Background
Alexander Mikhailovich Butlerov was born on September 6, 1828, in Chistopol, Kazanskaya. Butlerov’s father, Mikhail Vasilievich Butlerov, a retired lieutenant colonel, and mother, Sofia Mikhailovna, owned part of Butlerovka village.
Alexander Mikhailovich Butlerov was born on September 6, 1828, in Chistopol, Kazanskaya. Butlerov’s father, Mikhail Vasilievich Butlerov, a retired lieutenant colonel, and mother, Sofia Mikhailovna, owned part of Butlerovka village.
Butlerov received his primary education in a private boarding school, later attended a Gymnasium in Kazan, and studied at Kazan University from 1844 to 1849.
Butlerov became interested in chemistry while still at boarding school. He experimented independently and once, following an explosion in the boarding school kitchen, was placed in a punishment cell, from which he was led to dinner with a board inscribed “Great Chemist” tied to his chest. This ironic inscription proved to be prophetic. At Kazan University, Butlerov studied chemistry under N. N. Zinin, as well as Claus, the discoverer of ruthenium. Under Zinin’s influence, Butlerov decided to devote himself to chemistry; at home, he built a laboratory, where he prepared isatin, alloxazine, and other organic compounds. After Zinin left for St. Petersburg, however, Butlerov devoted his energies to another of his interests, entomology. His thesis, for which he received the degree of candidate of natural sciences, was published as Dnevnie babochki Volgo-Uralskoy fauny (“Diurnal Butterflies of the Volga-Ural Fauna”). He had collected the material for the thesis during his excursions around Kazan and during a trip to the steppes on the cast bank of the Volga River and near the Caspian Sea in the spring and summer of 1846.
As early as 1851 Butlerov defended his master’s dissertation, “Ob okisleny organicheskikh soedineny” (“On the Oxidation of Organic Compounds”). On the whole, this work was a historical survey. It includes few original thoughts, although his remarks that isomerism is based on molecular structure and that changes in chemical characteristics are associated with structural changes are worthy of mention. Butlerov included with his master’s dissertation his first experimental work on the oxidizing action of osmic acid on organic compounds. His doctoral dissertation, “Ob efirnykh maslakh” (“On Essential Oils”), which he defended at Moscow University in 1854, was also mainly a historical survey. Both of these remained in manuscript form and were not published until 1953 in Volume I of his Sochinenia (“Works”).
Immediately after graduating from the university, Butlerov began leaching chemistry there, at first (1849-1850) part-time, then as Carl Claus’s official assistant; from 1852, after Claus’s transfer to Dorpat University, he taught all the chemistry courses in the university. Between 1860 and 1863 he was twice rector of the university. From 1868 to 1885 Butlerov was a professor of chemistry at St. Petersburg University. In 1885, after thirty-five years of service, he retired but continued to teach special lecture courses at the university.
Butlerov’s teaching ability immediately attracted the attention of both his students and his colleagues, but initially, he taught by lecture only - work in the laboratory was not required of his students, and he himself worked there only sporadically. Until 1857, Butlerov devoted much more time to experiments set up in his greenhouses and in fields. He reported on this research in a great many articles and notices, most of which were published in the Zapiski (“Notes”) of the Kazan Economic Society in which he was active. In this period he made unsuccessful attempts to build a soap factory and to improve the production of phosphorus matches.
In the early 1850’s Butlerov adhered to obsolete theoretical views (he, as well as Claus, taught chemistry from a textbook by C. Lowig, the author of one version of the theory of radicals); but in 1854, on Zinin’s advice, he familiarized himself with the work of Laurent and Gerhardt and became one of their passionate supporters. However, the greatest changes in his work and thought resulted from his trip abroad in 1857-1858. During his travels Butlerov met such eminent young chemists as Kekule and Erlenmeyer and spent about half a year in Paris, participating in the meetings of the Paris Chemical Society, which had just been formed, and working for two months in Wurtz’s laboratory.
In Wurtz’s laboratory, Butlerov began his first series of experimental investigations. Discovering a new way to obtain methylene iodide, he studied many derivatives of methylene and their reactions. As a result, he was the first to obtain hexamethylenetetramine (urotropine) and a polymer of formaldehyde which in the presence of limewater is transformed into a sacchariferous substance. This was the first complete synthesis of a sacchariferous substance.
On the other hand, Butlerov did not succeed in obtaining either dihydroxy ethylene, CH2(OH)2, or the free methylene radical itself, instead of which he obtained its dimer - ethylene. However, both of these negative results served as material for future generalizations. These investigations showed the trait characteristic of Butlerov’s work, the effort to study a reaction in full, not neglecting its by-products. They were usually completed with very small quantities of the substances involved and enabled him to perfect his skill in experimentation.
