HISTORY OF THE CHAIR
The first founder and professor of the Chemistry Department of the University of Kyiv was Stepan Fedorovich Zenovich (1779–1856). Subject of scientific works S. F. Zenovich's mineralogy and mineral chemistry (at that time so-called inorganic chemistry), as reported by one of the first historians of the Kiev University V. Shulgin in the book "History of the University of St. Vladimir". While working at the University from 1834 to 1839, S. Zenovich taught inorganic (1-2 courses) and organic (2-3 courses) chemistry and enjoyed general respect among teachers and students. Lectures were held three times a week, one of which was necessarily accompanied by visual displays. During the lectures the professor was so enthralled that his voice acquired an unusual elevation, the person was reincarnated, and in his chemical laboratory he appeared to students in the form of an alchemist-wizard. "This is a great and important science of chemistry", - Professor Zenovich repeated to his audience.
After dismissal of S. Zenovich as a professor of chemistry, he was transferred from Vilna Medical-Surgical Academy to Gnat Matveevich Fonberg (1801‑1891), who worked at the University of Kyiv for 20 years. Unlike Zenovich, G. M. Fonberg, being well-informed of theoretical chemistry, was constantly engaged in experimental research, which for the most part had an inorganic-analytical character. He has published (in Polish) more than 20 works, of which the 3-volume "Course of Technical Chemistry" deserves attention. He raised the high level of chemistry teaching, organized a chemical laboratory, and for the first time in the Kyiv University introduced obligatory practical laboratory classes.
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Gnat |
The chemical laboratory, organized by G. M. Fonberg, was initially located in two small rooms of the basement of a private house in the Lypok district, and in 1845 it was transferred to a newly built educational building and was designed for the work of 22 students. Since 1848, in the university chemical laboratory, along with synthetic works, students are expected to perform practical tasks for analysis. "Rules for practical exercises of the students of St. Volodymyr's University" (1848) provided for the qualitative and quantitative analysis of minerals and soils, the study of poisons, various waters from wells and lakes, the determination of benign production of various chemical plants.
During this period at the university, the first chemical studies on inorganic chemistry were conducted to study the composition and synthesis of various substances or investigation of mineral raw materials. G. M. Fonberg himself paid much attention to the study of the waters of the Kyiv wells and ponds.
G. M. Fonberg attracted students to the research activity. From his students, who later were left to teaching at the university, one can name G. O. Chugaevich, who was the first adjunct of the chemistry department, and then ‑ a professor of chemical technology; V. Olevinsky (1834‑1884), with whom D. I. Mendeleev was friends when staying in Germany.
First in our University began studying molecular compounds professor Tymofiy I. Lonachevsky-Petrunyaka. In 1871 he described his experiments on chlorination of iron acetate-2 and the separation of iron-3 chloride-acetate crystalline hydrate. A number of works by T. I. Lonachevsky-Petrunyaka devoted to the problem of clearing the Dnipro water. By studying the absorption of carbon monoxide by hydrochloric and ammonium solutions of copper monohloride, he came to the conclusion that the formed systems are approaching the solutions and at the same time have the properties of the chemical compound.
A notable page in the development of chemistry of our university was the period from 1862 to 1869. In these years, the chemical laboratory was headed by Ivan Artamonovich Tyutchev (1834‑1893). With the transition to the University of Kyiv I. A. Tyutchev is fond of inorganic chemistry. He published a textbook on inorganic chemistry "Initial Fundamentals of Mineral Chemistry", Part I (Metaloids), studied titanium acid, investigated silicate minerals. In 1867, I. Tiutchev defended his doctoral dissertation "On the Chemical Formula of Vesuvian". Mineral Vezuvian has a rather complicated nature; its structure is still unclear. On the basis of studies conducted by I. A. Tyutchev, the correlation between the basic components of this mineral was established. He gave the same formula to Vesuvian on the basis of the then popular theory of types of Gerard.
The learner of I. A. Tyutchev was Mykola Andreevich Bunge (1842‑1914), who very warmly responded to his teacher as a man with encyclopedic education. Being a student, M. A. Bunge received a lot of inorganic preparations in the university, as well as in the home laboratory of the rector of the Kyiv University. He investigated the effect of sodium amalgam on the salt of various metals, and in 1866 published a study on the synthesis of potassium nitroprusside.
