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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
1. or on the electrode potential of the dropping electrode. original method to meet increasing requirements of science and technology. In the case of the current-controlled ("galvanostatic") electrolysis. Nernst. it is the time-change of potential of the dropping electrode. however. London (1911). Electrochemistry at the beginning of the 20th century In the course of the 19th century. and thereby the measurements taken with it are perfectly reproducible.dependence of the current. Hermann Helmholtz and Walther Nernst developed the concept of electrode potential and electrochemical polarization. . the relative simplicity of the apparatus and the rapidity of gaining results attracted attention of analytical chemists. By preparing the dropping mercury electrode (Figure 1). especially after an exact theoretical background was worked out. Briefly. The dropping mercury electrode keeps the interface always fresh between its constantly renewed surface and the solution. thanks to the high reproducibility of the curves. Technical progress has continued modifying the classical. then in Fig. Jaroslav Heyrovsky as a student at the University College. Encouraged by the results. Once the recording of polarization curves was made automatic. 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. passing through the system. even with a variety of solid electrodes and using various ways of polarization they were unable to achieve satisfactorily reproducible results. into the family of Leopold Heyrovsky. Polarography was created in 1922 when Jaroslav Heyrovsky used dropping mercury electrode for measuring polarization curves. C. Jaroslav Heyrovsky (1890-1967) and his life dedicated to polarography The early years Jaroslav was born on the 20th of December 1890. F. Dropping mercury electrode as collected from that electrode for measuring surface tension of polarized used by Bohumil Kucera. 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. Varley and Gabriel Lippmann gave scientists an intricate problem to study. Jaroslav Heyrovsky received the 1959 Nobel Prize in Chemistry for his discovery of polarography. the latest versions derived from the simple electrolysis with dropping mercury electrode belong to the most sensitive and versatile methods of analysis. 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". the basic theory and practice of electrolysis became understood. he dedicated the rest of his life to the development of the method he thus initiated. polarography has become and remains an appreciated and trusted method in laboratories all over the world. inspired by the then successfully spreading spectral analysis. and. such was the situation in electrochemistry when the international clan of scientific workers was joined by Jaroslav Heyrovsky. independent of the processes that were taking place at previous drops. mercury. professor of Roman law at Charles University in Prague. on the voltage applied to the electrodes. electrochemistry was established as a special branch of science and technology. Thanks to the work of Humphry Davy and Michael Faraday. 2. which is displayed by the curve.
over the entire voltage range of 2 to 3 volts. father Leopold agreed to support his son's continued studies at the University College in London (Figure 2). to record the weight. In 1913 Ramsay retired. A certain simplification was to measure drop-time.the Austro-Hungarian Empire. Donnan. as a fresh Ph. it occurred to him that this might indicate passage of electrolytic current. For the experimental measurement. The discovery of polarography After the war. this time in the new Czechoslovak Republic. to change the voltage by 10 mV. proportional to the surface tension. decided that in the future he would like to study physical chemistry. who asked the candidate about the method of measuring surface tension of polarized mercury by dropping mercury electrode. There the Czech student had the privilege to attend the great chemist's lectures. the younger one later became one of the leading Czech entomologists. Heyrovsky observed that the drop-weight. in military uniform and with a completed dissertation. in addition to the drop-weight or drop-time. after successful examination. His examiner in physics on that occasion was Professor Bohumil Kucera. Heyrovsky was called up to join the Austrian army and to serve in military hospitals as dispensing chemist and x-ray technician.D. passing through the cell.D. Donnan advised his student to use dilute aluminum amalgam slowly flowing out of a capillary tube thus constantly renewing its surface. examination at Prague University. his own not fully accomplished research – to solve the so-called "Kucera's anomaly" of electrocapillary curves obtained by the dropping mercury method. caught by the outbreak of World War I. under the assumption of constant rate of flow of mercury at various potentials. Heyrovsky. or drop-time-voltage curves had mostly the correct shape of the electrocapillary parabola. and so in last days of the war. Following Kucera's instructions. and he decided from then on to measure current. in rare moments of leisure. The dropweight-voltage. or the drop-time. strongly impressed. thesis the electrode potential of aluminum. to weigh it exactly. This acquainted Heyrovsky with the sphere of problems which he was later facing in his work with the dropping mercury electrode. 