Butlerov, Aleksandr Mikhailovich

(b. Chistopol, Kazanskaya [now Tatarskaya, A.S.S.R.], Russia, 6 September 1828; d.a Butlerovka, Kazanskaya, Russia, 17 August 1886)

chemistry.

Butlerov’s father, Mikhail Vasilievich Butlerov, a retired lieutenant colonel, and mother, Sofia Mikhailovna, owned part of Butlerovka village. Butlerovka received his primary education in a private boarding school, later attended a Gymnasium in Kazan, and studied at Kazan University from 1844 to 1849.

Immediately after graduating from the university, Butlerov began teaching 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.

In 1852 he married Nadezhda Mikhailovna Glumilina, niece of the writer S.T. Aksakov.

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. From 1857 he 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 societis. 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.

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 discoveror 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 interest, 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 east bank of the Bolga 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 ompounds. 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”).

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. Löwig, 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 Kekulé 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.

Markovnikov, in his reminiscences of Butlerov, gives this evaluation of the significance of Butlerov’s trip:

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 [Zhurnal Russkogo fiziko-khimicheskogo obshchestva, 19 (1887), supp., 76].

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 (containing, as was established by E. Fischer, α-acrose). This was the first complete synthesis of a sacchariferous substance.

On the other hand, Butlerov did not succeed in obtaining either dihydroxymethylene, 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 (Sochinenia, I, 561), 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 Kekulé 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 [Sochinenia, I, 70].

This proposition, as is evident from its wording, broke with the traditional view that the properties of molecules are determined principally by the nature of the space grouping of atoms in the molecules, by the relative position of the atoms, and by the distances separating the atoms; these problems could not be studied by methods then available. All the remaining propositions of the classical theory of chemical structure are directly or indirectly associated with this proposition.

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.

Leaving open the question of the preferred structural formulas, Butlerov explicitly expressed his opinion about their sense: When the general laws of the relationship between the chemical properties of substances and their chemical structure became known, the corresponding formula would be an expression of all these properties.

The only incorrect proposition in Butlerov’s paper was the supposition concerning the possibility of a primordial (i.e., inherent in free atoms) difference in units of affinity (valency). In connection with this hypothesis Butlerov was the first to produce a model of a carbon tetrahedron (it was irregular). Having subjected the hypothesis to experimental verification and having rejected it, he further developed the theory of chemical structure in a long article, “Über die verschiedenen Erklärungsweisen einiger Fälle von Isomerie”. However, the propositions stated in the article were implied in his paper delivered at Speyer.

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 Burtlerov’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. The formulas of his two butanes were represented as follows:

As early as 1866 Butlerov reported the synthesis of isobutane. Regarding this he wrote (Sochinenia, I, 199): “The principle of chemical structure… can now serve as the best guide in researching questions related to isomerism. Using this principle, one can predict phenomena that could be neither predicted nor explained by prior [theoretical] viewpoints”.

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 a 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 valency of atoms. It was forgotten, however, that in his textbook and in many magazine articles, Kekulé used the “theory of polyatomic radicals” even after 1861 and that, having changed his views in 1864, after Butlerov’s criticism, stated that in his textbook he “had always given preference to one form of rational formulas, specifically, to the one that reflects the views concerning atom bonds as the method of forming molecules” [Lehrbuch der organischen Chemie…, II, pt. 2 (1864), 244–245].

Markovnikov immediately spoke out against this historically incorrect contention, but the legend was nonetheless created. Kekulé gave the hint, L. Meyer developed it, and Schorlemmer reproduced it in The Rise and Development of Organic Chemistry (London, 1879). In his Benzolfest (1890) Kekulé told how the structural theory came to him as he rode on the top of a London bus in 1857 or 1858. Since then, this elegant tale has fluttered along the pages of histories of chemistry and of anniversary articles, although long ago Markovnikov indicated Butlerov’s Basic role in the creation and initial development of the classic theory of chemical structure.