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Mykola |
M. A. Bunge showed that under the action of nitric oxide on the red blood salt, potassium nitroprusside is formed. The latter can also be isolated when exposed to a yellow blood salt of a mixture of sulfuric and nitric acids. As a result of the study of nitrogen oxides, he came to the conclusion that nitrogen dioxide should be considered as a mixed anhydride of nitrate and nitric acids. This conclusion has not lost its significance now. The study of nitro compounds was devoted to the master's thesis Bunge, which he defended in 1868.
Later, while working at the Department of Chemical Technology, MA Bunge, in addition to the above-mentioned studies, issues "Essays on inorganic chemistry", ed. I (1867), studying graphite of the Kherson province (1874), graphite of the Volyn province (1881), publishes the "Chemical Technology of Water" (1879); in the paper "The course of chemical technology. Part inorganic "(1894‑1900) develops methods for clearing the Dnepr water.
During the reign of the chemical laboratory P. P. Alekseyev inorganic chemistry on the natural department of the Faculty of Physics and Mathematics and at the Faculty of Medicine was read by Fedor Minovich Garnich-Garnitsky, who in 1870 moved from Kharkiv. From his papers on inorganic chemistry, one can note the study of the solubility of acetylene and carbon monoxide in an ammonia solution of copper monohloride. He drew attention to the formation of new compounds. He reported on the results of this work at the 7th Congress of Naturalists in 1883 F. M. Garnich-Garnitsky also studied the chemistry of chloric carbonyl.
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Fedor |
Almost simultaneously with F. M. Garnich-Garnitskiy the position of associate professor of the department of chemistry, on the recommendation of O. Butlerov, was approved by the master of chemistry Alexander Ivanovich Bazarov.
A. I. Bazarov was mainly interested in theoretical questions of general and inorganic chemistry. Already the first of his performed works in Kyiv "On the structure of certain nitrogen compounds" (1871) and "On atomic and structure" (1873) are of great importance for the affirmation of atomic-molecular theory. Maintaining the theory of the chemical structure of Butlerov, A. I. Bazarov pointed out that for chemical testing of substances it is far from enough to know their empirical formulas. Very important property of substances is their structure, the best proof of this may be isomerism.
Interesting views of Bazarov were on valence. He successfully observes that the submission of chemists about the constancy of the valence elements is not substantiated, especially since they are not suitable for molecular compounds. In addition, he believed that the elements may have different values of valence and the nature of the valence may be twofold. These conclusions are very close to understanding the two-type nature of valence, which was first disclosed by D. I. Mendeleyev. Later, on this basis, the notion of negative and positive valence developed.
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Alexander |
A. I. Bazarov develops an advanced for the time look at the nature of the elements. He denies the widespread view of chemical elements as indivisible individuals. Such an interpretation of the concept of "chemical element", in his opinion, reminds those primitive judgments about the elemental nature of actually complex bodies expressed by chemists in the XVIII-th and early XIX-th centuries.
In 1873 A. I. Bazarov studied ortho-iodate acid and, contrary to the statement of the well-known scientist Yu. Thomsen, correctly established the seven-valent nature of iodine in it, as well as the absence of tetravalent oxygen. He gave the correct formula of this acid, but mistakenly believed that it was two-base. Study of this acid somewhat later led to the establishment of its fivefold.
A. I. Bazarov's Doctoral Dissertation (1874) is devoted to the study of fluoroborate acid. When distilling hydrogen fluoride boron, a colorless viscous fraction is obtained which does not emit glass (boiling point 160°). The individuality of this substance was proved only in 1935 Bazarov denied the existence of fluoroboric acid in such a composition, as was the case at that time. In his view, this acid is actually a solution of borate acid in the fluoroborate. Although this conclusion did not receive confirmation, however, his doubts about the identity of the oxyfluoroborate acid had a basis.
It is also interesting to note that A. I. Bazarov considered solutions as chemical compounds in accordance with the theory of Mendeleev, which only began to spread at that time.
So, as we see, already in the 70's of the last century, the main issues of inorganic and general chemistry Bazarov expresses the opinion that for many years ahead of his time. This is also noticeable in his experimental works.
In 1891, a chemical-inorganic department of the laboratory was created, which later turned into a separate department of inorganic chemistry. From 1894 to 1926, the department of inorganic chemistry was headed by Yakov M. Bardzilovsky, most of whose research is related to organic chemistry. For several years (1873‑1881) he studied azo-derivative toluene, the reaction between azobenzene and benzaldehyde, condensation of aldehydes with azo-compounds, condensation of aldehydes with aromatic amines. The last reaction served as the theme of his doctoral dissertation, which he defended in 1896.