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. was prepared for such question. succeeded by the electrochemist F. Back home for summer holidays in 1914. for a Ph. When William Ramsay was distinguished by the Nobel Prize for chemistry in 1904 for his discovery of rare gas elements. in the autumn of 1918. while the elder one's preferred subjects in school were biology. knowing Kucera´s work. In some cases. he could present himself. and the surprised examiner suggested that the student continue. Jaroslav. but sometimes their round maximum was overlapped by a secondary sharp maximum – the Kucera's anomaly. where William Ramsay held the chair of general chemistry. and to continue. He had three elder sisters and one younger brother. and physics (chemistry was not taught at that time). The two boys showed keen interest in nature from their childhood. . to work on his dissertation "On the electroaffinity of aluminum". mathematics.D. This position gave him the chance. while the layer of mercury at the bottom of the cell was connected to the positive pole. to dry the collected mercury. G. as physical chemistry was not an independent subject there. remained constant over a certain voltage range. who affected decisively the scientific orientation of young Heyrovsky by suggesting to him as topic for Ph. 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. Heyrovsky became assistant at the Department of Inorganic and Analytical Chemistry at the Prague University.. in order to avoid formation of passivation layers on the aluminum surface. After the first year of Jaroslav's study at Prague University.
to which each contributed with communication on electrolysis with dropping mercury electrode (Figure 4). After the successful initial experiment. 3. . to the electrolytic circuit with the dropping mercury electrode dipping into 1 M solution of sodium chloride (common salt). Heyrovsky was appointed assistant professor in the newly established Fig. Apparatus for measuring current-voltage curves in with the hitherto use of solid electrodes. After the mean values of the current oscillations were plotted as a function of the voltage applied to the electrodes. In November of the same year. The height of the current steps was proportional to oxygen concentration in the solution. Later it was shown that even oxidation processes can be followed. Usefulness for analytical chemistry of the electrolysis with dropping mercury electrode appeared straightforward. the 10th of February 1922. for which 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. 4. which later received the name "polarography". Masuzo Shikata and Jaroslav department of physical chemistry. Thanks to the minute size of the mercury drops the amount of oxygen consumed in the electrolytic reaction was completely negligible. reflected from the mirror of the galvanometer. and followed motions of the luminous spot. Heyrovsky continued a systematic research of electrolysis. In April of 1922. about 0.8 V apart. corresponding to the highest value of 2. with its highest hydrogen overpotential of all metals. he connected a sensitive mirror galvanometer. 1923). 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.0 applied volts. It was the first polarization curve obtained with the dropping mercury electrode. first with the dropping mercury cathode. and in a relatively narrow positive potential range. Masuzo Shikata. The latter article attracted the attention of a young Japanese scientist. to the extent that he came to Prague in 1923 to learn the new method on the spot. and students as well as interested colleagues were readily joining him in his original research. In contrast Fig. Dr. That day can be considered as the date of birth of the method. The instantaneous current oscillated rhythmically according to the regular growing and falling of the drops. curve turned out to be exactly reproducible.In the afternoon of Friday. the resulting polarization curve showed two equally high steps of current increase. although limited by anodic dissolution of metallic mercury. Heyrovsky and Shikata attended the "General Discussion on Electrode Reactions and Equilibria" of the Faraday Society in London. the dropping mercury electrode then can serve also as an anode. this electrolysis with dropping mercury electrode. an English version appeared in the "Philosophical Magazine" in (December. on the measuring scale (Figure 3). and the position of the steps on the voltage scale appeared to be values characteristic of oxygen. provided with a lamp irradiating the mirror. 1923. and a final steep increase of current out of scale. as at the beginning various reduction processes were studied. offers the widest attainable range of potentials in the negative direction.
