Alexander Frumkin

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Alexander Naumovich Frumkin (Алекса́ндр Нау́мович Фру́мкин) (October 24, 1895 – May 27, 1976), Russian/Soviet electrochemist, member of the Russian Academy of Sciences since 1932, founder of the Russian Journal of Electrochemistry Elektrokhimiya^[1] and receiver of the Hero of Socialist Labor award. The Russian Academy of Sciences' A.N. Frumkin Institute of Physical Chemistry and Electrochemistry is named after him.^[2]

Frumkin was born in Kishinev to a Jewish family; his father was an insurance salesman. His family moved to Odessa, where he received his primary schooling; he continued his education in Strasbourg, and then at the University of Bern. Frumkin's first published articles appeared in 1914, when he was only 19; in 1915, he received his first degree, back in Odessa. Two years later, the seminal article "Electrocapillary Phenomena and Electrode Potentials" was published.

Frumkin moved to Moscow in 1922 to work at the Karpov Institute, under A.N. Bakh. In 1930 Frumkin joined the faculty of Moscow University, where in 1933 he founded -- and would head until his death -- the department of electrochemistry.^{[citation needed]}

Frumkin's most fundamental achievement was the fundamental theory of electrode reactions, which describes the influence of the structure of the interface between electrode and solution on the rate of electron transfer. This theory has been confirmed and extended within the framework of contemporary physical electron transfer models. Frumkin introduced the concept of the zero charge potential, the most important characteristic of a metal surface. Alessandro Volta's question -- a topic of discussion for over 120 years -- about the nature of the EMF of electrochemical circuits was resolved using Frumkin's approach. Frumkin developed the Frumkin isotherm, an extension of the Langmuir isotherm in describing certain adsorption phenomena. Frumkin's students developed novel experimental methods that would, in time, become standard. Several applied electrochemical processes, including ones related to chemical sources of electrical power, industrial electrolysis, and anti-corrosion protection, were successfully developed under Frumkin's supervision.

Frumkin was married three times, including a brief first marriage to Vera Inber.

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Alexander Naumovich Frumkin (Алекса́ндр Нау́мович Фру́мкин) (October 24, 1895 – May 27, 1976), Russian/Soviet electrochemist, member of the Russian Academy of Sciences since 1932, founder of the Russian Journal of Electrochemistry Elektrokhimiya[1] and receiver of the Hero of Socialist Labor award. The Russian Academy of Sciences' A.N. Frumkin Institute of Physical Chemistry and Electrochemistry is named after him.[2]

Alexander Naumovich Frumkin b. October 24, 1895, Kishinev, Moldaviya, Russia d. May 27, 1976, Tula, Russia

Prof. A.N. Frumkin in the last years of his life Alexander Naumovich Frumkin was "father" of Russian electrochemistry. The most fundamental achievement of the outstanding work of A.N. Frumkin and his school was the creation of the fundamental theory of electrode reactions, which considers the influence of the structure of the electrode/solution interface on the rate of the elementary electron transfer event - the theory of the slow discharge. This theory didn't become obsolete, it even received confirmation and development within the framework of the contemporary physical models of the electron transfer and reorganization of polar medium. A.N. Fumkin introduced the concept of the zero charge potential, the most important characteristic of a metal surface. The Volta's problem about the nature of EMF of electrochemical circuits, which was the subject of scientific discussion for more than 120 years was successfully solved using the approach developed by Prof. Frumkin. Novel experimental methods that became classical were developed under supervision of Prof. Frumkin. Many applied electrochemical projects, for instance, projects related to chemical sources of electrical power, industrial electrolysis, protection against corrosion, etc., were successfully developed under supervision of Prof. Frumkin. The most famous Frumkin's book "Kinetics of Electrode Processes" was published in 1952. Alexander Naumovich Frumkin was born on October 24, 1895, in Kishinev, capital of Moldaviya (now Moldova), which was a part of Russian Empire. He was born in a Jewish family, the son of Naum Efimovich Frumkin (1857–1934), an insurance agent, and Margarita L’vovna Frumkina (1863–1949). His family moved to Odessa, where he attended the St. Paul’s gymnasium. Alexander Frumkin was already well known for his extraordinary intelligence. Once he got into a dispute with his teacher and appeared to be winning, so the teacher called in the local rabbi to adjudicate. When the rabbi realized that the young Frumkin was concerned he said that the pupil must be right, because he could not believe that Frumkin could be wrong.