Along with this, Y. M. Bardzilovsky studied various water and did their analyzes. He published an article "The Hypothesis on the Unity of Matter and Its Experimental Verification," in which he conceals the complex nature of the elements, emphasizes the existence of the smallest particles of atoms in the spirit of Prouta's hypothesis.
Since 1904 the conditions for conducting educational and scientific work on inorganic chemistry have considerably improved. In 1904 a new 4-storey building was added to the Department of Inorganic Chemistry. The equipment of the new laboratory was all necessary and, first of all, the gas-fired system, the water supply system, the gas-carburettor machine was carried out in the form of the best laboratories of the time.
In 1905, Y. M. Barzylovsky, studying the oxidizing properties of hexacyanophyrate potassium in an alkaline environment, received some new molecular salts of organic amines and hexacyanodiferite anion. He noticed that the organic amines of aniline, para-methachloride and methachloride do not interact with potassium hexacyanophorite in water and in alcohol solutions at normal temperature. Polyamines, however, interact much more energetically, giving the sediments a dark color.
The aforementioned experiments of Ya. M. Barzylovsky on molecular compounds in connection with the nature of their coloring continued Andriy Semenovich KOCHUBEY. The main direction of his research was the study of chemical compounds, the formation of which is characterized by a change in color.
In 1914 he published the results of a study on the nature of the color change of a solution of cobalt chloride under the influence of various factors. Considering that in this case the solvent is of negligible importance, he investigated the transfer of water by electrolysis of a solution of cobalt-2 chloride in the presence of phenol as an indifferent additive, in relation to which the change in the amount of water in the anode and cathode spaces was determined.
As a result of the experiments, A. S. Kochubey showed that the hydration of cobalt ions decreases with increasing concentration of cobalt chloride and temperature increase. At the same time there is a transition of six hydrates of cobalt ion in fourhydrates, as well as in bicars.
He reduces the number of cobalt transport he correctly explains the hydration of his ions; In blue, blue complexes of cobalt chloride with alcohol molecules, or tetrachlorohydroxycobaltate complex, are formed. True, he believed that he was not finally clarified the question of education from hydrochloric acid, calcium chloride or magnesium ions tetrachlorohydroxycobaltate complex.
In red solutions of cobalt chloride, which also contain zinc chloride, cadmium, stibium, mercury, according to Kochubey, double complexes must be formed, which, in addition to the tetrachloroxydroxycobaltate complex, include chlorides of the corresponding metals of zinc, mercury, and stibium, which cause reversed reddening of hydrochloric acid solutions of cobalt chloride.
Although the idea of the composition of the blue complexes of cobalt chloride, expressed by A. S. Kochubeyi, is not entirely correct, however, the association of the fact of the change of color with complex formation and the decrease in the hydration of cobalt ions is scientifically substantiated and is fully confirmed in studies of a later time.
From the theoretical works of this time in the field of inorganic chemistry, one should name the research of G. D. DAYN and S. V. DAYN (1913‑1914). University professor G. D. Dain in 1913 expressed an interesting idea about the electronic nature of the oxidation-reduction reactions. In his work "Concealed reactions or oxidation-reduction reactions from the electronic point of view of S. V. Dayn" (1914), he explained the oxidation-reduction reactions on the basis of contemporary ideas about the structure of the atom. According to Dain, any chemical reaction consists in the transfer of electrons from one atom to another.
During oxidation-reduction reactions, the separation of electrons from atoms can occur only when there are other atoms that can take them. Hence, as G. V. Dayn emphasizes, the intersection of the relationship between the reactions of reduction and oxidation is clear. The total number of electrons remains unchanged. In chemical reactions, the transition of electrons to elements in one row of the periodic system occurs, as a rule, in the direction from the first to the seventh group. In the same groups, the transition of electrons from atoms to the other occurs in two ways: in the first subgroups, the ability to give electrons is weakened in the direction of reducing atomic weight; in other subgroups of groups of elements, the ability to transition electrons is reversible. The exclusion of electrons characterizes the oxidation of atoms, and the joining of electrons causes the restoration of elements. The views expressed by S. V. Dayn and G. V. Dayn were fairly advanced at the time. This was one of the first attempts to explain the oxidation-reduction reaction in a new way. The basic idea of these scientists lives in our times.
