nikolai semenovich kurnakov

California Association of Chemistry Teachers

For more than six decades, Nikolai. Semenovich Iiurnakov, one of Russia's most distin- guished and versatile chemists, was an active force in the development of science and technology both in his homeland and abroad. He is regarded as the founder of a new chemical discipline, physicochemical analysis, probably the largest contemporary school of Soviet chemistry vith applications in numerous branches of technology.

George B. Kauffman Fresno State College

Fresno, California and Alexander Beck

University of California Berkeley

Nikoloi Semenovich ~ v r n o k b v 11 860-1 941). Academicion, Acodemy of Sciences of the U.S.S.R

Nikolai Semenovich Kurnakov

A beloved teacher as well as a creative theorist and experimentalist of the first rank, Kurnakov organized and served as director of a number of laboratories, research institutes, and national and international commissions. He was largely responsible for the construc- tion of several nenr chemical. mining. and metallurgical

Presented before the Division of the History of Chemistry at the 140th Meeting of the ACS, Chicago, September, 1961.

'Recent centennial articles include MAUROV, 5. Z., Izuesl. A h d . Nauk S.S.S.R., Otdel. Khim. Nauk, 2073 (1960); BEREZHNO?, A. S., Ukrain. Khim. Zhur., 26, 684 (1960); ZWAGINTSEV, 0. E., Z h w . Priklad. Khim., 33, 2285 (1960); IILOCRKO, M. A,, Zhw. Ob~hchei Khim., 30, 3509 (1960); and "Nikolai Semenovich Kurnskov v vospominaniyekh savremen- nikov i uchenikov," Akad. Nauk S.S.S.R., Moskva, 1961.

plants and was a pionecr in the systematic exploitation of Russian mineral resources, especially platinum, potassium, and magnesium. His more than 200 published articles and texts testify to his immense produc- tivity in the widely-scattered fields of mineralogy, metallurgy, metallography, and halurgy (salt t,ech- nology), and inorganic, analytical, organic, and physical chemistry. Through his active participation in scientific, public, and governmental affairs, he became a well-known public figure and a recipient of numerous honors.

Although many articles describing Kurnakov's achievements have appeared in Russian journals (1-%I).' some even before his untimelv death in 1941. no ackbunt of his life and work has yet been published in English. In their attempt to fill this gap, the present authors have made extensive use of these extremely informative articles, some of which are general and some highly specialized. The latter type often describe in minute detail the various aspects of his highly-diversified career.

Life

Kikolai. Semenovich Kurnakov was born in Kolinsk, Vyatka province, on December 6 (Sovember 24, O.S.), 1860, but spent his childhood in the village of Zhedrin, Kizhegorodskai3 province. His father, an army officer, died in 18li8, leaving him vith his mother (Varvara Aleksevna Kurnakova, nee Mezentseva) and brother. From 1871 to 1877 he received the eauivalent of our high school education a t the military gymnasium at Nizhni Kovgorod (now Gorki). Distantly related to the great organic chemist Markovnikov, he made an early choice of a career, setting up a home laboratory at the age of fourteen. Immediately after graduation, he entered the Saint Petersburg Gornyi Institut (hlining Institute) where independent research under chemiqts Sushiii and Lisenko and mineralogist Yeremyev resulted in his first publication, a crystallographic study of alum and Schlippe's salt (?rTaaSbSc.9HtO) (28). Aftergradua- tion from the Zarodskoe Otdelenie (Factory Section) in 1882 with the degree of Gornyi Inzhener (Mining Engi- neer), he was retained by the chemical laboratory of the institute.

Kurnakov's interest in chemical industry would not permit him to remain exclusively a laboratory worker,

44 / Journol of Chemical Education

and he now began the first of his many trips to plants and factories. In the summer of 1882, together with Prof. N. A. &a, he investigated the smelting operations a t the Altai (Siberia) refineries. The following year during a trip abroad, he toured the laboratories of the Frei- burg Akademie where he attended the lectures of Winkler and Richter. A detailed study of salt manufacturing in Prussia, Lorraine, Wiirtemberg, Baden, Bavaria, and the Austrian Tyrol made during the summer of 1884 resulted the following year in his dissertation for the position of ~ d z n k t (Assistant) in metallurgy, halurgy, and assaying, a post which he held for eight years. This work, "Isparitel'nye Sistemy Solanykh Varnits" (Evaporative Systems of Salt Boilers), containing the germs of Kurnakov's subsequent studies of salt equilibria, appeared long before van't Hoff's research on the Stassfurt salt beds. The eighties were years of great developments in physical chemistry; Kurnakov's work was in keeping with this trend.

