after the war,
Heyrovsky's junior coworker, electronic engineer Augustin Sevcik, began applying linear voltage pulses of large
amplitudes to slowly growing mercury drops and observed the resulting curves on the screen of an oscilloscope –
that was the "single-sweep" or "multi-sweep" oscillographic polarography, according to whether one or several
voltage pulses were applied to one drop, and one or more current-voltage curves appeared on the screen of the
oscilloscope. Instead of the polarographic waves, the curves were peak shaped, for which Sevcik derived a
corresponding equation; as the method and equation were published independently at the same time by A. Sevcik
in Prague and by Professor J. E. B. Randles in Birmingham, the mathematical formulation of the corresponding
current-potential curve is known as the Randles-Sevcik equation.

In addition to the original, or "dc", polarography, Professor Bruno

Breyer in Australia introduced "ac" polarography (Figure 10), in
which small amplitude ac voltage was superimposed on the dc
voltage applied to the dropping electrode, and, instead of direct
current, the ensuing alternating current was measured, as function
of the applied mean dc voltage. Such curves were characterized by
maxima, or peaks, in place of half-wave potentials of dc
polarography. Prominent peaks appeared on the curves also when
the electrode capacity was changed by fast adsorption or desorption
of a surface-active compound. Later, placed on a more rigorous
basis, two different alternating currents have been recorded
separately – that flowing in-phase with the applied alternating
voltage, and that flowing out-of-phase with it. In that way the
Fig. 10. Oscilloscope displaying an "a.c. complex impedance of the dropping electrode is measured which
oscillopolarographic" curve obtained with a provides exact data for electrode kinetics in general, and for study
mercury-jet electrode. In the background of adsorption processes in particular.
picture of professor B. Kucera.
Similar to ac polarography, though much more sophisticated in
detail, is the "square-wave polarography", developed by Dr. Geoffrey Cecil Barker in the Atomic Energy
Research Establishment at Harwell, UK. Instead of the usual sine-wave shape, the alternating voltage has here a
basically rectangular form and the current is measured during the short intervals before each change of the
rectangular voltage half-period. This way, the charging current has been eliminated to a large extent, and the
sensitivity of polarographic determinations was increased by about two orders of magnitude of concentration in
the solution. Barker's laboratory became a rich source of further development of polarographic instrumentation.
Pulse polarography, and especially its differential version, brought the sensitivity of polarographic analysis to its
limit – in these methods, a single potential pulse is applied to each mercury drop, and the current, or the
difference of currents in the differential version, is measured before the end of drop-time, essentially eliminating
the charging current component. "Radio frequency polarography" and "Intermodulation polarography" have been
introduced for solving problems in advanced electrode kinetics. Barker combined all his highly complex
electronic techniques solely with the dropping mercury electrode, as he trusted its exquisite properties as a
scientific tool.
In the nineteen-fifties, several polarographers – Drs. Vladimir Cermak and Jirí Vogel in Prague, and Dr. Zenon
Kublik and Professor Wiktor Kemula in Warsaw, started using the hanging mercury drop electrode instead of the
dropping mercury electrode. That meant that they recorded the whole curve with one single drop of mercury (like
in the single-sweep polarography); after the curve was completed, the used drop was knocked off and a new one
was produced from the capillary. As this time a stationary electrode has been used, according to the official
IUPAC nomenclature the method thus introduced is not "polarography" any more, it has to be called
"voltammetry". The curves are still reproducible, however, unlike the dropping electrode, the hanging drop carries
its whole "history" along. This simple fact has been utilized to produce a considerable increase of sensitivity in
electroanalysis: using a selected constant potential and controlled stirring, a product of the electrolytic process is
quantitatively accumulated at the electrode surface, either in the form of an amalgam or in the form of an
adsorbed layer; after an exactly measured time of electrolysis, a linear voltage scan is applied and the current-
voltage curve is recorded, displaying the electrode reaction in reverse. This voltammetric operation is known as
"stripping", of which three modifications are distinguished: anodic stripping (usually dissolution of a metal from
the previously formed amalgam), cathodic stripping (usually reduction of compounds with mercury, previously
formed at positive potentials) and adsorptive stripping (usually desorption of species previously accumulated by
controlled adsorption). The voltammetric stripping methods allow analytical determinations of species in dilutions
as low as one tenth of one billionth molar concentration (M) and lower. Professor Emil Palecek developed the
"adsorption transfer voltammetric stripping" in 1986 for electroanalysis of biological macromolecules – in this
technique, rare substances are accumulated by adsorption from a minute volume (millionth of a liter) of solution
to the surface of hanging mercury drop; that electrode with the adsorbed layer is then transferred to a normal cell
with usual volume of suitable electrolyte, for a proper study by some of the stripping techniques. The G. C.
Barker's instrumental techniques developed for the dropping electrode can be, and very often are, used with the
hanging mercury drop electrode, thus, for example, the very limits of analytical sensitivity can be reached with
the differential pulse adsorptive, cathodic or anodic, stripping voltammetry.