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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
especially after an exact theoretical background was worked out. inspired by the then successfully spreading spectral analysis. Polarography was created in 1922 when Jaroslav Heyrovsky used dropping mercury electrode for measuring polarization curves. Briefly. The dropping mercury electrode keeps the interface always fresh between its constantly renewed surface and the solution. 2. London (1911). Once the recording of polarization curves was made automatic. professor of Roman law at Charles University in Prague. or on the electrode potential of the dropping electrode. electrochemistry was established as a special branch of science and technology. the basic theory and practice of electrolysis became understood. Jaroslav Heyrovsky (1890-1967) and his life dedicated to polarography The early years Jaroslav was born on the 20th of December 1890. mercury. Thanks to the work of Humphry Davy and Michael Faraday. Varley and Gabriel Lippmann gave scientists an intricate problem to study. 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. thought of introducing its electrochemical analogy. the relative simplicity of the apparatus and the rapidity of gaining results attracted attention of analytical chemists. which is displayed by the curve. original method to meet increasing requirements of science and technology. passing through the system. By preparing the dropping mercury electrode (Figure 1). Electrochemistry at the beginning of the 20th century In the course of the 19th century. independent of the processes that were taking place at previous drops. the latest versions derived from the simple electrolysis with dropping mercury electrode belong to the most sensitive and versatile methods of analysis. C. thanks to the high reproducibility of the curves. even with a variety of solid electrodes and using various ways of polarization they were unable to achieve satisfactorily reproducible results. Jaroslav Heyrovsky as a student at the University College. Dropping mercury electrode as collected from that electrode for measuring surface tension of polarized used by Bohumil Kucera. and. Technical progress has continued modifying the classical. then in Fig. he dedicated the rest of his life to the development of the method he thus initiated.dependence of the current. Encouraged by the results. Hermann Helmholtz and Walther Nernst developed the concept of electrode potential and electrochemical polarization. F. such was the situation in electrochemistry when the international clan of scientific workers was joined by Jaroslav Heyrovsky. Jaroslav Heyrovsky received the 1959 Nobel Prize in Chemistry for his discovery of polarography. on the voltage applied to the electrodes. 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. into the family of Leopold Heyrovsky. however. it is the time-change of potential of the dropping electrode. 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". and thereby the measurements taken with it are perfectly reproducible. . Nernst. 1. In the case of the current-controlled ("galvanostatic") electrolysis. polarography has become and remains an appreciated and trusted method in laboratories all over the world.
mathematics. to change the voltage by 10 mV. to weigh it exactly. Following Kucera's instructions. caught by the outbreak of World War I. knowing Kucera´s work. This position gave him the chance. who asked the candidate about the method of measuring surface tension of polarized mercury by dropping mercury electrode. his own not fully accomplished research – to solve the so-called "Kucera's anomaly" of electrocapillary curves obtained by the dropping mercury method. In 1913 Ramsay retired.D. The two boys showed keen interest in nature from their childhood. the younger one later became one of the leading Czech entomologists. who affected decisively the scientific orientation of young Heyrovsky by suggesting to him as topic for Ph. There the Czech student had the privilege to attend the great chemist's lectures. over the entire voltage range of 2 to 3 volts. For the experimental measurement. The dropweight-voltage. this time in the new Czechoslovak Republic. After the first year of Jaroslav's study at Prague University. A certain simplification was to measure drop-time. it occurred to him that this might indicate passage of electrolytic current. in military uniform and with a completed dissertation. and so in last days of the war. remained constant over a certain voltage range.. or the drop-time. examination at Prague University. decided that in the future he would like to study physical chemistry. as physical chemistry was not an independent subject there. Jaroslav. The discovery of polarography After the war. while the elder one's preferred subjects in school were biology. Heyrovsky was called up to join the Austrian army and to serve in military hospitals as dispensing chemist and x-ray technician. Heyrovsky observed that the drop-weight. G. succeeded by the electrochemist F.the Austro-Hungarian Empire. and he decided from then on to measure current. When William Ramsay was distinguished by the Nobel Prize for chemistry in 1904 for his discovery of rare gas elements.D. for a Ph.D. thesis the electrode potential of aluminum. Donnan. 