This considerably spurred the further development and the spreading of polarography. which became the cornerstone of the Japanese polarographic school. and in a 1925 special issue of the Dutch journal "Recueil des Travaux Chimiques des Pays Bas". and on the 30th of March 1924. xray spectroscopist Dr. 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 in his luggage he carried one of the first polarographs. 5. were preoccupied with the search for the new chemical element No 75. The polarograph shortened the time of recording polarization curves from hours to minutes and. Vaclav Dolejsek. The result proved successful. were Dr. exactly reproducible measurements. Moreover. and polarography was going to be the primary subject of research in his department of physical chemistry. polarography brought the fulfillment of the Nernst's idea of an electrochemical analogy to spectroscopy (Figure 6). then author of the very first textbook on polarography. Fig. Noddack. In 1925 Shikata left Prague for home. The paper was entitled "The polarograph". it automatically provided an objective document of with polarograph. contrary to his previous belief. The problem of Kucera's anomaly was not forgotten: with Kucera´s assistant. Heyrovsky has proven with further polarographic experiments that. and I. who called it "rhenium". At that time. meaning an instrument for recording the process of electrolytic polarization. This aspect was discussed at length between Heyrovsky and Shikata. Thus. "Polarographic spectrum" – curve of polarographic reduction of seven different cations. and he conceded the discovery of the new element to W. a paper was published by Heyrovsky and his coworkers describing the new device of Heyrovsky and Shikata. However. polarographic analysis allowed determination of electroactive species in 10 µM concentration even in a minute volume of solution. Among other foreign scientists who visited Prague. Dr. accompanied by changes of . Fig. Wiktor Kemula from Poland. Although it was not specified in that paper that the instrument should be used solely for measurements with the dropping mercury electrode. as part of a special series of eleven papers on "Researches with the dropping mercury cathode". Rudolf Simunek.The only drawback of the promising new method was the cumbersome way of manual recording of the curves. Heyrovsky and his friend. and Dr. in order to learn polarography at the early stage and to introduce it in their own countries. The first decade In 1926 Heyrovsky became full professor. the method of electrolysis with that kind of electrode has gradually acquired the name "polarography". 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 manganese ores did not contain element No. 6. 75. 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. Later it was explained that both maxima were caused by the streaming of the solution around the mercury drops when electrolytic processes. Scheme of automatic measuring circuit moreover. Giovanni Semerano from Italy.
at lower concentrations the diffusion current is overlapped by higher charging current. Such titrations. the Ilkovic-Semerano circuit is included in commercially produced polarographs. by combination of the Nernst and the Ilkovic equations one arrives at the Heyrovsky-Ilkovic equation of the diffusion-controlled polarographic . and to measure the change of the limiting current as function of concentration in the course of a titration. For quantitative analytical measurements it is not necessary to record the whole curve. have later become known as "amperometric" titrations. When an electroactive substance is present in the solution. Thus. The charging current. 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. within the range of the limiting current. the currents should be about 10% higher than predicted by the Ilkovic equation. who in 1934 derived the equation of electrolytic current. two polarographic capillaries provide about the same current when the rate of flow of mercury through them (in milligram/second) is equal. Professor Kucera. Polarographic curves showing constancy of "halfwave potential" of Cd2+ ion reduction at different concentrations of CdCl2. were taking place at the electrode – the streaming was rinsing the mercury surface. it limits to this concentration the sensitivity of simple polarographic measurements. Theoretical explanation of these experimental facts was soon provided by Heyrovsky's assistant. Ilkovic with Semerano suggested sending through the galvanometer an empirically selected artificial counter-current decreasing with applied voltage. Almost twenty years later. Since then. Slovak physicist Dionyz Ilkovic. 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. and it increased transport of the electroactive substance to the electrode increasing the electrolytic current on the polarographic curves. it manifests itself on the polarographic curve as a stepwise increase of current. unfortunately. Jaroslav Koutecky. has an average value of the order of diffusion currents corresponding to about 10 µM concentration of an electroactive substance. in the same solution. The equation was derived under the simplifying assumption of linear diffusion. which would thus compensate to some extent the unwanted charging current. 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. unlike the diffusion current. Heyrovsky and Ilkovic considered the simple common case of an electroactive substance transported in the solution towards the electrode by diffusion. 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. 7. The first impulse came from Kemula. it is sufficient to apply to the electrode a constant potential. Fig. and undergoing a fast and reversible exchange of electrons with the electrode. or of the wave. Then.adsorption of the electroactive species. did not witness these results – he had passed away untimely in early 1921. the equation was precisely recalculated for spherical diffusion by another theoretician of the Prague group. 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. According to his results. increases linearly with applied voltage. originally called "polarometric". 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 shape of which can be regarded as a wave. He found that. who studied the most common type of polarographic currents where the electroactive species arrives to the electrode by diffusion. and agreed well with experimental results. a measure of concentration of the substance in the solution. is the limiting current. In the course of the first decade of polarography. The height of the step. controlled by the rate of diffusion of the electroactive species to surface of the dropping mercury electrode. seemingly increasing the surface tension on the electrocapillary curves. As the mean charging current. In order to derive an equation for the whole polarographic wave. which is basically inherent in polarographic measurements.