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 professional 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” (i.e., 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 in 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 bitted 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 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 I. 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.

Butlerov was 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.

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 recognition of their service by the academy weakened Butlerov’s position within the academy. For example, in 1874 Butlerov and Zinin failed in their advocacy of Mendeleev’s candidacy for membership. In November 1880 Mendeleev was again nominated by Butlerov to the seat that became vacant after Zinin’s death. The second blackballing of Mendeleev elicited a storm of indignation throughout the nation. At the same time, the faction within the academy that had prevented Mendeleev’s election proposed their own candidates for membership and for academic prizes. Thus, in January 1882, after Mendeleev’s failure to be elected Beilstein was nominated. Seeing Beilstein as a protégé of that same anti-Russian faction, Butlerov energetically opposed his candidacy and succeeded in depriving Beilstein of the requisite number of votes. In order to attain this end, however, Butlerov was forced to turn directly to public opinion, publishing in the Moscow newspaper Rus a long article with the provocative title “Russkaya ili tolko Imperatorskaya Akademia nauk v St.-Petersburge?” (“[Is There] a Russian or Merely an Imperial Academy of Sciences in St. Petersburg?”).

The work of Butlerov and his students can be classified as follows:

(1) Research designed to confirm the theory of chemical structure and to synthesize theoretically possible isomers. Trimethyl acetic acid was obtained, its genetic connection with pinacolone alcohol was established, and the correct structure of pinacolone alcohol and pinacol were given. In addition, Butlerov gave a general schema of pinacolin rearrangement. Concluding this set of experiments, pentamethylethanol was synthesized.

(2) Investigation of polymerization reactions. The possibility of the polymerization of ethylene (unsucessfully), propylene, butene-2, and isobutylene was studied. The mechanism of the polymerization of isobutylene was especially carefully studied, since the polymerization stops at the dimer and trimer stages; Butlerov sought to study “the simplest instance of pure and, perhaps, less complex polymeriziation of the ethylene series of hydrocarbons,” His students simultaneously studied the polymerization of amylene. Thus, 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.

(3) Secondary results of othe 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. Subsequently, C. Laar proposed the term “tautomerism” for these phenomena, but his representation of the mechanism of reversible isomerism proved to be less correct than Butlerov’s.

(4) Random research in chemistry (organic, inorganic, and physical) and even in physics. Thus, not considering the a priori rejection of Prout’s hypothesis to be possible, Butlerov arrived at the assumption of the possibility of changes in atomic weights—for example, under the influence of luminous rays. The experiments undertaken did not, of course, yield positive results.

To Butlerov’s St. Petersburg period belong his statements defending and substantiating the theory of chemical structure, from an epistemological point of view, against attacks by his colleagues Menschutkin and, to a lesser degree, Mendeleev. His speech “Sovremennoe znachenie teory khimicheskogo stroenia” (“The Contemporary Significance of the Theory of Chemical Structure,” 1879) and his article “Khimicheskoe stroenie i teoria zameshchenia” (“Chemical Structure and the Theory of Substitution,” 1885) include such statements. Against Menschutkin’s positivist orientation, which in this instance followed Berthelot, Butlerov advanced the thesis that chemists had not only the right, but also the responsibility, to speak of molecules and atoms as if speaking of things that in fact exist and, doing this, to preserve the conviction that this belief would not become a baseless abstraction.

A course of lectures (“A Historical Essay on the Development of Chemistry in the Last Forty Years”), given by Butlerov in 1879–1880 at St. Petersburg University, served as partial substantiation of the theory of chemical structure. In the end, Menschutkin, who was Butlerov’s successor in the chair of organic chemistry at St. Petersburg, changed his position, supporting the theory of chemical structure.

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”).

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 (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 deception.” P.D. Boborykin, a student of Butlerov’s at Kazan University, defined his passion as an “atavism of religiosity.”

