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By Academician Vladimir SHPAK, and Andrei MORACHEVSKY, "Applied Chemistry" Russian Scientific Center
St. Petersburg's scientists have made a notable contribution in the area of theoretical and applied chemistry. Let's look back at some of the milestone events of the 18th, 19th and 20th centuries showing the continuity of our research schools in the chemical science.
Chemical studies in Russia hark back to the great Russian savant Mikhail Lomonosov at whose initiative Russia's first chemical laboratory was set up in St. Petersburg (1748), which worked for nearly half a century. Actually without any assistants, single-handedly, Lomonosov carried out a wide range of research between 1748 and 1757, including the technology of colored glass production materialized in his famous mosaics (inlays) mounted there. Lomonosov also researched in the manufacture of glasses with different light refraction indices. In 1752 a glass-making works was built to his design near St. Petersburg. In 1752 to 1754 Lomonosov read the world's first course of lectures on physical chemistry to students of the Academy of Sciences University.
Applied studies were in the center of attention of Russia's chemists in the latter half of the 18th century. Thus Academician I. Lehman, involved mostly with assays of ores and minerals, wrote the first handbook on test-tube making. Another chemist, Academician E. Lacksmann, developed an innovative mode of glass production with the use of dehy-
drated (dewatered) sodium sulfate instead of potash (potassium carbonate). And yet another chemist, Academician T. Lowitz, discovered the phenomenon of charcoal- mediated adsorption of impurities present in solution. He was the first to obtain frozen acetic acid and suggested a number of refrigeration mixtures; besides, he worked to upgrade chemical analysis techniques. V. Severgin, elected to the Academy of Sciences as mineralogist, is also known for his works on the chemistry and technology of mineral salts and on test-tube production. A. Musin-Pushkin, honorary member of the Science Academy, was Russia's first scientist to take up research in the chemistry and technology of platinum group metals and developed a method of crude platinum purification from iron and iridium impurities, and suggested a technique for obtaining malleable platinum.
During the 19th century, too, St. Petersburg scientists made a big contribution to the development of chemistry. In 1808 Academician A. Sheerer wrote a handbook on chemistry, Russia's first manual on the subject, with a considerable attention given to the Russian chemical nomenclature. Subsequent discoveries were summed up by Academician H. Hess in his manual Fundamentals of Pure Chemistry (1831) which saw seven reprints and which had an appreciable influence on the scientific outlook of several generations of Russian chemists, among them scientists of world stature, such as N. Zinin, who discovered the method of obtaining aromatic amines; N. Beketov, who suggested the mode of reducing metals from oxides; A. Butlerov, who substantiated the theory of chemical structure and explained the phenomenon of isomerism; and the author of the Periodic Table D. Mendeleyev.
In October 1831 a practical technological institute was opened in St. Petersburg with the aim of "preparing people having a sufficient range of theoretical and practical knowledge for managerial jobs at factories". Russia had never had such kind of institutions before. H. Hess agreed to take the post of class inspector (assistant director) in it. He drew up curricula and invited the best tutors from civil and military schools of the capital for teaching the main disciplines. A chemical laboratory was set up in keeping with his recommendations. Thirty years later, the Technological Institute was elevated to the status of a higher school (college).
In 1832 Dr. Hess was elected professor of chemistry and technology at the Chief Pedagogical (founded in 1804) and Mining institutes (in 1834 the Mining Institute was given the name of the "Institute of the Corps of Mining Engineers"). He founded a chemical laboratory at the Mining Institute that for many years continued as a major research and teaching center in Russia. Among its alumni are such scientists as K. Lisenko (researching in fuel deposits, i.e. oil and coal), V. Alexeyev (who proved the existence of a critical temperature of dissolution), D. Konovalov (elected member of the
Academy of Sciences in 1923, studied vapor pressure in solutions), I. Schroeder (author of the ideal solution concept), N. Kurnakov (elected to the Academy in 1913, one of the founders of physical chemistry as a science).
