Zelinsky, Nikolay Dmitrievich
ZELINSKY, NIKOLAY DMITRIEVICH
(b. Tiraspol, Kherson province [now Moldavian S.S.R.], Russia, 6 February 1861; d. Moscow, U.S.S.R., 31 July 1953)
After graduating from the University of Odessa in 1884, Zelinsky was sent in 1885 to Germany, where he worked with Johannes Wislicenus at Leipzig and Victor Meyer at Göttingen. While trying to obtain tetrahydrothiophene in Meyer’s laboratory he synthesized di-(βchloroethyl) sulfide(mustard gas)-and became its first victim, receiving serious burns. In 1889 at Odessa he defended his master’s thesis, on isomers in the thiophene series, and, in 1891, his doctoral dissertation, on stereoisomers in the series of saturated carbon compounds. From 1893 to 1953 Zelinsky was professor at Moscow University, except for the period 1911-1917, when he headed the central laboratory of the Ministry of Finances in St. Petersburg and taught at the Polytechnical Institute.
In connection with the use of poison gases in World War I, Zelinsky in 1915 developed a method of obtaining activated charcoal and a universal gas mask that was used by the Russian and Allied armies. In 1918-1919 he devised a process for obtaining gasoline by cracking higher-boiling petroleum fractions in the presence of aluminum chloride. He was elected a corresponding member of the U.S.S.R. Academy of Sciences in 1926 and, in 1929, a full member. In 1934 he became department head at the Institute of Organic Chemistry (named for him in 1953) of the U.S.S.R. Academy of Sciences.
Zelinsky’s most important work dealt withthe chemistry of hydrocarbons and with organic catalysis. From 1895 to 1905 he was the first to synthesize many hydrocarbons of the cyclopentane and cyclohexane series, used as standards in the study of the composition of petroleum fractions. He subsequently synthesized other hydrocarbons, including cyclopropanes and cyclobutanes, as well as bicyclic spirane and bridged hydrocarbons, and studied their catalytic transformations, many of which are considered classical. In 1911 Zelinsky discovered the smooth dehydrogenation of cyclohexane (and its homologues) into benzene in the presence of platinum and palladium catalysts at 3000c. In the 1920’s and 1930’s he studied the selective character of this reaction, used it extensively to determine the content in gasoline of cyclohexane hydrocarbons and kerosene fractions, and proposed it as an industrial process for obtaining aromatic hydrocarbons from petroleum.
In the 1930’s Zelinsky investigated the reaction (that he discovered in 1911) of the disproportionation of hydrogen in cyclohexene with the simultaneous formation of benzene and cyclohexane. This reaction, which he termed “irreversible catalysis” and which occurred at room temperature in the presence of platinum and palladium, is peculiar to cyclohexane hydrocarbons containing double bonds, including many terpenes. In 1934 Zelinsky discovered the hydrogenolysis of cyclopentane hydrocarbons with their tranformatioin into alkanes in the presence of platinized carbon and hydrogen at 300–310°C.
Zelinsky showed the intermediate formation of methylene radicals in many heterogenous catalytic reactions: in the decomposition of cyclohexane, in the Fischer-Tropsch synthesis on a cobalt catalyst, in the hydrocondensation of olefins with carbon monoxide, and in the hydropolymerization of olefins in the presence of small quantities of carbon monoxide. A pioneer in the study of the reciprocal isomerization of cyclopentane and cyclohexane hydrocarbons in the presence of aluminum chloride and aluminum bromide, Zelinsky showed in 1939 that cyclohexene and its homologues are almost completely isomerized (in the presence of oxides of aluminum, beryllium, or silicon at 400–450°C.)into homologues of cyclopentene. As early as 19156 he used oxide catalyst in the cracking of petroleum, which led to a lowering of the temperature of the process and to an increase in the quantity of aromativ hydrocarbons formed. In 1915 he was the first to show that in the tranformation of organic compounds the reason for the poisoning of the catalyst is that a layer of carbon is deposited on its surface. By Oxidizing it, the catalyst can be regenerated. This method found wide application in connection with the extensive use twenty-years later of oxide catalyst in the petroleum processing industry
To confirm the organic theory ofthe origin of petroleum, Zelinsky in the 1920’s and 1930’s obtained artificial petroleum from plant and animal materials-cholesterol, fatty acids, beeswax, and abietic acid under the action of aluminum chloride. He developed the cyanohydrin method for obtaining alpha-amino acids and was the first to obtain a number of hydroxy amino acids. In 1912 Zelinsky achieved the hydrolysis of proteins using dilute acids and, in addition to amino acids, obtained their cyclic anhydrides, diketopiperazines. In connection with this he proposed the theory of the cyclic structure of protein molecules.