Further scientifically-fruitful summer travels in- cluded: a chemical study of therapeutic mineral muds in the Crimean salt lakes (1894), which resulted in Kurnakov's introduction of the coefficient of metamor- phization, a new and important unit for the characteri- zation of natural salt solutions; a study of firedamp (methane) in the Donets Basin anthracite mines (1895) (25); work as an expert a t the All-Russian Industrial and Artistic Exhibition a t Nizhni Novgorod (1896); a visit to Germany and France to study methods for the investigation of detonating (oxyhydrogen) gas (1898); a trip as delegate to the International Congress on Chemical and Mining Industries and member of the Commission of Experts a t the World's Fair, both in Paris (1900).

In 1893, Kurnakov was appointed Professor of Inor- ganic Chemistry following the successful defense of his dissertation "0 Slozhnykh Metallicheskikh Osnova- nLkhn (On Complex Metallic Bases) in which he de- scribed the reaction of Pt(I1) and Pd(I1) isomers with thiourea, now known as Kurnakov's reaction (24). In 1899, be was appointed Professor of Analytical Chem- istry a t the G m y i Institut and organized the teaching of physical chemistry at the Saint Petersburg Elelctro- tekhnicheshi Institut (Electrotechnical Institute). In 1902, he was appointed Professor of General Chemistry at the St. Petersburg Politekhnicheskii Institut (Poly- technic Institute), which he had organized together with Mendeleev and Menschutkin; he held this post until 1930.

During the first decade of the 20th century, Kurna- kov was concerned with the solution of industrial problems such as platinum refining, metallic alloys, metallography, and salt manufacturing. During the same period, he played a vital role in the planning and con- struction of new laboratories a t the three institutes. The general chemistry laboratory of the Politekhniche- skii Institut, one of the largest of its kind, was a mile- stone in the building of laboratories in Russia. The accumulated pressure of his many duties forced Kurna- kov to abandon teaching at the Elektrotekhnicheskii Institut in 1908.

In 1909, Kurnakov was awarded the degree of Doctor of Chemical Sciences honoris causa by Moscow Univer- sity, became a contributing editor of the Zeitsehn'ft ,fur

anorganische Chemie, and was appointed a member of the Gornyi i Nauchnyi Komitet (Mining and Scientific Committee). In 1910, he directed studies of the Rus- sian Council on Platinum Refining, and the following year he went abroad to study methods of transporting warm sulfur waters. In connection with his work on the Russian Commission for the Study of Toxic Proper- ties of Commercial Ferrosilicon, he carried out chemical- metallographic studies of alloys of iron with aluminum, phosphorus, and silicon (25).

Official recognition abroad followed recognition at home. In 1912, Kurnakov was elected a council member in the Socidtb ehimipe and became a member of the Russian Department of the International Commission on the Nomenclature of Inorganic Compounds. As a - c.

delegate of the Russkoe Fiziko-Khimicheskoe Obshchestuo (Russian Physical-Chemical Society), he participated in the meetings of the International Association of Chemical Societies held a t Berlin (1912) and Brussels (1913). In 1913, he was elected vice-president of the Russian Metallurgical Society and became Ordinarnyi Akademik (Ordinary Academician) in chemistry at the Akademiz Nauk (Academy of Sciences). The laboratory of the academy had been inactive for a number of years, but it experienced a rebirth as a result of Kurna- kov's extraordinary organizational talent.

World War I brought new tasks for Kurnakov. He mas instrumental in the creation of a number of new institutes and commissions. In 1915, together with fellow academicians V. I. Vernadskii and A. E. Fersman, he organized and became assistant chairman of Ko- miss& po ImeheniGi Estestuenno Proizuodstuennykh Sil Rossii, KEPS (Commission for the Study of Russian Natural Productive Sources), a t the Academy. At KEPS, he established a Salt Commission, and the study of salt solutions and related problems occupied much of his time for the next few years.