. Rudolf cirrhosis hepatic 6) atherosclerosis. it strongly depends on pH of the supporting solution. has been called the half-wave potential. at which the current reaches one half of the total waveheight. proteins yield a prominent catalytic "double-wave". included in 1936 in the second volume of the well known series Fig. In German speaking countries. Heyrovsky and his senior friend. as Carnegie Visiting Professor. and it occurs with compounds which are not necessarily electroactive. he also had Heyrovsky's Czech textbook from 1933 translated into Russian. containing ions of cobalt. polarography became first known from a chapter by Heyrovsky. Bottger from Leipzig University. P. lectured for five months at universities in California and in the middle and eastern States. 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 great number of diagnoses: 1) status febrilis 2) tumor hepatis electroinactive substances can thus be followed susp 3) ca. For a reversible redox-system the half-wave potential. 8. Brdicka. 9. edited by University. independent of concentration (Figure 7). is constant. Dissemination of polarography in USA was initiated in 1933 by Heyrovsky. this polarographic reaction was used in many countries over several decades as a diagnostic tool in treatment of cancer (Figure 8). Vernadskii. ventriculi susp 4) normal serum 5) polarographically. which accepted papers in English and French.wave. Heyrovsks's second assistant. mediates transfer of hydrogen ions from solution to close contact with Fig. Polarographic "Brdicka reaction" of negatively polarized mercury surface. and he invited Heyrovsky to lecture on polarography on the occasion of Mendeleev's 1934 centenary celebrations in Russia. Values of "E½" of various electroactive substances have been since listed in many textbooks and manuals. Professor Emil Votocek from the Prague Technical University. The potential. Dr. "E½"has become an important symbol in electrode kinetics. it appears in the negative range of potentials. 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. which became a model for W. this current is much higher than the diffusion current. polarography in Soviet Union was spurred by the Russian geochemist A. discovered a sensitive catalytic hydrogen-evolution reaction of proteins: in buffer solutions of pH about 9. also a different type of polarographic current was observed: as a rule. With the intention of making the results of Czechoslovak chemists known abroad. the "Collection" kept publishing all important results of the Prague polarographic school. the catalyst. indicating growing interest in the method. who. like proteins or alkaloids. denoted as "E½". Apart from diffusion currents. The main pioneer and teacher of polarography in the USA over several decades was Professor Isaak Maurits Kolthoff. The interest in commercial instruments. started in 1929 the monthly journal "Collection of Czechoslovak Chemical Communications". who sent his coworkers to learn the method in Prague. 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. where they undergo blood sera of different patients with following reduction to gaseous hydrogen. The first polarograph built at the "Physikalische Methoden der analytischen Chemie".