BIBLIOGRAPHY

1. Original Works. Butlerov’s writings include Vvedenie k polnomu izucheniyu organichieskoy khimy (“Introduction to the Complete Study of Organic Chemistry”), 3 pts. (Kazan, 1864–1866), trans. into German as Lehrbuch der organischen Chemie zur Einführung in das specielle studium derselben, 4 pts. (Leipzig, 1867–1868); Stati Po mediumizmu (“Articles on Mediumism”; St. Petersburg, 1889); Stati po pchpelovodstvu (“Articles on Apiculture”; St. Petersburg, 1891); Izbrannye raboty po organicheskoyo khimy (“Selelctled Works on Organic Chemistry”), in the series Klassiki Nauki (Moscow, 1951), with a bibliography of his chemical works; Nauchnaya i pedagogicheskaya deyatelnost. Sboronik dokumentov (“Scientific and Pedagogic Activity. A Collection of Documents”; Moscow, 1961), with a list of the archives where Butlerov’s MSS are preserved; and Centenary of the Theory of Chemical Structure. Collection of Papers of A. M. Butlerov, A. S. Couper, A Kekulé, and V. V. Markovnikov (Moscow, 1961). His writing are collected in Sochinenia (“Works”), 3 vols. (Moscow, 1953–1958); Volum III includes a complete bibliography of his works.

II. Secondary Literature. Works on Butlerov are A. M. Butlerov, 1828–1928 (Leningrad, 1929), a collection of articles on Butlerov; G. V. Bykov, Istoria klassicheskoyo teory khimicheskogo stroenia (“History of the Classical Theory of Chemical Structure”; Moscow, 1960); “La correspondance des chimistes étrangers avec A.M. Butlerov”, in Archives internationales d’histoire des sciences, 14 (1961), 85–97; Aleksandr Mikhailovich Butlerov (“A Sketch of his Life and Activity”; Moscow, 1961); and “The Origin of the Theory of Chemical Structure,”, in Journal of Chemical Education, 39 (1962), 220–224; G. V. Bykov and J. Jacques, “Deux pionniers de la chimie moderne, Adolphe Wurtz et Alexandre M. Boutlerov, d’aprés une corresponodance inéditie,” in Revue d’histoire des sciences, 13 (1960), 115– 134; G. W. Bykow und L. M. Bekassowa, “Beiträge zur Geschichte der Chemie der 60-er Jahre des XIX. Jahrhunderts. I. Briefwechsel zwischen E. Erlenmeyer und A. M. Butlerow (von 1862 bis 1876),” in physis, 8 (1966). 179–198; “II. F. Beilsteins Briefe an A. M. Butlerow,” ibid., 267–285; “III. Die im Briefform verfasste chronik der Herausagabe eines Lehrbuchs für Chemie,” ibid., 10 (1968), 5–24 G. V. Bykov and L.V. Kaminer, Literatura ob A. M. Butlerove i po istory klassicheskoy teory khimicheskogo stroenia (“Literature on A.M. Butlerov and the History of othoeo Classical Theory of Chemical Structure”; Moscow, 1962); W. N. Dawydoff, Über die Entstehung der chemischen Structurlehre unter besonderer Berücksichtigung der Arbeiten von A. M. Butlerov (Berlini, 1959); J. Jacques, “Booutlerov, Couper et la Société Chimique de Paris (notes pour servir á: I’histoire des théories de la structure chimique”, in Bulletin de la Société chimique de France (1953), 528–530; H. M. Leicester, “Alexander Mikhailovich Butlerov”, in Journal of Chemical Education, 17 (1940), 203–209; and “Contriobuotions of Buotlerov to the Development of Structural Theory,” ibid., 36 (1959), 328–329; “Pisma russkikh khimikoc k A. M. Bulterov” (“Letters of Russian Chemists to A. M. Butlerov”), in Nauchnoe nasledstvo (“Scientific Heritage”), Vol. IV (moscow, 1961); and Zhurnal Russkogo fizikokhimicheskogo obshchestva, 19 , supp. (1887), devoted to speeches and articles by G. G. Gustavson, A. M. Zaytsev, V. V. Markovnikov, and N. A. Menschutkin in memory of Butlerov.