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. and physics (chemistry was not taught at that time). to dry the collected mercury. or drop-time-voltage curves had mostly the correct shape of the electrocapillary parabola. and the surprised examiner suggested that the student continue. where William Ramsay held the chair of general chemistry. Heyrovsky became assistant at the Department of Inorganic and Analytical Chemistry at the Prague University. Heyrovsky. 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. but sometimes their round maximum was overlapped by a secondary sharp maximum – the Kucera's anomaly. in rare moments of leisure. in addition to the drop-weight or drop-time. proportional to the surface tension. His examiner in physics on that occasion was Professor Bohumil Kucera. in the autumn of 1918. Donnan advised his student to use dilute aluminum amalgam slowly flowing out of a capillary tube thus constantly renewing its surface. to record the weight. as a fresh Ph. under the assumption of constant rate of flow of mercury at various potentials. after successful examination. to work on his dissertation "On the electroaffinity of aluminum". Back home for summer holidays in 1914. father Leopold agreed to support his son's continued studies at the University College in London (Figure 2). he could present himself. strongly impressed. while the layer of mercury at the bottom of the cell was connected to the positive pole. . in order to avoid formation of passivation layers on the aluminum surface. This acquainted Heyrovsky with the sphere of problems which he was later facing in his work with the dropping mercury electrode. passing through the cell. was prepared for such question. and to continue. In some cases. He had three elder sisters and one younger brother.
Heyrovsky was appointed assistant professor in the newly established Fig. provided with a lamp irradiating the mirror. Apparatus for measuring current-voltage curves in with the hitherto use of solid electrodes. The height of the current steps was proportional to oxygen concentration in the solution. Thanks to the minute size of the mercury drops the amount of oxygen consumed in the electrolytic reaction was completely negligible. Dr. Heyrovsky and Shikata attended the "General Discussion on Electrode Reactions and Equilibria" of the Faraday Society in London. first with the dropping mercury cathode.In the afternoon of Friday. . he connected a sensitive mirror galvanometer. the dropping mercury electrode then can serve also as an anode. Heyrovsky continued a systematic research of electrolysis. to which each contributed with communication on electrolysis with dropping mercury electrode (Figure 4). although limited by anodic dissolution of metallic mercury. His first account Heyrovsky on the occasion of of "Electrolysis with the dropping mercury cathode" was published in Czech Faraday Discussion in London in 1922. corresponding to the highest value of 2. and a final steep increase of current out of scale. Later it was shown that even oxidation processes can be followed. 1923. about 0. and in a relatively narrow positive potential range. After the mean values of the current oscillations were plotted as a function of the voltage applied to the electrodes. curve turned out to be exactly reproducible. 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. on the measuring scale (Figure 3). Masuzo Shikata. offers the widest attainable range of potentials in the negative direction. 4. this electrolysis with dropping mercury electrode. and students as well as interested colleagues were readily joining him in his original research. and followed motions of the luminous spot. the resulting polarization curve showed two equally high steps of current increase. In April of 1922. as at the beginning various reduction processes were studied. Masuzo Shikata and Jaroslav department of physical chemistry. In November of the same year. Usefulness for analytical chemistry of the electrolysis with dropping mercury electrode appeared straightforward. for which mercury. In contrast Fig. to the electrolytic circuit with the dropping mercury electrode dipping into 1 M solution of sodium chloride (common salt).8 V apart. reflected from the mirror of the galvanometer. That day can be considered as the date of birth of the method. 3. the 10th of February 1922. an English version appeared in the "Philosophical Magazine" in (December. with its highest hydrogen overpotential of all metals. The latter article attracted the attention of a young Japanese scientist. The instantaneous current oscillated rhythmically according to the regular growing and falling of the drops. 1923). It was the first polarization curve obtained with the dropping mercury electrode. which later received the name "polarography". to the extent that he came to Prague in 1923 to learn the new method on the spot. and the position of the steps on the voltage scale appeared to be values characteristic of oxygen. After the successful initial experiment.0 applied volts.