Work on the methylene series ended in 1861 when Butlerov stated the basic ideas of the theory of chemical structure and directed his experimental investigations toward the verification and support of his new theory. He arrived at the theory of chemical structure through continuous research and a recognition of the unsatisfactory state of theoretical chemistry. Although he developed a theory of types similar to Gerhardt’s, defended it in print, and on returning from abroad employed it as the basis of a lecture course in organic chemistry, he clearly recognized that he must go beyond Gerhardt.
Butlerov attempted to develop Dumas’s theory of carbonaceous types, but all conventional viewpoints proved unsatisfactory for the explanation of addition reactions, which he had come across in describing the results of his work on the methylene series. Summing up his research, he arrived at the theory of chemical structure, which, according to Markovnikov, he began to expound in his lectures as early as 1860.
At the end of the 1850’s and the beginning of the 1860’s, the theoretical side of chemistry did not correspond to the sum of its empirical data and knowledge. Kekulé, Wurtz, and the majority of other chemists adhered to the theory of polyatomic radicals, which was a further development of Gerhardt’s theory of types; Kolbe and his school developed a unique theory of carbonaceous types; and Berthelot used “formation equations.” Several chemists - for example, Kekulé (in 1861) - began in despair to reject rational formulas, based on one or another theoretical representation, and turned to empirical formulas. At precisely this juncture Butlerov read his paper “O khimicheskom stroeny veshchestv” (“On the Chemical Structure of Substances”) at the chemical section of the Congress of German Naturalists and Physicians in Speyer (September 1861).
In this paper, Butlerov defined the concept of chemical structure: “Assuming that each chemical atom is characterized by a specific and limited quantity of chemical force [affinity], with which it participates in the formation of a substance, I would call this chemical bond or [this] capacity for the mutual union of atoms into a complex substance chemical structure.”
From this definition it follows that the concept of chemical structure (the term is found in the work of Russian chemists before Butlerov, but it is used in another sense) could be brought forward only after there had been a sufficiently clear definition of the concepts “atom” (the attribute “chemical” left open the question of the possibility of its further separation into “physical” atoms), “valency” (the quantity of an atom’s affinity), and “interatomic bond.” Thus, the following can be considered as the preconditions for the existence of a theory, within chemistry itself, of chemical structure: (1) sufficiently clear concepts of atomic theory and molecular theory- which was achieved at the Congress of Chemists in Karlsruhe (1860); (2) development of the study of valency in the form ascribed to valency by Kekulé (1857-1858); (3) the creation of the concept of interatomic bond, as it was formulated in the works of Kekule and Couper (1858).
Butlerov advanced the basic proposition of the classical theory of chemical structure:
“I consider it possible, for the time being, to change the well-known rule - to wit, that the nature of a compound molecule is determined by the nature, quantity, and arrangement of elementary component parts - in the following manner: the chemical nature of a compound molecule is determined by the nature of its component parts, by their quantity, and by their chemical structure.”
Butlerov noted means for determining the chemical structure of molecules and formulated the rules that should be followed in this determination. He gave primary importance to those synthetic reactions in which the participating radicals retain their chemical structure. He foresaw the possibility of regrouping but believed that after a detailed study of matter from the point of view of chemical structure, the general laws for regrouping would be deduced.
Guided by the propositions he had formulated, Butlerov explained the existence of isomerism, stating that isomers were compounds possessing the same elementary composition but different chemical structure. Discovery of the facts of isomerism, which did not correspond to this definition, led to the establishment by van’t Hoff and Le Bel of stereochemistry, which Butlerov did not accept immediately and, when he did, only in part; specifically, he accepted only the explanation of the optical activity of organic compounds as the result of the presence of asymmetric carbon atoms.
Butlerov explained the relationship of the properties of isomers - and of organic compounds in general - to their chemical structure by the existence of “the mutual influence of atoms,” which is transmitted along the bonds; as a result of this influence, atoms possess different “chemical values” depending on their structural environment. This general proposition was given concrete expression in the form of many “rules” by Butlerov himself and, especially, by his students Markovnikov and Popov. In this century these rules, as well as the whole concept of atoms’ mutual influence, have received an electron interpretation.
Of great importance for the consolidation of the theory of chemical structure was its experimental corroboration in the work of Butlerov’s school. Butlerov himself deserves credit for the prediction and proof of positional and skeletal isomerism. Having unexpectedly obtained tertiary butyl alcohol, he was able to decipher its structure and predicted (later proving, with the aid of his students) the existence of its homologues; he also predicted (1864) the existence of two butanes and three pentanes and, later, that of isobutylene.
