MENDELEEV, DMITRY IVANOVICH

[b. Tobolsk. Siberia [now Tyumen Oblast, R.S.F.S.R.], Russia, 8 February J 1834; d. St. Petersburg [now Leningrad], Russia. 2 February 1907)

chemistry.

Mendeleev was the fourteenth and last child of Ivan Pavtovich Mendeleev, a teacher of Russian literature, and Maria Dmiirievna Kornileva, who came of an old merchant family (she herself owned a glass factor) near tobolsk). His mother, who died when he was fifteen, plaved a large part in Mendeleev’s early education and was strongly influential in shaping the views that he held throughout his life. Mendeleev entered the “Tobolsk Gymnasium when he was seven, and graduated from it in 1849; while there he learned to dislike ancient languages and theology and to enjoy history, mathematics, and physics. In Tobolsk Mendeleev, who lived with his family near the glassworks, also acquired an interest in industrial affairs and, through the group of Decembrists exiled there, a love of liberty.

Shortly before her death, Mendeleev’s mother took him to St. Petersburg, where in 1850 he enrolled in the faculty of physics and mathematics of the Main Pedagogical Institute, a progressive institution in which the revoluionary democrat Nikolai Dobrolyubov was a fellow student. Among his teachers were the chemist A. A. Voskresensky. who gave his pupils a taste for chemical experiment (and of whose lectures Mendeleev wrote down detailed descriptions that are preserved in the Mendeleev Museum in Leningrad); the zoologist Brandt, who interested Mendeleev in the classification of animals (his notes on this subject are also preserved); the geologist and mineratogist Kutorga. who immediately assigned him the chemical anal)sis of orthosilicate and pyroxene, and thus introduced him to research techniques; and the pedagogue vyshnegradsky, who influenced his ideas on education.

Mendeleev graduated from the Institute in 1855 with a brilliant record, but his hot temper led him into a quarrel with an important official of the Ministry of Education, and his first teaching assignment was therefore to the Simferopol Gymnasium, which was closed because of the Crimean War.

After two months in the Crimea, where he was unable to work, Mendeleev went to Odessa as a teacher in the Iyceum. and there look up the continuation of his early scientific work. He had already begun to investigate the relationships between the crystal forms and chemical composition of substances. On graduating from the Institute, he had written a dissertation entitled “"Izomorfizm v svyazi s drugimi otno sheniami formy k sostavu” (“Isomorphism in Connection With Other Relations of Form to Composition”). It was published in Gorny zhurnal (“Mining Journal”) in 1856. The writing of this work in itself led Mendeleev still further into the comparative study of the chemical properties of substances; his master’s dissertation, prepared while he was in Odessa, was entitled “Udelnye obemy” (“Specific Volumes”) and was a direct extension of the earlier articles, in which he had raised the question of whether the chemical and crysialtographic properties of substances have any relation to their specific volumes.

During this same period, Mendeleev, in order to support himself, also wrote articles for Novosti cstestrenvhh nauk (“News of Natural Sciences”) and reviews for Zhurnal ministcrsfra naroduogo prosreshchetfia (“Journal of the Ministry of Public Education”), At a slightly later date he wrote an article on gas fuel and the Bessemer process for Promyshlenny Iistik (“Industrial Notes”), From this time, the application of science to industry and economics was a pronounced and recurrent preoccupation in his work.

In September 1856 Mendeleev defended a master’s thesis at the University of St. Petersburg, expressing his adherence to the chemical ideas of Gerhardt, to which he remained loyal throughout his life. Among other topics, he made known his agreement with unitary and type theories and his opposition to Berzelius’ electrolytic theory of the formation of chemical compounds. Mendeleev adhered to Gerhardfs ideas all his life, and in consequence later years found him resisting Arrhenius’ electrolytic theory, rejecting the concept of the ion as an electrically charged molecular fragment, and refusing to recognize the realitv of the electron, lie was opposed in general to linking chemistry with electricity and preferred associating it with physics as the science of mass. His predilection found its most brilliant vindication in the correlation he achieved between the chemical properties and the atomic weights of elements. Nor was he a chemical mechanist in the methodological sense then fashionable in certain quarters. Chemistry in his view was an independent science, albeit a physical one.