G. V. Bykov

BUTLEROV, ALEKSANDR MIKHAILOVICH

(b. Chistopol, Kazanskaya, Russia, 9 September 1828; d. Butlerovka, Kazanskaya, Russia, 17 August 1886)

chemistry, chemical structure, professionalization of Russian science. For the originalarticle on Butlerov see DSB, vol. 2.

Since G. V. Bykov’s study of Butlerov appeared in the original DSB, relatively few works have been published that have examined Butlerov and his outstanding contributions to chemistry. The most important of these studies concern the nature of Butlerov’s contribution to the the ory of chemical structure, but others address topics including Butlerov’s role in the professionalization of Russian chemistry, Butlerov’s involvement with spiritualism, and his ultimately futile efforts to secure Dmitri Mendeleev a full membership in the St. Petersburg Academy of Sciences.

The Theory of Chemical Structure. In his DSB study, Bykov forcefully argued that Butlerov was the originator of the concept of chemical structure. In doing so, he paid scant attention to Friedrich August Kekulé and other chemists who traditionally have been seen as the main contributors to the development of structure theory.

Bykov’s analyses in the DSB and elsewhere, as well as those of other Soviet historians of chemistry, were quite successful in bringing Butlerov’s name to the attention of scholars outside of the Soviet Union, and some of these began to give Butlerov credit for the theory of chemical structure. In the years since Bykov’s DSB article, however, other very careful work has shifted the balance of attention back to Kekulé and other scientists for the formulation of the original concepts that comprised the structural theory in the years around 1858. Nevertheless, Butlerov played a seminal role in establishing a coherent theoretical framework for understanding these ideas, as well as in his experimental work elucidating various aspects of the structure theory.

Butlerov’s interest in chemical structure undoubtedly arose during his first trip abroad in 1857–1858. Up to this time, he had focused his attention on teaching and finishing his master’s and doctoral theses, neither of which contained significant experimental work. During his trip abroad, Butlerov met several times with Kekulé and Richard August Carl Emil Erlenmeyer, and later worked for several months in Charles Adolphe Wurtz’s laboratory in Paris, conducting his first significant organic chemistry research there. It is clear that Butlerov’s attention had shifted as a result of these conversations and meetings early in his trip, as his official plan for the trip written before he left Kazan included no provision for laboratory work at all and strongly hinted that the most important goal of the trip was to visit prominent vacation spots in Europe! While in Paris, Butlerov deepened his interest in the theory of chemical structure through discussions with Archibald Scott Couper, who shortly after Butlerov’s departure published a paper that contained many of the essential features of Kekulé’s theory, but which appeared slightly later. Butlerov, along with Couper, was one of the earliest members of the Société Chimique de Paris and presented an early version of his structure theory at a meeting of the society in 1858.

Butlerov returned to Russia following his trip abroad with a desire not only to transform chemistry in Russia