In the second half of the 1860’s the nature of unsaturated compounds was still unexplained. A series of investigations conducted by Butlerov, completed at the beginning of the 1870’s, led to a conclusion supporting the hypothesis that they contain multiple bonds.
Butlerov’s indication that sulfur had a valence of six and his experimental proof of the tetravalence of lead must be considered contributions to the theory of valency. Throughout the 1860’s he gave much attention to organometallic compounds and developed methods, widely used by his school, for synthesizing organic zinc compounds.
In order to promulgate the theory of chemical structure throughout organic chemistry, Butlerov published Vvedenie k polnomu izucheniyu organicheskoy khimy (“An Introduction to the Complete Study of Organic Chemistry”), the second edition of which was published in German under the title Lehrbuch der organischen Chemie. E. von Meyer, a student of Kolbe’s school (which rejected the theory of chemical structure), considered the work to be a magnificent textbook on organic chemistry that greatly influenced the development and popularization of the structural theory.
In 1867-1868 Butlerov went abroad to aid in the publication of the German edition of his book; he traveled to Algiers for a rest but nearly perished on the way; the ship encountered a violent storm and was off course for several days, out of control and half swamped. There was another goal of his trip, however. The official decree concerning his mission stated that the purpose of the voyage was to enable him to explain to foreign chemists his right to major participation in the development of contemporary chemistry.
Thus, Butlerov’s trip was connected with the defense of his priority. Until then there had been a tendency to credit the creation of structural theory to Kekulé (Couper’s name was not yet known), for in 1857-1858 he had stated the theoretical propositions that served as the preconditions for the emergence of the theory of chemical structure, and in 1865 he had quite successfully extended the theory to aromatic compounds. Formulas representing conclusions drawn on the basis of several of Kekulé’s (and Couper’s) valency rules coincided with structural theory (in 1868 L. Meyer stated this viewpoint very clearly in opposition to Butlerov’s attempts to defend his priority), while within the framework of this theory, the deduction of formulas was based on the study of the properties of the relevant molecules, as well as on the valency of atoms.
Butlerov’s second great service - this time to chemistry in Russia - was the creation of the first Russian school of chemists. After his return from abroad in 1858, he equipped his laboratory with gas and expanded it; his students had to complete required practical work, and his first “disciples” appeared. Of these, V. V. Markovnikov, A. M. Zaytsev, and A. P, Popov occupied professorial chairs in universities during Butlerov’s lifetime.
Nonetheless, in the 1860’s Butlerov sought to leave Kazan. One reason for this was his unsuccessful term as rector. In March 1860 he had become the last “crown” (appointed by the imperial government) rector of Kazan University; however, striving not only to institute liberal changes but also to halt student abuse of individual teachers, Butlerov came into severe conflict with the student body. This forced him to request retirement, which was granted on August 1861.
Nonetheless, in November 1862 Butlerov became - against his wishes - the first elected rector of the university. The outbreak of a struggle between groups of professors and Butlerov’s clash with a trustee led to his retirement in July 1863. He was bitter about the experience and tried to find a position outside Kazan. Only the insistence of his friends (as well as the birth of a son in April 1864) stopped him from departing immediately.
In May 1868 Butlerov was made a professor of chemistry at St. Petersburg University. He continued teaching there until 1885 when he retired on pension but continued to give special lecture courses. His followers at St. Petersburg form a prominent group of Russian organic chemists - the most famous being A. E. Favorski and L. L. Kondakov. At various times G. G. Wagner, D. P. Konovalov, and F. M. Flavitsky worked in his laboratory. Butlerov’s outstanding characteristic as an instructor was that he taught by example; the students could always observe what he was doing and how he was doing it.
Surprisingly, election to the Academy of Sciences hardly aided Butlerov’s scientific activity, since the condition of its laboratory was so deplorable that not until 1882, after thorough repairs, could he transfer his experimental work there. A struggle for the right of Russian scholars to the recognition of their service by the academy weakened Butlerov’s position within the academy.
Butlerov was the first to begin the systematic study of the mechanism of polymerization reactions based on the theory of chemical structure; this was continued in Russia by his successors and was crowned by S. V. Lebedev’s discovery of the industrial means of producing synthetic rubber.
Secondary results of the study of polymerization. During the attempts to polymerize ethylene, the conditions were found under which it could be hydrated to obtain ethanol. Studying the polymerization of isobutylene and amylene, and having found their isomers in the reaction mixture, in 1876 Butlerov generalized that a dynamic equilibrium can exist between two isomeric forms. These ideas concerning reversible equilibrium isomerizations are found in Butlerov’s work as early as 1862-1866.