In October 1856 Mendeleev defended a thesis pro venia legendi to obtain the status of privatdocent in the university. His subject was the structure of silicon compounds. In January 1857 he began to give lectures in chemistry and to conduct research at the university’s laboratories. In 1859–1860 Mendeleev worked at the University of Heidelberg, where he first collaborated with Bunsen, and then established his own laboratory. He studied capillary phenomena and the deviations of gases and vapors from the laws of perfect gases. In 1860, he discovered the phenomenon of critical temperature—the temperature at which a gas or vapor may be liquefied by the application of pressure alone—which he called the “absolute temperature of boiling.” He was thereby led to consider once again the relationship between the physical and chemical properties of particles and their mass. He was convinced that the force of chemical affinity was identical to the force of cohesion; he looked upon his work, then, as falling within the realm of physical chemistry, the ground upon which chemistry, physics, and mathematics met.

Mendeleev took part in the first International Chemical Congress, held at Karlsruhe in 1860. The idea of the congress had been Kekulés; its purpose was the standardization of such basic concepts of chemistry as atomic, molecular, and equivalent weights, since the prevailing use of a variety of atomic and other weights had considerably impeded the development of the discipline. At the congress Mendeleev met a number of prominent chemists, including Dumas, Wurtz, Zinin, and Cannizzaro, whose championship of Gerhardt’s notions impressed him deeply. His account of the congress, in a letter to his teacher Voskresensky, was published in the St. Petersburg Vedomosti (“Record”) in the same year.

In February 1861, on his return to St. Petersburg, Mendeleev published Opyt teorii predelov organicheskikh soedineny (“Attempt at a Theory of Limits of Organic Compounds”), in which he stated that the percentage of such elements as oxygen, hydrogen, and nitrogen could not exceed a certain maximum value when combined with carbon—a theory that brought him into direct opposition to the structural theories of organic chemistry. On this theory he based his text Organicheskaya khimia (“Organic Chemistry”), which was published in the same year (a second edition was brought out in 1863) and which won the Demidov Prize.

From January 1864 to December 1866 Mendeleev was professor of chemistry at the St. Petersburg Technological Institute and a docent on the staff of the university. In addition, he traveled abroad on scientific assignments for three or four months of each year, wrote books, edited translations, and participated in the compilation of a technical encyclopedia, for which he wrote articles on the production of chemicals and technical chemistry, including the production of alcohol and alcoholometry. In 1865 he defended a thesis for the doctorate in chemistry, “O soedinenii spirta s vodoyu” (“On the Compounds of Alcohol With Water”). In it he first developed the characteristic view that solutions are chemical compounds and that dissolving one substance in another is not to be distinguished from other forms of chemical combination. In this thesis, he also adhered to the principles of chemical atomism.

At this same time Mendeleev, stimulated by the stormy social conditions that followed on the abolition of serfdom in Russia, became more strongly attracted to the practical problems facing the national economy. He began to study petroleum, traveling to Baku for that purpose in 1863; he attended the great industrial expositions held in Moscow in 1865 and in Paris in 1867; he purchased the estate of Boblovo, near Klin, in 1865 to demonstrate how agriculture could be put on a rational scientific basis; and he joined the Free Economic Society, where he lectured on such subjects as experimental agriculture, cooperative cheesemaking, and experiments with fertilizers. In 1862 he also married Feozva Nikitichna Leshchevaya; they had a son and a daughter.

It is appropriate here to consider how Mendeleev’s work was situated in the context of the major scientific advances of the earlier nineteenth century. He had learned of the cell theory in the lectures on botany given at the Pedagogical Institute. Out of a belief in the unity of forces of nature had developed the law of the conservation of energy, which was fundamental to the study of chemical transformations in their relation to physical properties. The Darwinian theory of evolution had come to dominate the study of living nature, and considering the way in which the periodic law in its turn followed out of these fundamental discoveries, William Crookes could later refer to Mendeleev’s theory as “inorganic Darwinism.”

Mendeleev was also active in the growth of Russian chemical organizations during the 1860’s. He participated in drawing up the bylaws of the Russian Chemical Society, which was founded in 1868, and he systematically presented the results of his researches at its meetings. The journal of the society was also important to the growth of the discipline within Russia, and Mendeleev chose to publish many of his findings in it. He further communicated his work to the chemical section of the Russian congresses for natural sciences, of which the first was held in December 1867.

A turning point in Mendeleev’s career occurred in October 1867, when he was appointed to the chair of chemistry at the University of St. Petersburg. In preparing for his lectures he found nothing which he could recommend to his students as a text, so he set out to write his own. He derived his basic plan for his book from Gerhardt’s theory of types, whereby elements were grouped by valence in relation to hydrogen. The typical elements hydrogen (1), oxygen (2), nitrogen (3), and carbon (4) were listed first, followed, in the same order, by the halogens (1) and the alkali metals (1).