Dr. A. Voskresensky, elected in 1864 to the Russian Academy of Sciences as corresponding member, did much in teaching chemistry at St. Petersburg University and at other schools of higher learning. He attended Prof. Hess's lectures and, in his turn, taught chemistry to D. Mendeleyev who entered the chief Pedagogical Institute in 1850.
Academician B. Yakobi, an erudite scientist, had a great role to play in the development of applied chemistry in 19th-century Russia. The man who invented galvanoplastics (electroforming), who studied the chemical sources of electric current and who developed methods for measuring electrochemical quantities.
In the latter half of the 19th century, the Academy of Sciences, St. Petersburg University, the Mining Institute, the Medicosurgical Academy (since 1881, the Academy of Military Medicine), the Artillery Academy, the Technological Institute, and the Land-Farming Institute (now, the Academy of Forest Engineering) pooled efforts and formed a major center of chemical research which has impacted a good deal the development of science both here and abroad.
Again, credit is due to Nikolai Zinin. He began his scientific career at Kazan University; in 1847 he became a professor at the St. Petersburg Medicosurgical Academy (chemistry and physics) and in 1865 was elected to the St. Petersburg Academy of Sciences as its full member.
Among other things, he researched in obtaining, via reduction of nitrogen-containing compounds, the primary amines in the aromatic series (aniline, aminonaphthaline, benzidine), which are very important stock materials for the synthesis of organic dyes. His innovative method, simple and low-cost, made it possible to produce aniline in huge amounts. Within a few years, a new major branch of the chemical industry, production of dyes, appeared, N. Zinin was among those at whose initiative the Russian Chemical Society was founded, and at the first meeting on December 5, 1868, was elected its president.
Alexander Butlerov, also a Kazan University graduate, was elected to the faculty of St. Petersburg University as professor in 1857, and years after, in 1874, to the Academy of Sciences. He is the author of the theory on the structure of organic compounds and of the classical work Introduction to a Complete Study of Organic Chemistry. In addition, Professor Butlerov carried out many experiments, including those on the synthesis of tertiary alcohols, and on polymerization where nonsaturated compounds were implicated.
Another great chemist, Dmitry Mendeleyev, discovered a periodic law in 1869, and substantiated it, both in theory and experimentally, within two or three years. This brilliant scientific discovery, based on the data obtained by the mid-19th century on the characteristics of elements, revealed their interconnections. It had a great impact on the theory of the structure of matter and relevant studies. Mendeleyev combined his research work with teaching activities at St. Petersburg University (1857 - 1890) and at the
Technological Institute (1864 - 1872). His fundamental work, Basics of Chemistry, had over ten repeat editions.
A pupil and close coworker of Mendeleyev's, Dmitry Konovalov, has done a lot for the development of physical chemistry, in particular, for the theory of solutions and applied problem solving. In 1884 in his M. Sc. dissertation (On Vapor Pressure of Solutions) Konovalov discovered major laws later named after him. Subsequently he furthered Mendeleyev's ideas on the interaction of dissolved substances with solvents. Konovalov formed a large following, among them A. Baikov (elected to the Academy of Sciences in 1832) and M. Vrevsky (elected corresponding member in 1929).
In October 1902 a Polytechnical Institute was opened in St. Petersburg. In the focus of curricula at its Department of Metallurgy were chemical disciplines. Taking part in preparing the syllabuses were D. Mendeleyev, P. Walden (expert in stereochemistry, elected to the Academy of Sciences in 1910) and D. Chernov (who pioneered in the metal science and in the theory of heat treatment of steel). A spacious Chemical Department building housed well-equipped laboratories. Nikolai Menshutkin was appointed (and then elected) dean of the Chemical Department. He was known for his works in organic and analytical chemistry and as lecturer at St. Petersburg University. He did a lot of good by inviting eminent scientists to lecture at the Polytechnical Institute: chemists N. Kurnakov, V Kistyakovsky and A. Baikov; mineralogist F. Levinson-Lessing and metallurgist M. Pavlov. All these men were then elected to the Academy of Sciences. Also, he invited V. Grum-Grzhimailo (metallurgy) and P. Fedotiev (chemical technology), subsequently elected to the USSR Academy of Sciences as corresponding members. N. Kurnakov introduced something quite new for Russia's higher technical colleges: undergraduates were given an opportunity to defend their research findings in a graduation paper for the qualification of a metal- making engineer.