Fig. Heyrovsky has proven with further polarographic experiments that. Vaclav Dolejsek. This considerably spurred the further development and the spreading of polarography. Although it was not specified in that paper that the instrument should be used solely for measurements with the dropping mercury electrode. The result proved successful. "Polarographic spectrum" – curve of polarographic reduction of seven different cations. were Dr. the method of electrolysis with that kind of electrode has gradually acquired the name "polarography". 5. then author of the very first textbook on polarography. 75. polarographic analysis allowed determination of electroactive species in 10 µM concentration even in a minute volume of solution. 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. and polarography was going to be the primary subject of research in his department of physical chemistry.The only drawback of the promising new method was the cumbersome way of manual recording of the curves. 6. which became the cornerstone of the Japanese polarographic school. This aspect was discussed at length between Heyrovsky and Shikata. as part of a special series of eleven papers on "Researches with the dropping mercury cathode". accompanied by changes of . Dr. The first decade In 1926 Heyrovsky became full professor. Later it was explained that both maxima were caused by the streaming of the solution around the mercury drops when electrolytic processes. Moreover. However. polarography brought the fulfillment of the Nernst's idea of an electrochemical analogy to spectroscopy (Figure 6). Fig. Rudolf Simunek. xray spectroscopist Dr. were preoccupied with the search for the new chemical element No 75. the manganese ores did not contain element No. and I. and he conceded the discovery of the new element to W. Heyrovsky showed that the pointed maxima on electrocapillary curves appeared with solutions with which similar maxima appeared also on polarographic curves – commonly it occurred when oxygen contained in the solution was reduced at the electrode. 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). and in a 1925 special issue of the Dutch journal "Recueil des Travaux Chimiques des Pays Bas". it automatically provided an objective document of with polarograph. in order to learn polarography at the early stage and to introduce it in their own countries. a paper was published by Heyrovsky and his coworkers describing the new device of Heyrovsky and Shikata. and Dr. Noddack. meaning an instrument for recording the process of electrolytic polarization. exactly reproducible measurements. The problem of Kucera's anomaly was not forgotten: with Kucera´s assistant. In 1925 Shikata left Prague for home. who called it "rhenium". Wiktor Kemula from Poland. Giovanni Semerano from Italy. Thus. and on the 30th of March 1924. contrary to his previous belief. The polarograph shortened the time of recording polarization curves from hours to minutes and. Among other foreign scientists who visited Prague. and in his luggage he carried one of the first polarographs. Heyrovsky and his friend. Scheme of automatic measuring circuit moreover. At that time. The paper was entitled "The polarograph".
and undergoing a fast and reversible exchange of electrons with the electrode. 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. which is basically inherent in polarographic measurements. 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. As the mean charging current. In the course of the first decade of polarography. it manifests itself on the polarographic curve as a stepwise increase of current. the currents should be about 10% higher than predicted by the Ilkovic equation. two polarographic capillaries provide about the same current when the rate of flow of mercury through them (in milligram/second) is equal. Since then. Thus. 7. originally called "polarometric". in the same solution. Ilkovic with Semerano suggested sending through the galvanometer an empirically selected artificial counter-current decreasing with applied voltage. Jaroslav Koutecky. Then. He found that. Polarographic curves showing constancy of "halfwave potential" of Cd2+ ion reduction at different concentrations of CdCl2. is the limiting current. unfortunately. and agreed well with experimental results. Theoretical explanation of these experimental facts was soon provided by Heyrovsky's assistant. were taking place at the electrode – the streaming was rinsing the mercury surface. For quantitative analytical measurements it is not necessary to record the whole curve. 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. a measure of concentration of the substance in the solution. Professor Kucera. Slovak physicist Dionyz Ilkovic. who studied the most common type of polarographic currents where the electroactive species arrives to the electrode by diffusion. the Ilkovic-Semerano circuit is included in commercially produced polarographs. it limits to this concentration the sensitivity of simple polarographic measurements. it is sufficient to apply to the electrode a constant potential. In order to derive an equation for the whole polarographic wave. The equation was derived under the simplifying assumption of linear diffusion. at lower concentrations the diffusion current is overlapped by higher charging current. Such titrations. unlike the diffusion current. When an electroactive substance is present in the solution. seemingly increasing the surface tension on the electrocapillary curves.adsorption of the electroactive species. the shape of which can be regarded as a wave. 