A.N. Frumkin at the beginning of his scientific career On leaving school in 1912, Frumkin went for further study to Strasbourg and then became a demonstrator in the University of Bern. There he worked on the oxidation of phosphorus with Kohlschütter, publishing two papers on this subject with him in 1914; he was then 19 years old. Back in Odessa, he obtained his first degree in 1915 from the Faculty of Mathematics and Physics in the Novorossiya University (now the University of Odessa). His subsequent job as a laboratory assistant in a metallurgical lab laid the foundations of his passion for electrochemistry. The first result was a 1917 paper on the movement of mercury drops under the influence of an electric current, a topic he returned to much later. From 1917 to 1922 Frumkin worked in the physicochemical laboratory of Prof. A.N. Sakhanov. There Frumkin wrote his first major work: his thesis “Electrocapillary Phenomena and Electrode Potentials,” published in Odessa in 1919. It became a classical work for many generations of electrochemists. Besides containing a masterly survey of current views on the title problems, it contains several notable contributions, among which many of the major themes of Frumkin’s later work may be seen to have their origin. The first of these was a careful experimental test of the basic equations of electrocapillarity. He showed that the charge, measured directly from the current required to keep a dropping mercury electrode at constant potential, was the same as that found from the slope of the electrocapillary curve, even in the presence of strongly adsorbed ions or molecules. At the same time he established the identity of the potential of zero charge (PZC) determined by several methods. He then discussed in detail the adsorption of inorganic ions and showed how Gibbs’ equation may be used to derive surface excesses from electrocapillary curves. These quantities were also calculated from the Gouy–Chapman diffuse layer theory and compared with his own experimental results. Measurements of the adsorption of organic non-electrolytes and electrolytes were used to show the nature of the potential dependence of the adsorption isotherm. Electrocapillary curves in nonaqueous solvents were used for the calculation of the double layer capacity which was then shown to have no relation to the bulk dielectric constant of the solvent. The final chapters on the electrocapillary properties of amalgams and molten metals and on electrode potentials go to the heart of one of the basic problems of electrochemistry: the origin of the emf of a galvanic cell. This led on the concept of PZC as a property of the metal. This thesis is an astonishing achievement for a young man of 24 isolated from contact with other workers on these subjects (although the isolation from current views may have been an advantage!). He published the first part of his thesis in English in the British journal Philosophical Magazine in 1920 and the part on non-aqueous solutions in German in the German journal Zeitschrift für physikalische Chemie in 1923. He sent the two papers off during the chaotic post-revolutionary time, wondering whether it would get to London and whether he would ever hear any more about them. Since the doctorate degree was abolished during the revolution of 1917, he did not get a degree. By the time it was reinstated, he had no need of one. After the revolution, a lot of state institutions of various kinds had been established in Russia in order to provide education for the working people who had no access to this under the Tsar’s reign. In 1920 Frumkin became professor in one such institution in Odessa, the Institute for People’s Education.

At that time Odessa was a center where young Soviet intelligentsia gathered, and he took an active part in its cultural activities. Outstanding in that intellectual society was the poetess Vera Mikhailovna Inber (b. Odessa 1890, d. 1972), later well known for writing about her experiences during the siege of Leningrad in WWII. Frumkin became friendly with her and in due course they married. This marriage, however, did not last long because of their incompatible natures. She was very keen on social life, while he was of course dedicated to science. ________________________________________ Vera Mikhailovna Inber - the first wife of A.N. Frumkin A.N. Frumkin moved to Moscow in 1922 on the invitation of Aleksei Nikolaievich Bakh, director of the Karpov Institute. This Institute was founded in 1918 to undertake fundamental research related to industrial problems. Frumkin arrived with well thought out plans for his research based on profound mathematical analysis coupled with elegant experiment. While continuing his investigation of the metal–electrolyte interface, he began work on the electrical properties of the air–electrolyte interface, using the technique devised in 1896 by F.B. Kenrick (of Toronto, while he was working in Ostwald’s laboratory in Leipzig) for measuring the Volta potential between two electrolytes. This was an experiment of great difficulty. Frumkin was successful in studying the change in surface potential due to the adsorption of ions at an aqueous surface and was the first to connect the observed shifts of the Volta potential with the orientation of molecular dipoles, but in 1926 he could not get satisfactory results for the contact potential between mercury and an electrolyte. He was delighted and full of admiration when, much later, John Randles, working in Birmingham, achieved this and provided the basis for the calculation of the real solvation energy of single ionic species as well as the only measurable “single electrode potential.” Frumkin and his co-workers made extensive measurements of the adsorption of organic compounds on mercury, for which he proposed a quantitative model based on a semi-empirical adsorption isotherm that is universally known as the Frumkin isotherm. He summarized his work on the double layer on mercury in a comprehensive review in the series Ergebnisse Exakten Naturwissenschaft in 1928. Following studies on liquid gallium and amalgams he proposed explicitly the concept of PZC as a characteristic property of the metal closely related to the Volta potential. During the 1920’s he also began work on porous solids, such as platinum black, charcoal, and silver iodide. His co-worker in this was his second wife, Amaliya Davydovna Obrucheva (b. 1894, d. 1968).