Upon mobilization, Kurnakov became chairman of the newly-created Artillery Commission for the Study of Asphyxiating Gases where he conducted research both in the field and laboratory on the physiological action of war gases. From 1916 to 1918, he participated in the work of the chemical plant of the Military Industrial Committee in Petrograd. During the Civil War following the October (1917) Revolution, a trying period of frost: famine, and other disasters, when all organized life was completely disrupted, research continued in Kurnakov's laboratories. He even organized an expedition to investigate the formation of Glauber's salt (NaBOa 10H20) at Kara-Bogaz (26).

In 1919, he organized and hecame director (a position held until 1927) of the Gosudarstuennyi Institut Prikla- dnoi Khimii, GIPKh (State Institute of Applied Chem- istry) with facilities located at Vasil'yevskii Island on the Neva a t Petrograd, which had grown out of the first Russian laboratory founded by Mikhail Vasil'ye- vich Lomonosov (1711-65). Here scientific workers from the provinces gathered, especially during the summers, to work under Kurnakov's guidance. In the fall, they returned home with ideas and projects for the next few years. In this manner, Kurnakov dissemi- nated hiq ideas and expanded his rapidly-growing school.

In 1918 a t KEPS, Kurnakov founded and became director of the initially-small Institut Fiziko-Khimi-

Volume 39, Number I, January 1962 / 45

cheskogo Anulira (Institute of Physicochemical Analy- sis), and the following year he became editor of its Imestiia Instituta Fiziko-Khimiche~ko~o Analiza (now Imestiia Sektora Fiziko-Khimicheskogo Analiza); he held both positions until his death. The first volume of this journal contained a classic in halurgy, uiz., Kurnakov and Zhemchuzhnyi's study of natural salt deposits of marine origin (27). The year 1922 saw Kurnakov become director of the General Chemistry Laboratory of the Academy, director of the Institut po Izuchenilii Platiny i Drugikh Blagorodnykh Metallou (Inst,itute for Study of Platinum and Other Noble Metals) at KEPS upon L. A. Chugaev's death, and a member of the Gdttingen Akademie.

In 1934, the Institute of Physicochemical Analysis, the Platinum Institute, and the General Chemistry Laboratory of the Academy merged into the Institut - ~bshchei i Neorganicheskoi Khimii, IONKh (Institute of General and Inorganic Chemistry) with headquarters in Moscow and with Kurnakov as its director. IOXI(h rapidly became one of the leading scientific research institutes in the USSR and a center for physicochemical investigations of metallurgy, halurgy, precious metals, organic substances, and other economically-significant problems ($8). Following Kurnakov's death in 1941, it was renamed the N. S. Kurnakov Institute, and under its present director, Academician I. I. Chernyaev, it has continued in the tradition of its founder.

From 1920 to the end of his life there were few cherni- cal or metallurgical conferences in which Kurnakov failed to parti~ipat~e as chairman, lecturer, or delegate. Prominent in his career were the Berthelot Centennial and the congress on the organization of the Intern* tional Chemical Association (Paris, 1928) and the International Congress on Applied Chemistry (Barce- lona, 1930).

Kurnakov was chairman of the Chemical Association of the Academy of Sciences of the USSR (193G38), vice-president of the D. I. Mendeleev All-Union Society, and in 193940 chairman of the society's All-Union Competition Jury for the selection of the best scientific research works. In addition to his industrial consult- ing, in which he gave technical advice to plants and factories throughout the USSR, Kurnakov was extremely active in public affairs.

Kurnakov's contributions were recognized on numerous occasions by the Soviet government. I n 1936, he received the First Mendeleev Prize. In 1939, he was awarded the Order of the Red Banner for Toil, and in 1940, he received the title of Meritorious Worker of Science of the Russian Socialist Federated Union Re- public. I11 1941, the USSR Council of Ministers awarded him the Stalin Prize, First Class, for the fourth edition of his "Vvedenie v Fizik~Khimicheskii Analiz" (Introduction to Physicochemical Analysis) (29), a book dedicated to the memory of his closest friend, his wife Anna Mikhailovna, who for more than half a century had accompanied him everywhere and supported him in all his endeavors. In 1951, Kurnakov's portrait appeared on a postage stamp, part of a commemorative issue honoring Mendeleev, Butlerov, Lobachevski, Kalinnikov, and other outstanding figures of Russian art and science.