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. within the range of the limiting current. The charging current. the equation was precisely recalculated for spherical diffusion by another theoretician of the Prague group. Almost twenty years later. or of the wave. did not witness these results – he had passed away untimely in early 1921. The height of the step. 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. by combination of the Nernst and the Ilkovic equations one arrives at the Heyrovsky-Ilkovic equation of the diffusion-controlled polarographic . who in 1934 derived the equation of electrolytic current. Fig. have later become known as "amperometric" titrations. controlled by the rate of diffusion of the electroactive species to surface of the dropping mercury electrode. Heyrovsky and Ilkovic considered the simple common case of an electroactive substance transported in the solution towards the electrode by diffusion. and it increased transport of the electroactive substance to the electrode increasing the electrolytic current on the polarographic curves. and to measure the change of the limiting current as function of concentration in the course of a titration. 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. The first impulse came from Kemula. increases linearly with applied voltage. which would thus compensate to some extent the unwanted charging current. has an average value of the order of diffusion currents corresponding to about 10 µM concentration of an electroactive substance. According to his results.
and it occurs with compounds which are not necessarily electroactive. discovered a sensitive catalytic hydrogen-evolution reaction of proteins: in buffer solutions of pH about 9. he also had Heyrovsky's Czech textbook from 1933 translated into Russian. Apart from diffusion currents.wave. who sent his coworkers to learn the method in Prague. independent of concentration (Figure 7). A great number of diagnoses: 1) status febrilis 2) tumor hepatis electroinactive substances can thus be followed susp 3) ca. has been called the half-wave potential. which became a model for W. "E½"has become an important symbol in electrode kinetics. Heyrovsky and his senior friend. proteins yield a prominent catalytic "double-wave". the "Collection" kept publishing all important results of the Prague polarographic school. is constant. 8. lectured for five months at universities in California and in the middle and eastern States. in the following years various foreign-made polarographs were appearing on the world market. indicating growing interest in the method. mediates transfer of hydrogen ions from solution to close contact with Fig. also a different type of polarographic current was observed: as a rule. and he invited Heyrovsky to lecture on polarography on the occasion of Mendeleev's 1934 centenary celebrations in Russia. containing ions of cobalt. which accepted papers in English and French. edited by University. 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). With the intention of making the results of Czechoslovak chemists known abroad. 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. Brdicka. The first polarograph built at the "Physikalische Methoden der analytischen Chemie". Vernadskii. The main pioneer and teacher of polarography in the USA over several decades was Professor Isaak Maurits Kolthoff. The interest in commercial instruments. Values of "E½" of various electroactive substances have been since listed in many textbooks and manuals. included in 1936 in the second volume of the well known series Fig. who. For a reversible redox-system the half-wave potential. Dr. as Carnegie Visiting Professor. The potential. Dissemination of polarography in USA was initiated in 1933 by Heyrovsky. where they undergo blood sera of different patients with following reduction to gaseous hydrogen. Professor Emil Votocek from the Prague Technical University. 9. Polarographic "Brdicka reaction" of negatively polarized mercury surface. ventriculi susp 4) normal serum 5) polarographically. Rudolf cirrhosis hepatic 6) atherosclerosis. polarography became first known from a chapter by Heyrovsky. In German speaking countries. the catalyst. this current is much higher than the diffusion current. denoted as "E½". at which the current reaches one half of the total waveheight. polarography in Soviet Union was spurred by the Russian geochemist A. Bottger from Leipzig University. it appears in the negative range of potentials. a commercial production of the photorecording instruments was started in Prague in 1929. like proteins or alkaloids. it strongly depends on pH of the supporting solution. P. started in 1929 the monthly journal "Collection of Czechoslovak Chemical Communications". . Heyrovsks's second assistant.