but also to contribute to chemistry’s general theoretical development. He continued the experiments he initiated in Paris and did not allow his geographical isolation in Kazan to isolate him from the chemical debates raging in western Europe, which often had happened to earlier Russian chemists when they returned from study abroad. When Butlerov next traveled abroad in 1861, he delivered a speech at the Speyer meeting of the Congress of German Naturalists and Physicians (Versammlung Deutscher Naturforscher und Aerzte), which Bykov took as the founding statement of the theory of chemical structure. However, Butlerov did not introduce any fundamentally new concepts in this speech. For example, while Butlerov insisted on the need to determine the chemical and not the actual physical arrangement of atoms in a compound, this distinction derived from a long line of his predecessors, including Jean Baptiste Dumas, Charles Frédéric Gerhardt, Auguste Laurent, Kekulé, Wurtz, and others. Moreover, Butlerov’s call for chemists to search for “truly rational formulae” was not so different from Kekulé’s use of formulas, even though the latter sometimes used different formulae for the same substance in order to illustrate differing functions or reactions. Furthermore, Kekulé did not at this time begin “in despair to reject rational formulas” (in Bykov’s phrase), but merely temporarily used empirical formulas in one paper because the substances he was addressing were too complicated for any other notational style to describe them simply. What was important about Butlerov’s 1861 speech was that it clearly and convincingly argued that chemical structure could be determined through a consistent application of the theory of atomicity. Alan Rocke suggests that Butlerov’s role here in the development of chemical structure was similar to the role Stanislao Cannizzaro had played only a few months earlier with respect to atomic and molecular magnitudes (1993). Finally, Butlerov himself in this speech disclaimed any priority to a new theory, but emphasized the need to consistently develop the existing theory of chemical structure.

In the years after 1861, Butlerov and his students conducted important experimental work that was designed to illustrate various aspects of the theory of chemical structure or its consequences. For example, Butlerov used structure theory to predict many different positional and structural isomers and he obtained many of them in the laboratory. One of the most famous of these was tertiary butyl alcohol, which Butlerov synthesized in 1863. The next year he was able to identify this compound as one predicted earlier by Hermann Kolbe. Butlerov and his students were able to synthesize and identify many homologues of this compound, greatly strengthening the structural theory. In the course of this work, Butlerov and his students formulated many different “rules” that showed how the specific structural environments of compounds help shape their chemical reactivity. Butlerov became, arguably, the most consistent and forceful advocate for the thorough use of the concepts of chemical structure. Butlerov himself never claimed to be the originator of the theory of chemical structure and did not deny Kekulé’s role, but rather wanted his own role as a major developer of the theory to be acknowledged. Butlerov’s goal was to clarify the confused and complex situation of organic chemistry by promoting a consistent use of standard terminology.

Professionalization of Russian Chemistry. Butlerov dramatically changed the style of his chemistry research after his trip abroad in 1857–1858, as well as its intellectual focus. Upon Butlerov’s return from abroad, he expanded the chemistry laboratory and began to attract his first student “disciples.” Of crucial significance for Russian science was his determination to professionalize chemistry at Kazan University by introducing various innovations that would put its teaching on the same basis as the most advanced university in Germany. First of all, this meant teaching chemistry through extensive laboratory exercises and practical work, including original research efforts, a pedagogical innovation of Justus Liebig and certain other German chemists of the 1830s and 1840s. Up to this time, chemistry laboratories at Russian universities largely were occupied with preparing items for lecture demonstrations, although a few students occasionally conducted some laboratory experiments, as did Butlerov when he was a student. Butlerov gradually persuaded the university to allocate more funds for the chemistry laboratory, which would permit all students to receive intensive practical training in the laboratory.

More importantly, Butlerov began to construct a stable pathway or career ladder for students who wished to pursue advanced training in chemistry. Over the course of several years, Butlerov obtained university funding to support a group of laboratory assistants who after several years of study and research work would be sent abroad to work for several years, usually in one of the best-known chemistry laboratories of western Europe. After returning to Kazan to finish their degrees, the young chemists would then be able to compete for a chemistry position at a higher educational institution in Russia. In spite of the relatively small number of chemistry students Butlerov was able to attract to his laboratory, he was spectacularly successful in producing future chemistry professors. His students became prominent chemists at Kazan, Moscow, and Warsaw Universities, among others. In addition, the tradition of excellence in chemistry continued at Kazan long after Butlerov’s departure.