His wife's death in 1940 had serious effects on Kur-

nakov's health. Ignoring the cancer which was soon to claim his life, he continued his full work schedule almost to the very end, and when his colleagues in- quired as to the state of his health, which was visibly deteriorating, he quickly shifted the conversation to scientific topics. At the beginning of March, 1941, he entered the sanitarium a t Barrikha where he died on March 19th. Although a scientist of international reputation, he remained a modest and considerate per- son, approachable to colleagues and students alike. He is survived not only by his son Nikolal Nikolaevich, a chemist presently working a t the Baikov Metallurgi- cal Institute, but by an extensive school of scientists armed with new research methods, new apparatus, new theories, and new applications which he himself had created.

Kurnakov's Work

The large volume of Kurnakov's research in a number of widely-diversified fields prohibits the authors from doing more than considering briefly his most representative and important studies.

Coordination Chemistry (1, 16, 17, 19). The mention of Kurnakov's name immediately brings to mind his later work on physicochemical analysis. However, his studies of complex compounds, rarried out largely during the years 1891-1902 and following closely upon his early works on halurgy, constitute his first mature research. Two factors attracted Kurnakov to the field of platinum complexes-his interest in Russian natural resources and the then current controversy between the widely-accepted Blomstrand-Jgrgensen chain theory and the revolutionary Werner coordination theory (SO). While not completely accepting or rejecting either theory, Kurnakov regarded complexes as intermediate between chemical compounds of fixed composition and phases of varying composition (SI), a harbinger of his later (1914) "berthollide-daltonide" dichotomy.

Kurnakov did not limit himself to the synthesis of new complexes, but he investigated and sought relation- ships between a number of their physical and chemical properties, a search which eventually led him to the development of physicochemical analysis. His analogy between complex ions and simple metallic ions was sub- sequently developpd by L. A. Chugaev and his school, while Kurnakov's investigation of the relationship between acid-base properties of complexes and their solubilities (52) opened an area later explored more fully by A. A. Grinberg and co-workers. Kurnakov's study of refractive indexes is still of importance in connection with dipoles. His use of color as a means of investigating complex species in solution (55) was later continued by Niels Bjerrum in his elucidation of the composition of chromium complexes.

Chemical reactions permitting a distinction between inorganic geometric isomers are unfortunately all too rare, and Kurnakov's discovery of a reaction still used to differentiate cis from trans isomers of divalent platinum or palladium undoubtedly represents his most widely-known contribution to coordination chemistry (24). While investigating the substitution of ligands by thiourea and thioaeetamide, Kurnakov found that replacement occurred with all the ligands of the cis compound, but only w:th acid radicals of the trans compound:

46 / Journal of Chemical Education

( A = NHa or nn amine, X = halogen or acid radical, tu = thiourea)

Kurnakov's classic reaction later played a crucial role in Werner's proof of the square planar configuration of Pt(I1) and in the formulation of 'hernyaev's trans effect.

Kurnakov is regarded as one of the principal founders of the platinum industry in the USSR. While directing IOXKh, he did much to facilitate the development of coordination theory and the application of complexes to the refining of the platiuum metals. The Sverdlovsk Refinery, utilizing methods developed by his co-workers N. I. Podkopaev and X. X. Baraboshkin, made Russia independent of other nat,ions for its platinum refining (54).

Halurgy (3, 7, 10, 11). Contemporary halurgy is based largely on Kurnakov's research on salts, which began when he was still a studeut and continued throughout his leugthy scientific career. While studying a number of Crimean salt lakes during the period 1893-98, Kun~akov developed a general approach which made possible the correlatiou of hitherto unrelated facts into a significaut and meaningful whole. He regarded salt deposits not as static systems but as dynamic laboratories in which extremely complex chemical reactions were occurring. I t is difficult to select the most valna- ble of the numerous salt equilibria which he studied, but worthy of special ment,ion is his detailed investigation of the reversible reaction, MgClz + XalSOI g MgSOl + 2XaC1, an equilibrium of fundamental im- port,ance in the formation of salt lakes and in the pro- duction of table salt and Glauber's salt (27).