By 1933, research at the Department of Inorganic Chemistry was distinct in nature. Among them are the works of D. K. HORALEVICH, who studied (1924‑1926) higher oxygen compounds of the elements of the 8th group of the periodic system of chemical elements. He described the preparation of a green product of iron oxidation in the presence of a alkali by melting stalled with a saltpeter or potassium chlorate. The author concluded the existence of 8-valence nickel and iron and gave the formula as if he had been allocated a superscription of barium (IV) ferrate. Attempts by other authors to confirm this result did not have positive effects. In addition, Goralevich studied the compounds of uranium.
After the university's renewal, scientific work on inorganic chemistry is somewhat revived.
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Volodymyr A. |
Volodymyr A. IZBEKOV investigated electrolytic properties of melted salts, chemical interactions of salts in meltdowns, as well as changes in the range of metal stresses in melted systems compared with aqueous solutions. He first showed the dependence of the electrochemical range of metal volumes on the solvent, and also established the connection between the decomposition potentials and the heat of formation of the corresponding compounds.
V. A. Izbekov was interested in the electrolyte nature of melted and liquid under normal conditions of salt systems. According to his advice, L. N. Einhorn investigated tetrachloride and quaternary titanium as solvents in the study of non-electrolytes. The brilliant lecturer, Izbekov has trained a lot of talented chemists-inorganics who work in Ukraine and abroad.
At the department of inorganic chemistry in the first years after the university's restoration research was applied. V. A. Izbekov and M. V. Vovk in 1934‑1935 were engaged in the allocation of rare elements from the raw material.
Since 1950, Yuriy K. DELIMARSKY, being the head of the department of inorganic chemistry, continues research on electrochemistry of melted salts, which he began earlier at the Institute of General and Inorganic Chemistry of the Academy of Sciences of the USSR. This becomes the main direction of the department's research, and work on the electrochemical study of complex compounds in various solutions is adjacent to it, as well as the study of the influence of non-aqueous solvent additives on the size of the electrode potential of the metal.
The department of inorganic chemistry has clearly identified one problem of the study of chemical transformations in a homogeneous liquid medium. Most of the staff of the department participated in the development of issues that united this problem.
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Yuriy K. |
In 1949, Yu. K. Delimarsky published a great deal of work on electrode potentials and an electrochemical series of metal in melted bromides, in which the results of determining the series of metals in melted bromides at various temperatures and in different melted electrolytes are presented, and various methods of determination are compared series of metal in melted salts. It is shown that in one and the same solvent, the order of metals in series can vary depending on temperature. But a deeper influence on a series has a solvent. For each solvent there must be a specific range of series, the position of metals in which is entirely due to the interaction of the components of the solution, as well as the nature of the ions that are formed at the same time.
Yu. K. Delimarsky introduces a polarographic method in the chemistry of melted salts. He showed that the Geyrovsky-Ilkovich equation describes sufficiently the polarographic wave obtained by using a solid electrode for melted salts. Polarographic studies have been conducted on the background of melted chlorides, nitrates, borates (Yu. K. Delimarsky and colleagues).
In the laboratory of inorganic chemistry, a number of experiments were conducted on the study of melted fluorides. Yu. K. Delimarsky and F. F. Grigorenko for the first time determined the stresses of the decomposition of melted fluorides and somewhat improved the method of removing polarization curves. When considering the issue of the electrochemical series for the separation of metals from melted fluorides, they showed that the fluorides of alkaline and alkaline earth metals in the melted form formed complexes. On the basis of certain stresses of the decay, the values of the individual relative electrode potential of metals in the corresponding melted fluorides (taking the electrode potential of sodium for zero) are calculated. It turned out that for heavy metals in corresponding melted fluorides the values are more negative than for iodides. This was explained by the one-sided polarization of fluoride-ion.
In the study of melted fluorides, an analogy of the electromotive force of polarization is established at a temperature close to the point of crystallization of the salt. This fact deserves attention in connection with the study of the nature of the melted state of salts and the structure of maturation.
In the study of the properties of melted borates showed a good solubility of oxides of various metals in the melting borax, determined the stresses of the decomposition of these melts, shows the chemical interaction of even acidic metallic oxides with borax. Based on the found values of the stresses of the decay, the heat formation of metal oxides was determined. Comparison of the values of the heat formation of pure oxides with those values of heat formation, which were calculated on the basis of electrochemical data, gave rise to the conclusion that the chemical interaction of oxides of most metals with borax, which is accompanied by the release of heat. In the case of such interaction, the heat formation of oxides dissolved in melting borax is more important than the formation of pure oxides.