to introduce and supervise its practical applications in the country. and intending to try another type of electrolytic polarization. polarography. and due to forced isolation of Czech experts from their western colleagues. nevertheless. As a guest of the British Council in 1946. 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. During World War II. The task of the newly established academic Institute was to carry out basic research in all fields of polarography. as institute director. and. to collect and publish polarographic bibliography. His teaching duties at the University were reduced. In the years after the war. according to Soviet example. and accelerated polarographic analysis from minutes to seconds. he introduced the concept of polarographic currents controlled by adsorption of the electroactive species. Heyrovsky was appointed director of the institute. Because of political division of the world. with his junior coworker Karel Wiesner. the electrolytic processes appeared as indentations. The dropping mercury electrode was thus supplying new topics for general electrode kinetics. and the directorship of the Department of Physical Chemistry was taken over by Brdicka. 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. after ten years it was already at 900. He provided a general treatment of a two-stage reversible polarographic reduction with formation of semiquinones and their dimers. Heyrovsky was able to continue working in his laboratory. he introduced what he called "oscillographic polarography". He used this time. The next year he was invited by Svenska Institutet to lecture in Sweden and in Denmark. The French chemist Dr. with cathodic and anodic branches opposite each other. Czechoslovakia was occupied by the German army. Edgar Verdier spent several months in Prague before the outbreak of World War II doing research in polarography. By that time. and Heyrovsky. with his coworker Dr. Complying with the possibilities of electronic technology at that time. the Institute of Polarography was included in it. This sounded very good. When the new Academy of Sciences. to finish his major textbook on polarography. as he was not politically trusted by the regime. he visited Heyrovsky's laboratory several times in the nineteen-thirties. and the Czech universities were taken over by Germans. lecturing on polarography. polarography was among the five most often used methods of chemical analysis. free of teaching duties. was using a mercury jet electrode. his further invitations to conferences and to lecture tours abroad were being turned down without official reason. with which the contact between the electrode surface and the solution lasted only fractions of a second. as a modern analytical technique. for that purpose. however. German physical chemist Professor Johann Bohm. Minnesota. which appeared in three volumes. one of eight new institutes founded in 1950 by the communist government in order to boost research in science and technology. Thanks to the help of his anti-nazi colleague. which appeared in German published by Springer in Vienna. most of them submitted their contributions to the congress proceedings. after returning home he wrote the first French textbook on the subject. The organizer of the congress was the "Institute of Polarography". Heyrovsky visited several universities in the UK. Czechoslovakia had become part of the Soviet bloc and potential participants from abroad were not admitted to the country. and to control the state-organized production of polarographs. That method allowed the study of fast electrode processes.an analytical chemist at the University of Minneapolis. the progress of technology in the entire eastern . who had in the meantime become full professor. The first international congress on polarography was organized in Prague in February of 1951. That technique clearly displayed reversibility of the processes involved. the world situation was not very favorable for such a project. 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. Jindrich Forejt. Ilkovic's work in building the polarographic theory was continued by Rudolf Brdicka. 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. on such a curve. however. and he began to use cathode-ray oscilloscope in polarographic research. he opened the wide field of polarographic currents controlled by chemical reactions. was nominated for membership in the Academy. For analytical purposes the potential dependence of the first derivative of electrode potential by time was used – it formed a closed. was established in the country in 1953. Heyrovsky. oval-shaped curve.