Knrnakov's profound understanding of natural processes, his refined scientific intuition, and his ability to relate industrial and economic needs to chemical theory played a vital part in the solution of one of the USSR's thorniest technological problems. As early as 1912, on the basis of studies of solid salts and solutions, Kurna- kov predicted that someday the Xortheni Urals would become an ecouomically-profitable sonrce of potassium salts. His prophecy has been fulfilled by the construc- tion of the huge salt combines a t Solikamsk (55).

Metallography (5, 9, 10, 17, 20). Kurnakov was a pioneer in the creatiou of scientific metallography, along with Le Chitelier, Roozeboom, Roberts-Austen, and Heycock and Xeville, and one of the founders of a theory of alloys. Following closely upon his research on halurgy and iuorganic complexes, Knrnakov, in the period 1900-1910, began physicochemical studies of alloys (%), intermetallic compounds, heterogeneous equilibria, alkali metal amalgams (37), phases of constant and varying composition (%), solid solutions, and other topics of both theoretical and technological value. A small but active metallurgical research group quickly developed a t the PolitekhnicheskiZ Institut and engaged in friendly competition with G. A. Tammann's similar group a t the Got,tiogen Institute. Despite the marked superiority of t,he German group in facilities and number of personnel, victories in this scientific rivalry were

won by Kurnakov's laboratory. During this period, in addition to his laboratory work, Kurnakov made use of his organizational talents in collecting, edit,ing, classifying, and publishing fragmentary metallographic data.

The problem of the composition of intermetallic compounds presented a number of difficulties to early metallographers. In one of his first works in t,his field (39), Kurnakov examined the situatiou in which varying amounts of components A and B dissolve in the compound AB,, a study which eventually led him to a formulation of the concept of a chemical compound. Kurnakov's modification of the Eschenhagen-Toepfer pyrometer in 1904 (4O), now universally used in metallographic and physical chemistry laboratories, provided a means of studying equilibria not only of alloys but also of any system and, incidentally, gave impetus to his own metallographic research. I t was almost immediately adopted by industrial laboratories where it facilitated the rapid and accurate determination of critical points in steels and other alloys. Kurnakov repeatedly investigated the relationship between alloy composit,ion and mechanical and chemical properties, a topic of tremendous practical significance (41). Prob- ably the first to recognize the importance of the vapor phase in eutectic fusion were Kurnakov and Efremov (4%.

At the beginning of the nineteenth century, the composition of pure compolmds constituted a major chemical problem. In one of the most famous con- troversies in the history of chemistry, Claude Louis Berthollet (1748-1822) affirmed that the composition of a chemical compound could vary, while his o p ponent, Joseph Louis Proust (1754-1826) maintained that it was constant. Proust's view prevailed, and the Law of Definite Proportions furnished one of the empirical cornerstones of Dalton's Atomic Theory (1808). A century later, Kurnakov realized that Berthollet's ideas contained some truth, and he sug- gest,ed that alloys and other substances of indefinite composition be called "chemical compounds" or "berthollides" and ordinary compounds of fixed composition, "chemical individua" or "daltonides" (43, 44). "Berthollides" or Kurnakov phases, a major concern of solid state chemistry, are extremely common both in nature and in industrial products (45).

Physicochemical Analysis (1-4, 6, 8-11, 14, 18-20). This area of chemistry, a logical outgrowth of van't Hoff's earlier research on phase equilibria, developed (to quote Kurnakov) "from the needs of practical metallography" (29). The relationship between composition and properties of equilibrium systems, nsually expressed graphically in the chemical diagram, "sostav- suoistvo" (composition-property), constituted the heart of the new approach. Originally applied to alloys, this general method, being iudependent of the system under investigation, was soon transferred to other syst,ems such as silicates, glasses, molten salts, aqueous salt solutions, and organic substances. The complex approach to a given single system from different view- points fonud almost instantaneous technological applications.

From 1899, the year in which he published T o m - pounds of Metals with Themselves" (@), a study which formed the basis of physicochemical analysis, Kurnakov

Volume 39, Number I , Jonuary 1962 / 47

i~~arcasingly abandoned preparative methods in favor of the new method. During the period 1908-1910, physicochemical analysis, a term first used by Kurnakov in 1916, assumed its basic fosm. Investigations were made of previously-neglected physical properties such as elcctroconductivity (47), hardness (481, pressure of flow (@),and internal friction (50).