Since 1956, studies on electrochemistry of melted sulphides of heavy metals have been started in order to use the latter for technological purposes. The electric conductivity of melted sulfides of tin, stibium, bismuth, nickel and silver was studied. It is shown that the electrical conductivity of melted sulfides of bismuth and nickel far exceeds the electrical conductivity of melted salts, which are typical electrolytes, and is close to the electrical conductivity of some metals. For spilled sulfides of tin and stibium, electrical conductivity is less important. The electrical conductivity for these sulphides varies in the same manner as the basic nature of the corresponding oxides, ie, it increases from stibium sulfide to nickel sulfide (Yu. K. Delimarsky and A. S. Velikanov).
An important direction of the department's activity was also the study of complex polyhalogenide-type compounds, which was conducted under the direction of Professor Yakov Anatolievich FIALKOV. Studying interhalogenic compounds and phenomena of complex formation with their participation, Ya. A. Fialkov together with his staff performed a lot of works in the laboratory of the Institute of General and Inorganic Chemistry of the Academy of Sciences of the USSR.
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Yakov |
In 1949, investigating the electrical conductivity of systems of tetrachloride titanium bromine and tetrachloride titanium monohloric iodine, he showed that the solution of tetrachloride titanium in bromine does not conduct current. The electrical conductivity of these solutions at various ratios of the components is less than 10-8 Ohm-1 at + 20° and at -20° C. But despite this, as the author emphasized, complex polyhalogenide-type compounds are formed in this system. The introduction of tetrachloride titanium in monochloric iodine reduces the electrical conductivity of the latter. I. A. A. Fialkov concluded that the results refuted the widespread assertions about the connection between the electrical conductivity of solutions of halides in bromine and iodine and the formation of complex solutions in these solutions.
Ya. A. Fialkov and F. D. Shevchenko (1948‑1950) studied the formation of poly iodide salts with cations such as polynitronmetal-ion. It was found that cadmium and zinc can give salts, which contain a heptaiod anion, and for nickel it was possible to obtain even the salt of octoiodium iodide hexanitrinonickel-2. The existence of these compounds has been proven in solutions by solubility, cryoscopy and electroconductivity. In this case, systems of polynitrinometal-ion – iodine – organic solvent were studied. The formation of compounds of ammonium tetraiodoiodide was found in a similar way.
In the study of the transport of ions in nitrobenzene solutions of complex ion polyiodides for systems of iodine iodide of the nitrino complex of nickel, zinc, cadmium, and ammonium iodide, a large similarity in these systems of chemical processes occurring on electrodes was established. In all these systems, the cation is transferred to the cathode, and the iodine content increases in the anode. Based on these experiments it can be concluded that the formation of poly-iodide complexes in these systems, as well as their electrolytic nature.
The study of complex and molecular compounds at the Department of Inorganic Chemistry has become to some extent a tradition that originated in the last century and was secured by I. Bazarov, T. G. Lonachevsky-Petrunyaka, Ya. Bardzilovsky, A. S. Kochubey. Investigations of complex compounds continue in the postwar years. In 1949, 1950, under the direction of V. L. Pavlov, a study was conducted on the separation of thiophosphate compounds of copper, lead, manganese, cadmium, barium, calcium, magnesium. It was shown that in water and alcohol solutions sodium thiophosphate forms sediments that differ in their properties from sulfides and phosphates, that is thiophosphates. Lead salt of lead tetratiophosphate was first obtained in a similar way.
Ya. A. Fialkov and V. V. Grigorieva studied iron, cobalt, copper and nickel trioxiglutarates with the help of spectrophotometry, measurement of electrical conductivity and acidity of aqueous solutions. As a result, the formation of complexes, their composition and stability were revealed. The authors attempted to isolate molecular trioxiglutarates from the solution. The above studies are the first in the study of the complexing properties of trioxyglutaric acid.
In 1954 studies on the kinetics of isotopic metabolism in inorganic compounds were initiated at the Department of Inorganic Chemistry. With ion radioisotope, iodides of silicon and tin were studied, as well as kinetics of exchange in iodine compounds of various oxidation states (Yu. P. Nazarenko, V. L. Pavlov, and others).