On the initiative of Drs. A. Krakau and N. Pushin, at the turn of the 20th century, the St. Petersburg Electrotechnical Institute started training engineers.
The chemical laboratories of the Mining, Polytechnical and Electrotechnical Institutes were a good experimental base for N. Kurnakov in rearing a Russian school of inorganic chemistry scientists who, studying the characteristics of metal-containing and other compounds, formulated the general principles of physicochemical analysis, for metal systems in particular.
Meanwhile research continued with much success in the field of organic chemistry. The works of the representatives of the Butlerov school, A. Favorsky (elected to the Science Academy in 1929) and V. Ipatiev (elected to the Academy in 1916), proved to be of much significance. A. Favorsky, a St. Petersburg University professor, is one of the pioneers in the chemistry of nonsaturated organic compounds and acetylene; he discovered a large number of isomerization processes in the series of nonsaturated hydrocarbons, and founded a research school of his own. As to V. Ipatiev, he was an Artillery Academy professor and had a lieutenant-general's rank. He was the first to synthesize isoprene, the principal monomer of natural rubber. He studied organic reactions on solid catalysts, effected ethanol decomposition with the formation of ethylene, and developed a range of important industrial technologies. V. Ipatiev's research works on chemical processes at high pressure and the experimental equipment developed for the purpose meant much for the development of petrochemistry.
The discovery of the phenomenon of radioactivity by Antoine Becquerel and of radioactive elements (polonium and radium) by Pierre and Marie Curie set the stage for a new chemical discipline, radiochemistry. On the initiative of Vladimir Vernadsky, geochemist and mineralogist (elected to the Academy in 1912), the Academy of Sciences formed a Radium Commission in 1910. Vernadsky took an active part
in its work. Addressing an annual meeting of the Academy in December 1910, he said in particular, "Opening before us in the phenomena of radioactivity are sources of atomic energy, millions of times superior to the sources of power which have ever been pictured in human imagination... It is by no means indifferent to us how radium beams are going to be studied. They should be investigated by us, Russian scientists..." Vernadsky took charge of exploration for radioactive materials and headed this work for the rest of his life.
The First World War showed up the technical and economic backwardness of Russia, and the weakness of its chemical industry. Many useful minerals had to be imported from other countries. Therefore it was important to find deposits at home and start mining and processing industries. At Vernadsky's initiative upheld by other eminent scientists of the day, the Academy of Sciences established a special commission for exploring Russia's productive forces (KEPS), and a military-chemical committee under N. Kurnakov so as to "unite efforts of Russian chemists for joint work in matters related to the needs of state defense". This happened in February 1915. In turn, the chief Artillery Department set up a chemical committee under V Ipatiev to control the production of explosives, fuels and lubricants. Russian chemists had another achievement to their credit-the gas mask and its full-scale production for servicemen. This work was guided by Nikolai Zelinsky (elected to the Academy of Sciences in 1929), who lived in Petrograd (St. Petersburg) then.
In 1918 - 1920, despite economic dislocation and civil war, a number of scientific institutions were set up in Petrograd, which subsequently evolved into major research centers. Thus, N. Kurnakov organized an Institute of Physicochemical Analysis that was to attack urgent problems in the production of new metals and alloys, and in the utilization of mineral deposits of our salt lakes. At about the same time another center involved with the study of platinum and other noble metals was established; it was headed by Lev Chugayev, a Petrograd University professor and the author of fundamental works on the chemistry of complex compounds. One urgent problem was to upgrade the techniques of refining platinum metals to high purity. Outstanding scientists began their research career at that center: Academicians A. Grin-berg and I. Cherniayev, and V. Lebedinsky, corresponding member of the USSR Academy of Sciences. A string of other research institutions appeared in those years: the State Optical Institute (1918); the Russian Institute of Applied Chemistry (set up in 1919, it was then reorganized into the State Institute of Applied Chemistry; today this is the "Applied Chemistry" Russian Scientific Center); the State Radium Institute (1922). Owing to the work done by Professor I. Bashilov and V Khlopin (elected to the Science Academy in 1939), Russia's first high-activity preparations of radium were obtained from domestic material already in December 1921.