Mendeleev entitled his book Osnovy khimii (“Principles of Chemistry”); he finished the first part of it, ending with the halogens, at the end of 1868. During the first two months of 1869 he wrote the first two chapters—on alkali metals and specific heat—of the second part. In spite of their common univalency, he organized the halogens and alkali metals so as to point up their contrary chemical relationships. It then remained to organize them according to another, more basic quantitative variable (or system of ordering), namely, their atomic weight. It may be noted that all Mendeleev’s early work—his studies of the chemical properties of substances, his work on specific weights and their relationships to atomic and molecular weights, his investigations of the limits of compounds, and his study of atomic weights and their correlation with elements—had fitted him to undertake such a task, which was to culminate in the grand synthesis of the periodic law.

On 1 March 1869 Mendeleev was making preparations to leave St. Petersburg for a trip to Tver (now Kalinin) and then to other provincial towns. The free Economic Society had given him a commission to investigate the methods in use for making cheeses in artels. It was on the very day of his departure that he realized the answer to the question of what group of elements should be placed next after the alkali metals in his Osnavy khimii. The principle of atomicity required treating copper and silver as a transitional group, since they gave compounds of both the CuCl₂ and AgCl types; it therefore seemed logical to place them next to the alkali metals, which they most closely resemble in chemical properties. In seeking a quantitative basis to justify such a transition, Mendeleev had the crucial idea of arranging the several groups of elements in the order of atomic weights, a sequence which gave him the Following tabulation:

Ca = 40 Sr = 87.6 Ba = 137

Li = 7 Na = 23 K = 39 Rb = 85.4 Cs = 133

F= 19 C1 = 35.5 Br = 80 Te = 127

Clearly there was a regular progression in the differences between the atomic weights of the elements in the vertical columns (the future periods), and this arrangement made it possible to place other elements of intermediate atomic weight in the gaps in the table. In working out the final stages of his discovery, Mendeleev used the method of “chemical solitaire,” writing out the names or symbols of the elements, together with their atomic weights and other properties, on cards. The procedure was an adaptation of the game of patience, which he liked to play for relaxation.

Mendeleev’s work toward the Osnovy khimii thus led him to the periodic law, which he formulated in March 1869: “Elements placed according to the value of their atomic weights present a clear periodicity of properties.” The work of the Karlsruhe congress had contributed to its discovery; clearly, it would have been impossible to find any relationship between the elements using the old atomic weights—Ca = 20, Sr = 43.8, and Ba = 63.5, for example. The necessity to establish correct atomic weights was indeed what first led Mendeleev to investigate the connections among the elements; from this investigation he proceeded inductively to the periodic law, upon which he was then able to construct a system of elements. He used deduction, however, to predict consequences from his still incomplete discovery, moving from the general to the particular to test the validity of the law. For example, immediately Following his discovery of the periodic law, Mendeleev proposed changing the generally accepted weight for beryllium—14—to 9.4, ascribing to its oxide (after I. Avdeev) the formula BeO (by analogy with magnesia, MgO) and not Be₂O₃ (by anatogy with alumina, Al₂O₃). He thus correctly determined the place of beryllium in his system of elements. He also predicted three undiscovered elements in the future groups III and IV of his system, which he called eka-aluminum, ekasilicon, and ekazirconium.

Mendeleev’s first report of his discovers was “Opyt sistemy elementov, osnovannoy na ikh atomnom vese i khimicheskom skhodstve” (“Attempt at a System of Elements Based on Their Atomic Weight and Chemical Affinity”); he presented it in more detail in “Sootnoshenie svoystv s atomnym vesom elementov” (“Relation of the Properties to the Atomic Weights of the Elements”), which was read to the Russian Chemical Society in March 1869 by N. A. Menshutkin (since Mendeleev himself was away visiting cheesemaking cooperatives). In preparing the latter report, Mendeleev developed several variant tables of elements, including one in which even- and odd-valenced elements were placed in two separate columns. He discovered gaps at three points—between hydrogen and lithium, between fluorine and sodium, and between chlorine and potassium—and predicted that these lacunae would be filled by then-unknown elements having atomic weights of approximately 2, 20, and 36—that is, by helium, neon, and argon.