Ya. A. Fialkov and K. V. Panasyuk studied the isotopic exchange of sulfate ions in aqueous solutions of sulfatonitrinocomplexes and cobalt sulfatoaquanitrinocomplexes using a radioactive isotope of sulfur. It has been shown that the isotopic exchange in these sulfates has an ionic nature. The influence of acidity, ionic strength and salt concentration on the rate of exchange was also studied. The mobility of complexly bound sulfate groups in the studied middle and acid sulfate nitrinocomplexes and sulfatoaquanitrinocomplexes of cobalt under the same conditions is different. The mobility of these sulfate ions is largely dependent on the nature of the additions included in the internal coordination sphere of the complex compound.
The department also studied iodide, rhodanide and selenocyanate complexes by the method of potentiometry, spectrophotometry, electrical conductivity, solubility and synthetic in both aqueous and in mixed and non-aqueous solutions. In this case, the dependence of complexation on the temperature and solvent was established and it was shown that the temperature increase may cause a noticeable weakening of the bond in the complexes and a decrease in the number of coordinated anions. Introduction of large concentrations of non-solvent solvent (alcohol, acetone) not only increases the stability of the complex, but also contributes to increasing the coordination number. So, for the first time we managed to establish the existence of complexes with coordinate numbers 6 (mercury, cadmium), 8 (lead), etc.
As a result of the study of the influence of non-aqueous solvents of alcohol, acetone, dioxane on the magnitude of the electrode potential, it was shown that at high concentrations of non-aqueous solvents, the latter cause the weakening of the hydration of complexing ions and thus facilitate the formation of more complex complexes. At the same time, investigations of complex compounds in non-aqueous solutions were performed by solubility, electrical conductivity, potentiometry and spectrophotometry. At the same time, regularities concerning the influence of the solvent on the occurrence of complex formation reactions were established. In particular, it has been shown that the stability of complexes in different solutions can not be characterized only by the value of the dielectric constant solvent, as generally assumed.
In the study of rhodanide and selenocyanate complexes in different solutions, the differences between the results of the same system by the solubility method and the method of potentiometry under different conditions in which the research was carried out by these methods was first discovered. In the case of low-strength complexes, the solubility method and the potentiometry method (at constant concentration of the central ion) can be detected in a solution of high-coordination complexes. If in the solution a very stable complex is formed, then only the simpler anionic complexes and even multi-nucleus complexes are detected by the solubility method. In this case, new molecular rhodanides and selenocyanates of many metals have been isolated.
As a result of the study of the conditions for the occurrence of complex formation reactions in the fiber, new definitions of the concepts of "complex" and "molecular" compounds were given.
Among the other theoretical conclusions that were made in the electrochemical investigation of chemical transformations in a liquid homogeneous medium, one can name the explanation of the reasons for changing a number of metal voltages in different environments. It was shown that both in melted systems and in aqueous, mixed and non-aqueous solutions, the main factor that most acutely affects the size of the electrode potential is the complex formation, the mutual polarization between the ions.
Contrary to the statement of some chemists, Yu. K. Delimarsky showed that the displacement in a number of metal voltages may occur in solvents, both with small ones and with large dielectric constant. It is interesting to note that taking into account the high stability of the electronic shell of fluoride-ion for fluorides compared to other halides in the melt, one could expect the highest concentrations of the potential determinants of metal ions. That is why electrode metal potentials should seem to be more positive than other halogens. However, experiments do not confirm this. Electrode potentials in melted fluorides appeared to be more negative than in melted iodides. This fact is explained satisfactorily on the basis of the assumption of the mutual polarization of ions.
The study of melted systems and various solutions made it possible to calculate thermodynamic characteristics for a number of compounds, to theoretically substantiate the electrolytic production of pure metals. The latter is especially true for the study of melted fluorides, borates, and sulfides.
From studies of inorganic chemistry, it is worthwhile to note the study of heavy metal chlorates and their molecular compounds with dioxane that have been conducted over recent years.
The department also conducts research on the applied nature: studying the conditions for the restoration of barite to obtain barium sulfide, studying the solubility of barium chloride in the presence of calcium chloride to improve the purification and crystallization scheme of barium chloride when obtained from barium sulfide. Several studies of historical and methodological nature (Yu K. Delimarsky, Ya. A. Fialkov, V. L. Pavlov, F. D. Shevchenko, etc.) have been fulfilled, issues of the nomenclature in inorganic chemistry have been developed.
In recent years, the department has focused its efforts on the study of rare elements, primarily zirconium, selenium, vanadium, germanium, chemical processes in solutions and meltdowns, in order to find convenient methods for separating close 'by their nature of elements.