Our Petrograd scientists, who achieved much success in their studies, made good spadework for launching refined platinum production at a mill in Yekaterinburg in the 1920s. Yet the real break for the Kurnakov and Chugayev schools came in 1943 - 1944, when a unique enterprise was commissioned in Krasnoyarsk for extracting platinum metals from sulfide ores mined at Norilsk.
All the way back in 1915 Vernadsky pointed to the need of producing aluminum from the home material. By that time N. Pushin at the Electrotechnical Institute and P. Fedotyev (elected to the USSR Academy of Sciences as corresponding member in 1933) at the Polytechnical Institute, jointly with V. Ilyinsky, conducted wide laboratory studies into obtaining aluminum via electrolysis of electrolyte-alumina melts. Their works are considered to be classical.
A bauxite deposit was found at Tikhvin (now Leningrad region) in 1916. Geological surveys carried out in 1923 showed it could satisfy this country's immediate needs in aluminum at low cost. Yet in the concentration of silica (up to 18 percent) the bauxite proved to be low-grade, and that called for a new technology of refining. So, Leningrad researchers turned to this job. An original method was developed at the State Institute of Applied Chemistry by a team of A. Yakovkin (elected to the USSR Academy of Sciences as corresponding member in 1925). Their pilot-production plant obtained the first lot of aluminum in June 1929. The following year, in 1930, work began on the construction of Russia's first aluminum mill near the river Volkhov, and it was put into commission on May 14, 1932. Its rated capacity amounted to 5 thousand tons of aluminum a year.
As early as 1917, proceeding from preliminary assays of brine, N. Kurnakov concluded that the deposit of potassium salts in the upper reaches of the Kama (Perm region) could be of commercial interest. Close geological and chemical studies became necessary for defining the boundaries of the deposit and its occurrence. This job was done in 1925 by a field party under Professor P. Preobrazhensky, a Leningrad geologist. This is how one of the world's largest deposits of potassium and magnesium salts was discovered and explored. Two years later, ground was broken for a potassium mine and a mill which was commissioned early in 1934. Leningrad chemists lent a hand in getting on top of the problem of an all-out refining of the potassium salts, sylvinite and carnallite, found in that deposit. The technology of magnesium production from carnallite was developed by a team of Leningrad researchers under P. Antipin (corresponding member of the USSR Academy of Sciences since 1939).
The Solikamsk-based magnesium mill produced the first batch of aluminum in March 1936, and Solikamsk, one of the oldest towns in the Urals, turned into a major center of the chemical industry.
N. Kurnakov and coworkers looked much farther south, as far as Kara-Bogaz-Gol, a unique gulf in the Caspian with huge deposits of sea type salts. Following several field expeditions there, commercial extraction of sodium sulfate, an important raw material for the chemical industry, was started in 1924.
Up in the Far North, geological teams under Academician Alexander Fersman, a pupil and close associate of Vernadsky's, had been exploring the Kola Peninsula beginning in 1920. Several field parties of Leningrad research scien-
tists sent there in the 1930s helped develop the apatite-nepheline deposits of the Khibiny mountain range, the deposits of copper-nickel ores of Monche-tundra, and the ores of rare metals in Lovozersk tundras. The Kola Peninsula grew into a significant production base of phosphorous fertilizer and other important chemicals.
The production of synthetic rubber in the USSR came as a momentous event of world significance. Back in 1913, Sergei Lebedev (elected to the Academy of Sciences in 1932) arrived at the conclusion that polymerization capacity is proper to hydrocarbons having a conjugated system of double bonds. He formulated principles concerning the nature, rate and mechanism of the polymerization process. By January 1928 Lebedev had obtained the world's first 2 kg batch of synthetic sodium/butadiene rubber on the basis of ethanol, and in another three years, he managed to get as much as 260 kg at a pilot production unit. In this process- that's the main point! - divinyl was polymerized under the effect of a sodium catalyst. Three rubber production plants operating by the Lebedev method were under construction soon. In 1932 the Leningrad Technological Institute opened an academic department (chair) of synthetic rubber. Later on, two Leningrad scientists, Academician B. Dolgoplosk and Corresponding Member of the USSR Academy of Sciences A. Korotkov, upgraded the techniques of getting this precious material with different characteristics. Our country coped with the important problem of launching a rubber industry for making tyres and other rubber articles.