Frumkin's isotherm

Frumkin isotherms for various values of g. The dotted line corresponds to g = 0, which is identical to the Langmuir isotherm. The Frumkin's isotherm that describes adsorption phenomena taking into account interactions between the adsorbed species became the well known and important development of the Langmuir's isotherm. To make a realistic model of adsorption, Frumkin assumed that there is some interaction between the adsorbates. Using a mean-field approach, let G = G0 + . If the adsorbates attract one another, then  > 0. If they repel, then  < 0. In the case that  = 0, we recover the Langmuir result. Typically this isotherm is written as

where g = / kT. This is known as the Frumkin isotherm.

Prof. A.N. Frumkin - a young, but already famous scientist These first years of work at the Karpov Institute established Frumkin as a leader in the surface electrochemistry, and in 1928 he was invited to the University of Wisconsin at Madison as a visiting professor of colloid chemistry. When he returned to Moscow, he was made Deputy Director of the Institute, a post he would hold until 1946. In 1930 he was elected professor of the Lomonosov Moscow State University, where he was head of the department of electrochemistry which he founded. These distinctions culminated in 1932 when he was elected as full member of the Academy of Sciences of the USSR.

A.N. Frumkin with the colleagues, the Department of Electrochemistry (1967) Prof. Frumkin began to work at the Moscow State University in 1930. In 1933 he established the Department of Electrochemistry that was headed by him till the last days of his life. Fundamental study of electrochemical kinetics and adsorption on charged electrode surfaces was conducted under his supervision in this department. Prof. A.N. Frumkin was an outstanding organizer of science. He was the scientific director of the Karpov Institute of Physical Chemistry. In 1958 Prof. A.N. Frumkin established the Institute of Electrochemistry - the first electrochemical institute in Russia. A.N. Frumkin possessed surprising active creative activity even in the most difficult historical periods of Russia.

Although Frumkin’s work up to 1930 was so remarkable that it ensured his recognition as an international authority, there is some justification in regarding his work in the following decade as exceeding the earlier work in importance, since it provided the foundation stones of modern electrochemistry. The first of these in 1932 was the bridge between homogeneous catalysis and electrochemical kinetics in the identification of the Broensted coefficient with the electrochemical transfer coefficient. The second in 1933 was the marriage of the fields of surface chemistry and electrode reactions in a paper, which brilliantly used the earlier polarographic measurements of Herasymenko and Slendyk to give a quantitative account of the salt effect on electrode kinetics. This “Frumkin effect” is probably the most widely known of his work, papers are still being devoted to this effect. The most dramatic demonstration of the effect of the double layer potential on electrode kinetics came with the study of anion reduction by Kryukova in 1949, which was explained shortly after by Frumkin and Florianovich. Here the effect of a negative outer Helmholtz potential in repelling the reacting anion in dilute solution led to a sharp decrease of the rate of reduction as the potential became more negative. Studies on different metals having different PZC’s gave unambiguous proof of the origin of this effect. These kinetic and double layer studies led to his third major contribution, which was to show the necessity for rigorous cleanliness in work on surface electrochemistry. Thus his co-workers achieved the first reproducible results on electrode kinetics on solid electrodes as well as demonstrating that directly measured capacities on a stationary mercury electrode agreed with the second differential of the electrocapillary curve. In achieving these conditions for a smooth platinum electrode, he and Ershler invented the thinlayer electrode, which was rediscovered decades later. Having established the direct measurement of the double layer capacity as a valid method, Frumkin and Vorsina studied the concentration dependence and showed that the diffuse layer capacity, calculated from the Gouy–Chapman model, played an important role in dilute solution — the sharp minimum of the capacity. He realized that this was an important method for determining PZC, especially for solid metals, and in 1948, with Borisova and Ershler, demonstrated this for a lead electrode. It is particularly noteworthy that he remarked on the broader minimum for the solid compared with that of the mercury electrode and attributed this to the heterogeneity of the surface, which would consequently have regions of different PZC. In his studies of electrode kinetics he analyzed the steady-state behavior, adapting the kinetic schemes used in heterogeneous catalysis; but most importantly, in 1940, with Ershler and Dolin, he was the first to use a relaxation method for the study of fast kinetics, when they used impedance measurements to study the kinetics of the hydrogen discharge on a platinum electrode. This was a decade before the work which gained Eigen, Norrish, and Porter the Nobel prize. In this work he also used the idea that the heterogeneity of the surface played a significant role. In 1951, with Melik-Gaikazyan, he extended the impedance method to the study of the kinetics of adsorption of neutral molecules. During the second World War, Frumkin was directed to Kazan where he undertook research of national importance connected with radiation chemistry. On this he worked with Natal’ya Alekseevna Bakh (the daughter of A.N. Bakh) who became head of the department of radiation chemistry at Moscow State University in 1949. When he returned to Moscow, he moved to the Institute of Physical Chemistry where he remained until 1958 when his own Institute of Electrochemistry was founded. Prof. A.N. Frumkin led a group of several hundred Russian scientists at the Institute of Electrochemistry of the Academy of Science in Moscow.