At the Department of Inorganic Chemistry, which was headed by Yu K. Delimarsky from 1950, research was carried out on electrochemistry of molten salt, which became the main focus of scientific research of the department. Along with this, on the initiative of Professor Ya. A. Fialkov began studying complex compounds, which later became dominant in the scientific activity of the department. In 1960-1977, the department of inorganic chemistry was headed by Professor Andriy Matveyevich GOLUB, from 1978 to 1998 Academician of the National Academy of Sciences of Ukraine, Honored Scientist of Ukraine Viktor Vasilyevich SKOPENKO, now - Corresponding Member. NAS of Ukraine Mykola Semenovich SLOBODYANIK. The following general courses were taught and read at the department: "Inorganic Chemistry", "Informatics and Programming", "Mathematical Methods in Chemistry", "Structure of Substances", "Materials Science", "Physical Methods of Research of Chemical Compounds", "Fundamentals of Ecology", "Chemical technology". The course of inorganic chemistry at the Faculty of Chemistry was read by Academician NAS of Ukraine Yu. K. Delimarsky, Professors A. M. Golub, V. V. Skopenko, V. O. Kalibabchuk, M. S. Slobodyanyk. Among the textbooks given by the teachers of the department: A. M. Golub “Inorganic Chemistry”, V. V. Grigorieva, V. M. Samoilenko, A. M. Sych. “General Chemistry”, V. V. Skopenko, V. V. Grigorieva “Major classes of inorganic compounds”, S. A. Nedilko, P. P. Popel “General and inorganic chemistry. Collection of problems”, S. A. Nedilko, P. P. Popel. “General and inorganic chemistry. Tasks and Exercises”, K. M. Boyko, V. M. Samoilenko, M. S. Slobodyanik, N. V. Ulko “General and inorganic chemistry. Workshop”.
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Andriy |
In the early 1960s, two main areas of scientific research were the main ones at the Department of Inorganic Chemistry: chemistry of coordination compounds and oxide materials with special electro-physical properties. Investigations in the field of coordination compounds are associated with the names of A. M. Golub and V. V. Skopenko. Under their leadership, a scientific school was created, which is considered one of the most authoritative not only in Ukraine, but also far beyond its borders. Achievements of the school were awarded with two State Prizes of Ukraine in the field of science and technology (1990 – A. M. Golub, V. V. Skopenko, V. M. Samoilenko, T. P. Lishko, 1995 – V. V. Skopenko, V M. Kokozay) and the V. Vernadsky Prize (2000 – V. V. Skopenko). for services in scientific-pedagogical work and building of the university Academician V. V. Scopenko was awarded the title Hero of Ukraine with the Order of the State (1999), was awarded the Order of “Merit of ІІІ, ІІ and I degrees”, was elected an Honorary Doctor of Bratislava, Yagelon, Chernivtsi, Chaotong (Taiwan), Tauride, Moscow, Jilinsky (Republic of China), Rostov Universities and Honorary Professor at the International University of Plato.
The first period of the school's development was associated with a systematic study of coordination compounds with pseudo-halide ligands and obtained its logical conclusion in the monograph "Chemie der Pseudohalogenide", published in 1979 in Berlin, which was later published in Ukrainian and English. The second period of the school's development can be characterized by the creation of new scientific areas: bio-coordination chemistry, coordination chemistry on the surface of a solid, direct synthesis of coordination compounds. Thus, finding out the biochemical role of amino acids and biological functions that carry metals in living organisms, gave impetus to the study of coordination compounds with amide, hydrazide, oxime and carbacylamidophosphate ligands. In the direction of coordination chemistry on the solid state surface, studies of complex formation processes on the surface of silica, modified with N-, O-, S- and P-containing organic and inorganic ligands are carried out.