At first Mendeleev could subsume under the periodic law only isomorphism and atomic weight; in each of these early papers, too, he presented only the quantitative argument for the analytical expression of the law in the form of the increase of atomic weights. The first paper in particular contained many ambiguities and imprecisions; lead, for example, was placed in the same group as calcium and barium, while thallium occupied the same group as sodium and potassium, and uranium was grouped with boron and aluminum. Having been occupied with studies leading up to the law for fifteen years—since 1854—Mendeleev then formulated it in a single day. He spent the next three years in further perfecting it, and continued to be concerned with its liner points until 1907.

In the work that immediately followed his statement of the law, Mendeleev returned to his earlier investigation of specific volumes, studying the physical function of the rule that showed that uranium should be ascribed a doubled atomic weight. Many elements, including tellurium and lead, had therefore to be assigned new places on the table. Mendeleev presented this new result to the Second Congress of Russian Natural Scientists in August 1869, in a report entitled “Ob atomnom vese prostykh tel” (“On the Atomic Weight of Simple Bodies”). He then proceeded to use the same argument to determine chemical functions; having recognized the importance of the simplicity of oxides as compound types, he proceeded to clarify the seven fundamental groups that extend from the alkali metal oxides of form R₂O to the hatogen oxides of form R₂O₇. Mendeleev communicated this finding to the October meeting of the Russian Chemical Society in the memoir “O kolichestve kisloroda v solyanykh okislakh i ob atomnosti elementov” (“On the Quantity of Oxygen in Salt Oxides and on the Valence of Elements”). By 1870, he had taken into account the presence of compounds of the type RO₄ for osmium and ruthenium, and had therefore introduced an eighth group into his classification.

Mendeleev himself summarized the studies that had brought him to the periodic law in a later edition of Osnovy khimii, in which he commented on “four aspects of matter,” representing the measurable properties of elements and their compounds: “(a) isomorphism, or the similarity of crystal forms and their ability to form isomorphic mixtures; (b) the relation of specific volumes of similar compounds or elements; (c) the composition of their compound salts; and (d) the relations of the atomic weights of elements.” He concluded that these “four aspects” are important because “when a certain property is measured, it ceases to have an arbitrary and subjective character and gives objectivity to the equation.”

Since the periodic law was dependent upon the quantitative relation between atomic weight, as an independent variable, and its physical and chemical properties, Mendeleev in 1870 took up the problem of developing an entire “natural system of elements.” He emptoyed deduction to reach the boldest and most far-reaching logical consequences of the law that he had discovered, so that he might, by verification of these consequences, confirm the law itself.

Mendeleev simultaneously described various groups of elements for inclusion in the Osnovy khimii and made them the subject of extended laboratory research. He examined molybdenum, tungsten, titanium, uranium, and the rare metals, and in November 1870 he wrote two articles. In the first, “O meste tseria v sisteme elementov” (“On the Place of Cerium in the System of Elements”), he introduced a theoretically corrected value for the atomic weight of cerium—138, instead of the previously accepted 92—and determined its new place within his system. In the second article, “Estestvennaya sistema elementov i primenenie ee k ukazaniyu svoystv neotkrytykh elementov” (“The Natural System of Elements and Its Application to Indicate the Properties of Undiscovered Elements”), Mendeleev predicted that because of the volatility of its salts, eka-aluminum would be discovered by spectroscopic means.

The Osnovy khimii was finished in February 1871. Among the important ideas that the work embodied was Mendeleev’s notion of the complexity of the chemical elements and their formation from “ultimates.” He stated that the bivalence (II) of magnesium and calcium could be explained as a result of the close blending of monovalent (I) sodium and potassium with monovalent (I) hydrogen:

a formulation that may be seen as a confused premonition of the later rule of displacement.

In March 1871, two years after his discovery of the law, Mendeleev first named it “periodic.” That summer he published in Justus Liebigs Annalen der Chemie his article “Die periodische Gesetzmässigkeit der chemischen Elements,” which he later characterized as “the best summary of my views and ideas on the periodicity of the elements and the original after which so much was written later about this system. This was the main reason for my scientific fame, because much was confirmed—much later.” In the fall of that year Mendeleev turned to conducting research on rare earth metals to determine their place among the elements of group IV. One of his goals was to find the ekasilicon (later called germanium) that he had predicted. He also conducted research on hydrates and complex compounds, especially those of ammonia, and gave public lectures in which he combined chemical topics with philosophical ones.