UK. two different alternating currents have been recorded separately – that flowing in-phase with the applied alternating voltage. in which. Such curves were characterized by maxima. Professor Bruno Breyer in Australia introduced "ac" polarography (Figure 10). 10. E. the curves were peak shaped. Another Heyrovsky's pre-war assistant at the University. This way. and rapid methods of analysis. and especially its differential version. 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. Prominent peaks appeared on the curves also when the electrode capacity was changed by fast adsorption or desorption of a surface-active compound. the charging current has been eliminated to a large extent. the Prague polarographic school was gradually losing its exclusive position in instrumental and theoretical polarography. Oscilloscope displaying an "a. Pulse polarography. essentially eliminating the charging current component. Barker's laboratory became a rich source of further development of polarographic instrumentation. placed on a more rigorous basis. Mirko Kalousek. or "dc". or the difference of currents in the differential version. introduced the "commuter polarography". in which small amplitude ac voltage was superimposed on the dc voltage applied to the dropping electrode. as function of the applied mean dc voltage. electronic engineer Augustin Sevcik. a single potential pulse is applied to each mercury drop. oscillopolarographic" curve obtained with a mercury-jet electrode. is the "square-wave polarography". Similar to ac polarography. Barker combined all his highly complex electronic techniques solely with the dropping mercury electrode. as he trusted its exquisite properties as a scientific tool. Instead of the usual sine-wave shape. polarography.c. especially in the field of electronics. Sevcik in Prague and by Professor J. brought the sensitivity of polarographic analysis to its limit – in these methods. and the sensitivity of polarographic determinations was increased by about two orders of magnitude of concentration in the solution. and for study of adsorption processes in particular. In this way. the ensuing alternating current was measured. In the background picture of professor B. and the current. Kucera. . Geoffrey Cecil Barker in the Atomic Energy Research Establishment at Harwell. In addition to the original. "Radio frequency polarography" and "Intermodulation polarography" have been introduced for solving problems in advanced electrode kinetics. for which Sevcik derived a corresponding equation. in place of half-wave potentials of dc polarography. the resulting curve could then indicate reversibility of the studied electrode reaction. 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. Later. according to whether one or several voltage pulses were applied to one drop. though much more sophisticated in detail. and electroactivity and other properties of its prospective intermediates. and. and one or more current-voltage curves appeared on the screen of the oscilloscope. Instead of the polarographic waves. specific. developed by Dr. simple form of polarography needed further modifications to meet these requirements. instead of direct current. From the nineteen-fifties on. B. The technical progress of the post-war world required highly sensitive. 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. the potential of the dropping electrode could be commuted with variable frequency to a certain selected constant potential. The original. and that flowing out-of-phase with it. Shortly after the war. Heyrovsky's junior coworker. was lagging behind. In that way the complex impedance of the dropping electrode is measured which provides exact data for electrode kinetics in general. the mathematical formulation of the corresponding current-potential curve is known as the Randles-Sevcik equation. as the method and equation were published independently at the same time by A. Members of the Heyrovsky's group tried to keep pace with the international development. is measured before the end of drop-time.bloc. Dr. in course of recording the curve. Randles in Birmingham. Fig. or peaks.
however. the very limits of analytical sensitivity can be reached with the differential pulse adsorptive.In the nineteen-fifties. cathodic stripping (usually reduction of compounds with mercury. The G. for example. thus. and very often are. Barker's instrumental techniques developed for the dropping electrode can be. either in the form of an amalgam or in the form of an adsorbed layer. after the curve was completed. after an exactly measured time of electrolysis. started using the hanging mercury drop electrode instead of the dropping mercury electrode. unlike the dropping electrode. several polarographers – Drs. the used drop was knocked off and a new one was produced from the capillary. That meant that they recorded the whole curve with one single drop of mercury (like in the single-sweep polarography). Vladimir Cermak and Jirí Vogel in Prague. . 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. This simple fact has been utilized to produce a considerable increase of sensitivity in electroanalysis: using a selected constant potential and controlled stirring. stripping voltammetry. that electrode with the adsorbed layer is then transferred to a normal cell with usual volume of suitable electrolyte. rare substances are accumulated by adsorption from a minute volume (millionth of a liter) of solution to the surface of hanging mercury drop. for a proper study by some of the stripping techniques. displaying the electrode reaction in reverse. cathodic or anodic. used with the hanging mercury drop electrode. a linear voltage scan is applied and the currentvoltage curve is recorded. the hanging drop carries its whole "history" along. previously formed at positive potentials) and adsorptive stripping (usually desorption of species previously accumulated by controlled adsorption). of which three modifications are distinguished: anodic stripping (usually dissolution of a metal from the previously formed amalgam). C. according to the official IUPAC nomenclature the method thus introduced is not "polarography" any more. This voltammetric operation is known as "stripping". and Dr. a product of the electrolytic process is quantitatively accumulated at the electrode surface. it has to be called "voltammetry". As this time a stationary electrode has been used. Zenon Kublik and Professor Wiktor Kemula in Warsaw. The curves are still reproducible.
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