During this period he was joined by Veniamin Grigor’evich Levich who had studied with the great theoretical physicist Landau. This was the beginning of a close cooperation between experiment and theory. The first fruit in 1945–1946 was a fundamental analysis of the motion of mercury drops in an electric field, the topic of Frumkin’s first publication in electrochemistry. He regarded these papers with Levich as among his finest. This work led on to a quantitative analysis of the polarographic maximum. The collaboration with Levich also led to the development of the rotating disk electrode and the ring-disk electrode. As the number of his collaborators increased into the hundreds, many fine papers appeared. In 1960, with Gokhshtein, he used the negative resistance occurring in the reduction of peroxodisulphate to obtain an oscillating system. This has been much studied by others, but perhaps its most significant sequel is the vast study that Gokhshtein has made of the mechanical properties of solid electrodes, using vibrating electrodes. Once Frumkin was faced with a major non-scientific problem: the request of Levich to the authorities for permission to emigrate to Israel. After 30 years of close co-operation, this was a severe personal blow which he felt as a betrayal. Even in this he retained his sense of humor. Levich had been on holiday in Georgia where, he said, he had visited eight churches and one synagogue. When he related this, Frumkin said “I thought he would have visited eight synagogues and one church.” For some 20 years, particularly in the 1950s and 1960s, the huge group of Russian electrochemists headed by Prof. A.N. Frumkin was at the cutting edge of physical electrochemistry and stimulated much of the post-WWII work in this field in Europe and eventually also in the United States, where its influence was felt on work leading to the fuel cells used in NASA's early space flights. The domination of the Russian group was relinquished only when spectroscopic and computer-based techniques, which were easily available in the West, became essential to research in physical electrochemistry but were not available (because of the supply problems in Communist countries) to scientists in the Soviet Union. A.N. Frumkni was married third time on Emiliya Georgievna in 1968.

A.N. Frumkin in Chegem mountains (1938) Prof. Frumkin had very broad education and various interests. He loved painting, poetry, history, passionately loved journeys, particularly in mountains. Academician Semenov and other outstanding scientists were Frumkin's companions in these journeys. Besides literature, Frumkin was also enthusiastic about pictures, and his colleagues celebrated his seventieth birthday in 1965 with pictures of him in the styles of Gauguin (by A.A. Lopatkin) and Picasso (by O.A. Petrii and R.V. Marvet).