Academician Nikolai Semenov and his colleagues achieved much success in chemical kinetics studies at the Institute of Chemical Physics set up in 1931. They developed a theory of branching chain reactions, one of the most significant achievements of theoretical chemistry in the first half of the 20th century. Accordingly, Nikolai Semenov and Sir Cyril Hinshelwood of England merited a Nobel Prize in 1956 for parallel work in chemical reaction kinetics (Sir Hinshelwood was elected to the USSR Academy of Sciences in 1958 as foreign member).
Way back in 1902 - 1904 V. Kistyakovsky (elected to the Science Academy in 1929), opened Russia's first laboratory of physical chemistry and theoretical electrochemistry at the St. Petersburg Polytechnic. His multifarious scientific interests included above all the electrochemical behavior of metals in water media. By 1925 he had conceptualized a film theory (of passivity) in its relation to corrosion processes. He explained the cause of the passive state by the formation of an oxide film (amorphous, vitreous) covering metal in a thick layer. In 1930 Kistyakovsky organized a laboratory of colloid electrochemistry in Leningrad (today, the RAS Institute of Physical Chemistry in Moscow). It thus became possible to solve difficult technical problems of protecting metals in highly aggressive media used in innovative technologies.
After 1945 another problem moved to the forefront, and that was obtaining structural materials for atomic engineering. Technologies for high-purity substances had to be developed, and high-quality materials with different physical and chemical properties had to be synthesized for radioelectronics and other purposes. The collectives of Leningrad's research centers and higher schools made a good contribution toward the solution of these tasks.
A research team under Academician V. Khlopin working at the Radium Institute, developed a technology for extracting plutonium from irradiated uranium. Leningrad scientist-Academician B. Nikolsky, Corresponding Member of the USSR Academy of Sciences B. Nikitin, I. Starik and V. Vdovenko-participated in bringing this technology to commercial status at Russia's first radiochemical plant.
In 1948, at the initiative of S. Ushakov, corresponding member of the USSR Academy of Sciences, and other scientists, the Institute of High Molecular Compounds (under the USSR Academy of Sciences) was founded in Leningrad. The theoretical and practical projects carried out there prepared the ground for a large group of polymer products*. The R&D Association PLASTPOLYMER launched full- scale production of polyethylene (its output soon topped 3 mln tons) and polystyrene.
Academician I. Grebenshchikov took an active part in setting up the Institute of the Chemistry of Silicates (opened in Leningrad, 1948) which conducted wide-ranging studies into the structure, chemistry and thermodynamics of glass-forming melts and glasses. It also developed a kit of new materials against corrosion. Grebenshchikov was succeeded as the Institute's head by N. Toropov, Corresponding Member of the USSR Academy of Sciences, an authority in the field of the inorganic material science and the technology of silicate systems.
Looking back into the past, we can say that the chemical materials developed by scientists working in our city and elsewhere have changed people's life styles. These innovative substances have allowed to manufacture a huge number of household articles, they have enabled man to blaze the trail into outer space, and have helped to solve with much success the problems of nuclear and laser engineering. Such mass information media of the 20th century as radio, cinema, television, computers and Internet would have been inconceivable without new synthetic materials. Chemical research and development has become a significant element of human activities in medicine, power engineering, mechanical engineering and in national defense.
The immense scientific and technical potential amassed by St. Petersburg's chemists in the past two centuries by so much effort on the part of many research scientists instills hope that it will be used reasonably for further problem solving in the development of our city, our country and the world at large.
* See: Ye. Panarin, N. Kuznetsova, "Polymer Drugs", Science in Russia, No. 2, 2003.- Ed.
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