Butlerov's major achievement was in advancing the theory of structure in chemistry, especially with regard to tautomerism, the facile interconvertibility of certain structurally similar compounds.
Another achievement came in 1861 when Butlerov stated his concept of chemical structure: that the chemical nature of a molecule is determined not only by the number and type of atoms but also by their arrangement. He foresaw and demonstrated the existence of isomers (molecules composed of the same atoms but in different arrangements), such as the two butanes and three pentanes. He is also regarded for synthesizing isobutane in 1866 and in his discovery that he made in 1868 stating that unsaturated organic compounds contain multiple bonds.
Butlerov’s chemical structure theory was first to look at the chemical structure. He demonstrated the existence of isomers where molecules could have the same molecular formula, but different structures.
Butlerov was also the first to synthesize formaldehyde. Formaldehyde (CH2O) is the simplest aldehyde and is used as a basic building block in several organic chemical syntheses. It is also used as a stabilizer in photography and histology and as a biocide to kill bacteria and fungi.
Another Butlerov's achievement was in being an advocate of higher education for women; he participated in the organization of university courses for women (1878) and lectured to them on inorganic chemistry. He also created laboratory courses in chemistry. In addition, Butlerov delivered in St. Petersburg, as he had earlier done in Kazan, a large number of public lectures, most of which had a chemical-technical basis.
Butlerov was the organizer and propagandist for scientific apiculture in Russia. He published many articles and notices in the Russian and foreign press, and in 1886 founded the Russkii pchelovodnyi listok (“Russian Apiculture Leaflet”).
The crater Butlerov on the Moon is named in his honor.
Quotations: "I would... change the accepted rule that the nature of a complex molecule is determined by the nature, quantity, and position of its elementary component parts, by the following statement: the chemical nature of a complex molecule is determined by the nature of its elementary component parts, their quantity, and chemical structure."
From 1857 Butlerov was a member of the Chemical Society of Paris, and from 1869 of the Russian Chemical Society. He was chairman from 1878 to 1882 of the chemistry section of the Russian Physics and Chemistry Society, formed in 1878 by the merging of the chemistry and physics societies. Butlerov was also an honorary or foreign member of the Chemical Society of London (from 1876), the American Chemical Society (1876), the Czech Chemical Society (1880), the German Chemical Society (1881), the Russian Physics and Chemistry Society (1882), the Russian Technical Society (1885), and of many others.
In 1870 Butlerov was selected a junior scientific assistant of the St. Petersburg Academy of Sciences; the following year he became an associate member and in 1874 a full member.
While in St. Petersburg, Butlerov had yet another unusual interest - spiritualism. He was convinced that “medium” phenomena could be studied by scientific methods and even spoke on this theme at the seventh conference of Russian naturalists in Odessa, August 1883. However, experiments with mediums, conducted in the presence of a scientific commission, ended in complete failure. Mendeleev, who participated in the commission, later wrote, “Our spiritists obviously do not see the deception.” P. D. Boborykin, a student of Butlerov’s at Kazan University, defined his passion as an “atavism of religiosity.”
Quotes from others about the person
Markovnikov, in his reminiscences of Butlerov, gives this evaluation of the significance of Butlerov’s trip to Paris to participate in the meetings of the Paris Chemical Society: "He did not have to finish his education, as did most of those [Russians] sent abroad. He had to see, rather, how scientific experts worked, to observe the origin of ideas and to enter into intimate relations with these ideas, which the scientists readily exchanged in personal conversations... that were often held privately and not committed to print... With a basic reserve of scientific knowledge, and possessing absolute fluency in French and German, he had no difficulty standing on an equal footing with the young European scientists, and owing to his outstanding abilities, choosing the correct direction."
In 1852 Butlerov married Nadezhda Mikhailovna Glumilina, niece of the writer S. T. Aksakov.
Karl Ernst Claus (23 January 1796 – 24 March 1864) was a Baltic German chemist and naturalist. Claus was a professor at Kazan State University and a member of the Russian Academy of Sciences. He was primarily known as a chemist and discoverer of the chemical element ruthenium, but also as one of the first scientists who applied quantitative methods in botany.
Nikolay Nikolaevich Zinin (25 August 1812 in Shusha – 18 February 1880 in Saint Petersburg) was a Russian organic chemist. In St. Petersburg, professor Zinin was a private teacher of chemistry to the young Alfred Nobel. He is known for the so-called Zinin reaction or Zinin reduction, in which nitro aromates like nitrobenzene are converted to amines by reduction with sodium sulfides. In 1842 Zinin played an important role in identifying aniline.