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Viktor |
Investigation of complex formation reactions involving metal powders and metal oxides gave an opportunity to form a new scientific direction – direct synthesis of coordination compounds. The results of the research are summarized in the monographs: V. V. Skopenko, V. M. Kokozay, O. Yu. Vasilieva, V. O. Pavlenko and others. "Direct synthesis of coordination compounds" (1997), V. V. Skopenko, V. M. Kokozay, O. Yu. Vasilieva, V. O.Pavlenko and others. "Direct synthesis of coordination and organometallic compounds" (1999), Yu. V. Kholin, V. M. Zaitsev. "Complexes on the surface of chemically modified silica" (1997), V. Zaitsev. "Complex-forming silicas: synthesis, structure of the graft layer, chemistry of the surface" (1997). Doctoral theses were defended by V.M. Kokozay (1994), R. D. Lampeka (1997), V. Zaitsev (1997), A. K. Trofimchuk (1997), K. V. Domasevich (1998), A. I. Brusilovets (2000), O. A. Golub (2002), V. M. Amirkhanov (2002), I. O. Fritsky (2003). Among the published textbooks: Golub A. M., Skopenko V. V. "Fundamentals of coordination chemistry" (1977), V. V. Skopenko, L. I. Savransky "Coordination chemistry" (1997), V. V. Skopenko, V. Ya. Zub. "Coordination chemistry. Workshop"(2002).
In the early 60's, A. M. Golub initiated a new scientific direction at the Department - material science. The rapid development of new branches of science and technology required the creation of new inorganic materials with special optical, electro-physical, magnetic and other properties. It was then that intensive studies began, which could be formulated as follows: "composition-structure-properties". To solution this problem, extensive research has begun on promising oxide materials based on REEs, such as aluminates, galatians, chromites, chromates, vanadates, molybdates, tungsten, manganites, niobates, tantalates, cobaltites, and the like. At the same time, studies on the clarification of the laws of the synthesis of phosphates in solutions and melts began, the study of the relationship between the composition, structure and properties of double phosphates of single- and polyvalent metals began.
It was in the sixties that the Department synthesized a variety of materials for a new technology with a wide range of physical and chemical properties, such as semiconductors, ferroelectrics, piezoelectrics, ferrites, thermistors, nonlinear optical and other optical materials, luminophores.
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Mykola |
In the second half of the seventies (under the direction of the academician of the National Academy of Sciences of Ukraine Skopenko V. V.) and from the end of the twentieth century (under the direction of the member of the NAS of Ukraine Slobodyanik M. S.) material science research began to cover new fields. In this direction, the physicochemical bases of controlled synthesis of crystalline phosphates of single- and polyvalent metals as well as of functional oxide materials (professors M. S. Slobodyanik, P. G. Nagornyi, S. A. Nedilko, associate professors F. F. Grigorenko , K. M. Boyko, A. M. Sych, doctor of sciences Yu. O. Titov). In particular, the regularities of the crystallization of complex phosphates in the solution-melting of systems of the type MIO-P2O5-MxOy have been determined. Relationships between composition, structure and properties of synthesized double phosphates of mono- and polyvalent metals are established. New approaches to the synthesis of hetero-substituted phosphates with crystalline frames such as KTP, Nasicon and Langbeinit have been developed. A series of new phosphate matrices was synthesized and investigated, the effect of homo- and heterovalent substitution and conditions of growing crystals on the nonlinear-optical characteristics of complex phosphate type KTP (KTiORO4) (professors M. S. Slobodyanik and P. G. Nagornyi) was determined. Energy-saving methods for the synthesis of particularly durable structural ceramics, oxide materials with metallic, and then high-temperature superconductivity are being developed (Prof. Nedilko S. A., Associate Professor Drozd V. O.). The dependence of the synthesis conditions and different types of substitutions on the physico-chemical properties of complex substituted compounds is investigated. The peculiarities of the formation of representatives of the family of layered perovskite-like ferro-piezoelectrics of type AnBnO3n + 2 from the systems of co-deposited components are established. A series of new compounds, solid solutions and polymorphic modifications of the general composition AnBnO3n + 2 was synthesized and investigated, their crystalline structure was determined. Relationships between the composition, the type of heteroatoms, the method of their localization in perovskite blocks and the degree of agnosticity (the magnitude of the spontaneous polarization) of the substitutable phases of the type AnBnO3n + 2 are established. The criteria for the implementation of layered compounds of the type AnBnO3n + 2 (Dr.S. Yu. O. Titov) are determined.
The cycle of works on the chemistry of phosphates of polyvalent metals was noted in 1989 by the prize of them. L.V. Pisarzhevsky of the National Academy of Sciences of Ukraine (V. V. Skopenko, M. S. Slobodyanik, P. G. Nagornyi). Doctoral dissertations defended: S. Nedilko – 1994, P. G. Nagorny – 1998, Yu. O. Titov – 2003, I. V. Zatovsky – 2012.
In the nineties of the twentieth century, the scientists of the department participated in the implementation of international projects under the INTAS program. The results of scientific research are published in international and domestic journals.