Other Aspects of Butlerov’s Career. After Butlerov moved to St. Petersburg in 1868, he became heavily involved with spiritualism, an interest that lasted until his death. Until recently this aspect of Butlerov’s career has not attracted much attention from scholars, and most historians of science tend to ignore or minimize any possible impact on or connection of spiritualism with his other more “scientific” activities. Butlerov was introduced to spiritualist phenomena by his cousin through marriage, Alexander N. Aksakov, a member of a very prominent cultural family in Russia at that time. Butlerov believed that spiritualist phenomena could be studied scientifically, but a scientific commission to investigate mediumistic phenomena organized by Mendeleev in 1875–1876 ended in mutual recriminations over deception and unfair practices. Bykov implies that this commission revealed the mediums as hoaxers and that the episode ended with a victory for the opponents of spiritualism. The verdict at the time, however, was not so clear-cut. The spiritualists claimed that Mendeleev and the commission had not followed the ground rules for séances, and so the results of their experiments were invalid; whether the spiritualists’ objection was legitimate remains a matter of controversy.

While it is abundantly clear that Butlerov devoted considerable time and effort to spiritualism, the full extent of his activities and correspondence with other spiritualists likely will remain a mystery, as much of Butlerov’s personal papers concerning spiritualism were destroyed after his death.

Perhaps surprisingly, considering Butlerov’s clashes with Mendeleev over spiritualism, Butlerov took the lead only a few years later in trying to have Mendeleev elected to a full chair in the St. Petersburg Academy of Sciences. Butlerov had become involved with the Academy of Sciences shortly after his arrival in St. Petersburg and by 1874 had been elected to the highest (full chair) position in chemistry. Butlerov soon began to promote Mendeleev for an adjunct position at the Academy, but this failed in 1874, although a later vote for Mendeleev as a corresponding member in 1876 was successful. Soon after the death in 1880 of N. N. Zinin, a prominent chemist who held the chair of technology at the Academy, Butlerov proposed Mendeleev’s candidacy for the vacant technology chair. However, the Academy declined to elect Mendeleev, despite Butlerov’s vociferous advocacy. The result was a firestorm of protest in the media, which continued for months. Butlerov was convinced that an anti-Russian faction at the Academy was responsible for Mendeleev’s rejection, although the situation was more complicated than only a conflict over nationalism. Butlerov continued to press for the election of Russians to the Academy until his death.

SUPPLEMENTARY BIBLIOGRAPHY

WORK BY BUTLEROV

Lektsii organicheskoi khimii, Nauchnoe nasledstvo 18, ed. O. D.Sterligov. Moscow: Nauka, 1990.

OTHER SOURCES

Brooks, Nathan M. “Alexander Butlerov and the Professionalization of Science in Russia.” Russian Review 57 (1, 1998): 10–24.

Bykov, G. V. “K istoriografii teorii khimicheskogo stroeniia.”Voprosy istorii estestvoznaniia i tekhniki 4 (1982): 121–130. A response to Rocke’s 1981 article written shortly before Bykov’s death.

Dmitriev, Igor S. “Skuchnaia istorii (o neizbranii D. I.Mendeleeva v Imperatorskuiu akademii nauk v 1880 g.).”Voprosy istorii estestvoznaniia i tekhniki 2 (2002): 231–280.

Gordin, Michael D. A Well-Ordered Thing. Dmitrii Mendeleev and the Shadow of the Periodic Table. New York: Basic Books, 2004. Includes information about Butlerov’s involvement with spiritualism and his efforts to have Mendeleev elected to the Imperial Academy of Sciences in St. Petersburg.

Rocke, Alan J. “Kekulé, Butlerov, and the Historiography of the Theory of Chemical Structure.” British Journal for the History of Science 14 (1981): 27–57. A detailed examination of the competing claims for Kekulé and Butlerov as the originator of the theory of chemical structure.

———.The Quiet Revolution. Hermann Kolbe and the Science of Organic Chemistry. Berkeley: University of California Press, 1993.

Nathan Brooks