The next year he was invited by Svenska Institutet to lecture in Sweden and in Denmark. polarography. and Heyrovsky. he introduced what he called "oscillographic polarography". was established in the country in 1953. for that purpose. 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. Heyrovsky was able to continue working in his laboratory. Heyrovsky was appointed director of the institute. which appeared in German published by Springer in Vienna. after ten years it was already at 900. That technique clearly displayed reversibility of the processes involved. his further invitations to conferences and to lecture tours abroad were being turned down without official reason. most of them submitted their contributions to the congress proceedings. the world situation was not very favorable for such a project. oval-shaped curve. and the directorship of the Department of Physical Chemistry was taken over by Brdicka. Heyrovsky. and due to forced isolation of Czech experts from their western colleagues. Minnesota. Thanks to the help of his anti-nazi colleague. and accelerated polarographic analysis from minutes to seconds. The dropping mercury electrode was thus supplying new topics for general electrode kinetics. In the years after the war. with cathodic and anodic branches opposite each other. and he began to use cathode-ray oscilloscope in polarographic research. Czechoslovakia was occupied by the German army. German physical chemist Professor Johann Bohm. Complying with the possibilities of electronic technology at that time. to introduce and supervise its practical applications in the country. Heyrovsky visited several universities in the UK. As a guest of the British Council in 1946. which appeared in three volumes. to finish his major textbook on polarography. with his coworker Dr. he opened the wide field of polarographic currents controlled by chemical reactions. That method allowed the study of fast electrode processes. This sounded very good. was using a mercury jet electrode. as he was not politically trusted by the regime. and intending to try another type of electrolytic polarization. By that time. however. as institute director. When the new Academy of Sciences. who had in the meantime become full professor. and to control the state-organized production of polarographs. free of teaching duties. The task of the newly established academic Institute was to carry out basic research in all fields of polarography. Because of political division of the world. During World War II. nevertheless. the electrolytic processes appeared as indentations. lecturing on polarography. The organizer of the congress was the "Institute of Polarography". 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. on such a curve. Czechoslovakia had become part of the Soviet bloc and potential participants from abroad were not admitted to the country. 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. with his junior coworker Karel Wiesner. Edgar Verdier spent several months in Prague before the outbreak of World War II doing research in polarography. Jindrich Forejt. The French chemist Dr. and. the progress of technology in the entire eastern .an analytical chemist at the University of Minneapolis. polarography was among the five most often used methods of chemical analysis. The first international congress on polarography was organized in Prague in February of 1951. according to Soviet example. was nominated for membership in the Academy. He used this time. the Institute of Polarography was included in it. after returning home he wrote the first French textbook on the subject. 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. as a modern analytical technique. He provided a general treatment of a two-stage reversible polarographic reduction with formation of semiquinones and their dimers. he visited Heyrovsky's laboratory several times in the nineteen-thirties. Ilkovic's work in building the polarographic theory was continued by Rudolf Brdicka. however. one of eight new institutes founded in 1950 by the communist government in order to boost research in science and technology. he introduced the concept of polarographic currents controlled by adsorption of the electroactive species. to collect and publish polarographic bibliography. His teaching duties at the University were reduced. 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. and the Czech universities were taken over by Germans.