Thermal analysis, one of the characteristic experi- mental methods of the new school, was applied to natural formations (51) such as bauxite (52), hydrated oxides and silicates of iron (53), clay soils, pyrophyllite, and talc (54); these are materials which, because of their highly dispersed state, cannot be studied by the usual mineralogical and petrographic procedures. The foundations of physicochemical analysis were first syst,ematically presented in ICnrnakov's "Vvedenie v Fiziko-Khimicheskii Analiz" (1925) (29).

I<urnakov's graphical expression of the results of physicochemical analysis formed a bridge between chemistry and mathematics, two sciences which had hitherto grown along separate pat,hs. Many terms of physicochemical analysis (transformation, system, number of factors of equilibrium, etc.) correspond to basic concepts of algebraic theory (transformation, group, number of symbols, etc.). Chemical transformations and changes of state occur in a manner analogous to uninterrupted geometric transformations of space. Apparent breaks in continuity which are found in the formation of certain chemical compounds ("daltonides") represent merely invariable points ("singular points2" "knot points," or "Daltou points") in these transformations. Kumakov thus demonstrated that earlier concepts of integral stoichiometry and con- stancy of composition only represented rather special situations, that compounds of varying composition ("herthollides") are of importance equal to compounds of constant composition ("daltonides"), and that the use of topology permits a ready interpretation of phase transformations (55).

Teaching (10). I t is not surprising that the man who orgauized the largest school of Russian chemists should have been an excellent teacher who stimulated and inspired beginning students and seasoned scientists alike. Starting in 1898, Kurnakov began to attract an ever-increasing number of followers, many of whom are now prominent scientists or industrial leaders and some even founders of their own schools. Throughout his long career, Kurnakov's personal and painstaking attention to the education of young scientists was an invariable concomitant of his research. He repeatedly declined a number of extremely attractive offers in order to continue his teaching and research.

ICurnakov was one of the first (1899) to introduce the teaching of physical chemistry in Russia. In his popular lectures a t the Politekhnicheslcii Institut he made extensive use of well-integrated and thought- provoking demonstrations, even to the extent of presenting complete miniature factories to illustrate industrial processes. He never allowed the demands of his research to interfere with his teaching; despite his phenomenal memory and encyclopedic erudition, he always insisted on writing out his lectures, and he scrupulously studied these notes before every lecture.

Kurnakov, whose patience and empathy were proverbial, also devoted considerable time to question-

ing and instructing students in the lnhoratory. He readily admidted the younger students t,o research, a practice which a t that time mas not only uncommon but which met wit,h hostile criticism from the more conservative faculty, a situation difficult for us to conceive today when undergraduate and even fresh- man research is becoming commonplace. Many research works of Kurnakov's young students were awarded ~r izes bv the RussAoe Fiziko-Khimicheskoe - Obshchestuo.

Today, in our efforts to promote basic research, TTe take great pains to differentiate science from technology. S o such dichotomy existed for Kurnakov, for whom the txvo were inextricably linked. This extremely versatile teacher always warned his students that technology could not develop without a theoretical basis. At the same time, he cautioned them against isolating themselves and their science from everyday life and recommended that they visit fact,ories, mines, and industrial plants, a practice which he himself followed throughout his life. Kusnakov's t,echno- logical application of his theoretical results did not lower the staudards of his investigat,ions, but on the contrary, increased their value and led to ideas for further work.

The two-volume "Collection of the Selected Works of N. S. Ihnakov" (66), issued in 1938-39, contains a complete list of his research published up t,o that time. Although one must allow for the inevitable over- valuation found in the Russian articles which were an important source of information for this paper, the majority of ICurnakov's works, even those published as much as a half century ago, are still of great theoretical and practical interest.

Acknowledgments

The authors wish to acknowledge the assistance of Akademik Ilya I. Chernyaev, Direktor of the Institut - Obshchei i Neorganicheskoi Khimii imeni N . S . Kurna- kova Akademii Nauk S.S.S.R., Moscow, who gra- ciously provided information, reprints, and the photo- graph which appears in this article. The present study resulted from interest in Kurnakov aroused by a research project on the separation of inorganic geometric isomers sponsored by the Research Corporation and the Xational Science Foundation (NSF-G-11241).

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Volume 39, Number I , January 1962 / 49

nikolai semenovich kurnakov

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