I. Original Works. Zelinsky’s writings were published as lzbrannyue trudy (“Selected Works”), 2 vols. (Moscow-Leningrad, 1941); Sobranie trudov (“Collection of Works”),4 vols. (Moscow-Leningrad, 1954-1957);and lzbrannye trudy(“Selected Works” ; Moscow 1968);all three eds.include biography, bibliography, and a sketch of his career.
II. Secondary Literature. On Zelinsky and his work, see the following: A. A. Balandin, “Akademik Nikolay Dmitrievich Zelinsky,” in Vestnik Akademii nauk SSSR, 16 , nos. 5–6 (1946),80–90, published on his eighty-fifth birthday; N. A. Figurovsky, Ocherk razvitia ugolnogo protivogaza (“A Sketch of the Development of the Charcoal Gas Mask” ; Moscow, 1952); and Zamechatelnnoe russkoe izobretenie (k 40-letiyu izobretenia ugolnogo protivogaza N. D. Zelinskogo (“A Remarkable Russian Invention [on the Fortieth Anniversary of the Invention of the Charcoal Gas Mask by Zelinsky” ]; Moscow,1956); B. A. Kazansky. “Roboty N.D.Zelinskogo i ego shkoly v oblasti kataliticheskikh prevrashcheny uglevodorodov” (“Work of Zelinsky and Hius School in the Field of Cataytic Tranformatioins of Hydrocarbons”), in Yubileyny sbornik, posvyashchennytraidtsatiletiyu Velikoy Oktyabrskoy sotsialisticheskoy revoluyutsii(“Jubilee Collection Dedicated to the Thirtieth Anniversary oif the Great October Socialist Revolution”), Sovoetskuy ucheny akademik Nikolay Dmitrievich Zeklinsky (“The Distinguished Soviet Scfientist Academician …” ; Moscow, 1951, published on his ninetieth birthday; B. A. Kazansky, A. N. Nesmeyanov, and A. F. Platé, “Raboty akademika N. D.Zelinskogo i ego shkoly v oblasti khimii uglevodorodov i organicheskogo kataliza” (“The work of Academician Zelinsky and His School in the Field of the Chemistry of Hydrocarbons and Organic Catalysis”), in Uchenye zapiski Moskovskogo gosudarstvennogo universiteta no. 175 (1956), 5–53; Y. G. Mamadaliev, Akademik Nikolay Dmitrievich Zelinsky (Baku,1951); A. F. Platé, “N. D. Zelinsky i sovremennoe razvitie neftekhimii” (“Zelinsky and the Contemporary Development of Petrol Chemistry”), in Neftekhimia1 (1961), 7–14, published on the centenary of his birth; V. M. Rodionov, “Nikolay Dmitrievich Zelinsky (vospominania i vstrechi)(“…[Reminiscences and Meetings” ]), in Soobschenie o nauchnuykh rabotakh chlenov Vsesoyuznogo Khimicheskogo obshcherstva im.D.I.Mendeleeva,no. 12(1951; N. I. Shuykin, “Pamyati akademika Nikolaya Dmitrievicha Zelinskogo” (“Memories of Academician …”), in Zhurnal obshchei khimii, 31 (1961),i-vii, published on the centenary of his birth; V. A. Volkov and A. N. Shamin, “Novye dokumenty o deyatelnosti N. D. Zelinskogo (“New Documents on the Activities of Zelinsky”),in Voprosy istoirii estestvoznania i tekhniki (1975), no. 1, 54–56; and Y. K. Yuriev and R. Y. Levina, zhizn i deyatlnost akademika Nikolaya Dmitrievicha Zelinskogo(“Life and Activities of Academicin Zelinasky” ; Moscow, 1953), also in English (1958).
A. F. PlatÉ