Graphically represented electrochemical functions studied by Prof. Frumkin are easily recognized by electrochemists. Some of these typical electrochemical plots have been collected in the portrait of Prof. Frumkin painted in the Picasso's manner. In this portrait you can also find two traditional electrochemical components: a capillary with a moving mercury drop that results in the polarographic maximum and a rotating-disk-ring electrode. Prof. Frumkin has greatly contributed in the development of these techniques. ________________________________________ Portrait of A.N. Frumkin in "Picasso's" style

Prof. Frumkin greatly contributed to the creation and development of scientific societies in many regions and cities of the USSR, particularly in Tartu, Riga, Alma Ata, Tbilisi. The theme of Frumkin-traveller inspired Prof. Aleksey A. Lopatkin to paint the Frumkin's portrait in the Gogen's manner. ________________________________________ "Frumkin on Tahiti island" painted by Prof. Lopatkin in the Gogen's style Frumkin himself has been called in an obituary, "The Great Academician", not only because of his wide knowledge, including contact with the current humanistic literature in Russia, England, Germany, and France (he spoke fluently the language of all four), but because he was a leading member of the Academy of Sciences of the Soviet Republics, the most prestigious organ of Russian science. He was in the best sense an active intellectual, and it seems appropriate to regard Frumkin as the successor to the great Nernst. He was eager to discuss virtually any subject. He did not agree with Darwinian theory of evolution, asking how it would be possible for the mechanism of the human eye to develop via a series of accidental changes in gene structure. He showed an encyclopedic knowledge of flowers and trees. In spite of these virtues, Alexander Naumovich (his name to close colleagues) did not believe in the objective evaluation of a scientist's work. Asked his view of a specific scientist, his reaction was a frown or a smile. The frown was succeeded by a terse expression of disgust and the phrase "Terrible work.," the smile was succeeded by a lively "Him I like. Excellent work."

Late photos of Prof. A.N. Frumkin

Alexander Naumovich Frumkin , the academician of the USSR Academy of Science since 1932, the member of ten foreign scientific academies, the laureate of many Soviet prizes, the laureate of the Palladium medal of the American Electrochemical Society, was the most important Russian physical chemist and the founder of the large number of the most important directions of contemporary electrochemistry. Two volumes of the Journal of Electroanalytical Chemistry were published to the Frumkin's eighty year anniversary collecting scientific papers dedicated by the leading scientists to the anniversary date. ________________________________________ A.N. Frumkin and J. O'M. Bockris (U.S.A. 1960)

Till the last days of his life he preserved the outstanding scientific activity and bright mind. He died on May 27, 1976 during the scientific conference on Electrochemistry of Organic Compounds in Tula (a city in 200 km south from Moscow). (I was also at this conference and saw him in his last day.) The monument of the work of sculptor Sidur, a symbolic image of Frumkin's creativity stands on Alexander Naumovich's grave in the Novodevich'ye cemetery in Moscow. ________________________________________ Monument on the grave of Prof. A.N. Frumkin

This picture was made much before Prof. Parsons was awarded the medal and when A.N. Frumkin was still alive. Late in 1999, in order to honor Professor Alexander Naumovich Frumkin and his many contributions to science, particularly to the field of fundamental electrochemistry, the International Society of Electrochemistry (ISE) has established the “Frumkin Memorial Medal.” The award was founded by Professor E.G. Perevalova-Frumkin, the Frumkin Institute of Electrochemistry of the Russian Academy of Sciences, and the Department of Electrochemistry of the Faculty of Chemistry, Moscow State University. According to the Medal Statute adopted by ISE, the award, to be given once every two years, recognizes the outstanding contribution of a living individual over his/her life in the field of fundamental electrochemistry. The first Frumkin Memorial Medal has been awarded to Prof. Roger Parsons (Great Britain). It was presented on September 5, 2000, during the 51st ISE Meeting in Warsaw. ________________________________________ Professor Roger Parsons (left), the first recipient of the Frumkin Memorial Medal of the International Society of Electrochemistry, Prof. Lev I. Krishtalik (center), Prof. Alexander Naumovich Frumkin (right)

This page was created by translation of the original Russian pages devoted to Prof. A.N. Frumkin: Frumkin's official biography, Frumkin in mountains, Frumkin's unofficial biography, one more Frumkin's biography. Some additional photos have been found in different Russian books and journals and were scanned. A part of this text originates from the book: J.O'M. Bockris, A.K.N. Reddy, M.Gamboa-Aldeco, Modern Electrochemistry, Second Edition, Fundamentals of Electrodics, Vol. 2A, Kluwer Acad., 2000, p. 1070-1071. A large fragment from the paper of Roger Parsons (Russian Journal of Electrochemistry, Vol. 37, No. 6, 2001, pp. 549–553. From Elektrokhimiya, Vol. 37, No. 6, 2001, pp. 647–652) was also used. ________________________________________

(updated & corrected on April 16, 2003)