In addition to the original. introduced the "commuter polarography". developed by Dr. oscillopolarographic" curve obtained with a mercury-jet electrode. Kucera. Shortly after the war. for which Sevcik derived a corresponding equation. B. Professor Bruno Breyer in Australia introduced "ac" polarography (Figure 10). Geoffrey Cecil Barker in the Atomic Energy Research Establishment at Harwell. the curves were peak shaped. and rapid methods of analysis. This way. or "dc". especially in the field of electronics. 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. essentially eliminating the charging current component. instead of direct current. Barker's laboratory became a rich source of further development of polarographic instrumentation. in which small amplitude ac voltage was superimposed on the dc voltage applied to the dropping electrode. or peaks. Dr. the charging current has been eliminated to a large extent. is the "square-wave polarography". and electroactivity and other properties of its prospective intermediates. Prominent peaks appeared on the curves also when the electrode capacity was changed by fast adsorption or desorption of a surface-active compound. in which.bloc. In this way. Later. polarography. .c. In the background picture of professor B. placed on a more rigorous basis. Mirko Kalousek. Oscilloscope displaying an "a. Heyrovsky's junior coworker. 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. and the sensitivity of polarographic determinations was increased by about two orders of magnitude of concentration in the solution. Instead of the polarographic waves. E. 10. as the method and equation were published independently at the same time by A. two different alternating currents have been recorded separately – that flowing in-phase with the applied alternating voltage. and for study of adsorption processes in particular. and that flowing out-of-phase with it. the Prague polarographic school was gradually losing its exclusive position in instrumental and theoretical polarography. as function of the applied mean dc voltage. The technical progress of the post-war world required highly sensitive. From the nineteen-fifties on. Such curves were characterized by maxima. Barker combined all his highly complex electronic techniques solely with the dropping mercury electrode. Instead of the usual sine-wave shape. as he trusted its exquisite properties as a scientific tool. or the difference of currents in the differential version. and one or more current-voltage curves appeared on the screen of the oscilloscope. brought the sensitivity of polarographic analysis to its limit – in these methods. in course of recording the curve. Another Heyrovsky's pre-war assistant at the University. simple form of polarography needed further modifications to meet these requirements. a single potential pulse is applied to each mercury drop. is measured before the end of drop-time. The original. Similar to ac polarography. "Radio frequency polarography" and "Intermodulation polarography" have been introduced for solving problems in advanced electrode kinetics. according to whether one or several voltage pulses were applied to one drop. In that way the complex impedance of the dropping electrode is measured which provides exact data for electrode kinetics in general. and the current. Pulse polarography. Fig. Randles in Birmingham. the ensuing alternating current was measured. was lagging behind. electronic engineer Augustin Sevcik. UK. Members of the Heyrovsky's group tried to keep pace with the international development. and. the potential of the dropping electrode could be commuted with variable frequency to a certain selected constant potential. Sevcik in Prague and by Professor J. in place of half-wave potentials of dc polarography. 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. specific. and especially its differential version. the mathematical formulation of the corresponding current-potential curve is known as the Randles-Sevcik equation. though much more sophisticated in detail.
. however. a linear voltage scan is applied and the currentvoltage curve is recorded. stripping voltammetry. previously formed at positive potentials) and adsorptive stripping (usually desorption of species previously accumulated by controlled adsorption). That meant that they recorded the whole curve with one single drop of mercury (like in the single-sweep polarography). according to the official IUPAC nomenclature the method thus introduced is not "polarography" any more.In the nineteen-fifties. Professor Emil Palecek developed the "adsorption transfer voltammetric stripping" in 1986 for electroanalysis of biological macromolecules – in this technique. cathodic stripping (usually reduction of compounds with mercury. the used drop was knocked off and a new one was produced from the capillary. of which three modifications are distinguished: anodic stripping (usually dissolution of a metal from the previously formed amalgam). Barker's instrumental techniques developed for the dropping electrode can be. the hanging drop carries its whole "history" along. C. As this time a stationary electrode has been used. after the curve was completed. used with the hanging mercury drop electrode. displaying the electrode reaction in reverse. the very limits of analytical sensitivity can be reached with the differential pulse adsorptive. This voltammetric operation is known as "stripping". for a proper study by some of the stripping techniques. thus. after an exactly measured time of electrolysis. several polarographers – Drs. and Dr. The G. The curves are still reproducible. rare substances are accumulated by adsorption from a minute volume (millionth of a liter) of solution to the surface of hanging mercury drop. Zenon Kublik and Professor Wiktor Kemula in Warsaw. started using the hanging mercury drop electrode instead of the dropping mercury electrode. a product of the electrolytic process is quantitatively accumulated at the electrode surface. unlike the dropping electrode. 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. This simple fact has been utilized to produce a considerable increase of sensitivity in electroanalysis: using a selected constant potential and controlled stirring. and very often are. either in the form of an amalgam or in the form of an adsorbed layer. for example. that electrode with the adsorbed layer is then transferred to a normal cell with usual volume of suitable electrolyte. cathodic or anodic. it has to be called "voltammetry".
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