The reception of the periodic law caused Mendeleev considerable mental anguish. In the sharp and prolonged battle that was soon joined, the law at first had lew advocates, even among Russian chemists. Its opponents, who were especially vocal in Germany and England, included those chemists who thought in exclusively empirical terms and who were unable to acknowledge the validity of theoretical thinking; Bunsen, Zinin, Lars Nilson, and Carl Petersen were prominent among them. Petersen not only doubled the generality of the periodic law but also defended the contradictory view of the trivalence of beryllium. In Germany, Rammelsberg also look issue with a particular point, attempting in 1872 to refute Mendeleev’s proposed correction for the atomic weights of cerium and its close neighbors. Mendeleev answered this charge the following year in an article entitled “O primenimosti periodicheskogo zakona k tseritovym metallam” (“On the Application of the Periodic Law to Cerite Metals”), in which he demonstrated that the facts introduced by Rammelsberg “strengthen, not refute, my proposed changes in the atomic weight of cerium.”

A number of other chemists specializing in the system of the elements either attacked Mendeleev’s law or disputed his priority. Lothar Meyer, for example, proposed in 1870 a representation for the atomic volumes of the elements in the form of a broken zigzag line. Blomstrand and E. H. von Btomhauer developed a spiral system, also in 1870. Mendeleev answered these and other claims to the periodic law—and also claims against it—in the article “K voprosu o sisteme elementov” (“Toward the Question of a System of Elements”), published in March 1871. Basically, however, he had no patience with disputes over priority, and although by taste an internationalist in science, he engaged in such disputes only when others denigrated Russian achievements.

The years 1871 to 1874 saw the acceptance by a number of chemists of Mendeleev’s corrected atomic weights for several elements. Bunsen consented to Mendeleev’s value for indium; Rammelsberg and Roscoe, to that for uranium; Cleve, to that for the rare earth metals (which for yttrium confirmed the values found earlier by Marc Delafontaine, Bunsen, and J. F. Bahr); and Chidenius and Delafontaine, to that for thorium. Nevertheless, the majority of scientists did not accept Mendeleev’s discovery for some time; the first textbook on organic chemistry to be based on the law was published in St. Petersburg by Richter only in 1874. Wurtz’s Théorie atomique further helped to propagate Mendeleev’s ideas. At about the same time, Brauner spoke in favor of Mendeleev’s corrected weight for chlorine and set out to determine the density of the vapors of beryllium chtoride, as Nilson and Petersen had also done—Brauner’s determination of the weight of beryllium was a major confirmation of the generality of Mendeleev’s law.

The discovery of the three elements predicted by Mendeleev was, however, of decisive importance in the acceptance of his law. In 1875 Lecoq de Boisbaudran, knowing nothing of Mendeleev’s work, discovered by spectroscopic methods a new metal, which he named gallium. Both in the nature of its discovery and in a number of its properties gallium coincided with Mendeleev’s prediction for eka-aluminum, but its specific weight at first seemed to be less than predicted. Hearing of the discovery, Mendeleev sent to France “Zametka po povodu otkrytia gallia” (“Note on the Occasion of the Discovery of Gallium”), in which he insisted that gallium was in fact his eka-aluminum. Although Lecoq de Boisbaudran objected to this interpretation, he made a second determination of the specific weight of gallium and confirmed that such was indeed the case. From that moment the periodic law was no longer a mere hypothesis, and the scientific world was astounded to note that Mendeleev, the theorist, had seen the properties of a new element more clearly than the chemist who had empirically discovered it. From this time, too, Mendeleev’s work came to be more widely known; in 1877 Crookes placed in the Quarterly Journal of Science an abstract, entitled “The Chemistry of the Future of Mendeleev’s summarizing article of 1871, while in 1879 a French translation of the full article, with a new introduction, was published by G. G. Quesneville in the Moniteur scientifique.

The discovery of gallium was incorporated into the third edition of Osnovy khimii in 1877. The fourth edition, of 1881–1882, mentioned the discovery of scandium—the ekaboron predicted by Mendeleev—by Nilson, in 1879. Winkler discovered germanium in 1886; its properties matched precisely those of Mendeleev’s ekasilicon, and the discovery of germanium figured in the fifth edition of Mendeleev’s book in 1889. This edition also contained, within a single frame, reproductions of portraits of Lecoq de Boishaudran, Nilson, Winkler, and Brauner. The composite bore the caption “Reinforcers of the Periodic Law.”

The periodic law might now be considered proven, and Mendeleev presented a summary of the research leading to it in his Faraday lecture, “The Periodic Law of the Chemical Elements,” which he delivered at the invitation of the Chemical Society of London on the occasion of the twentieth anniversary of his discovery. He spoke of the scientists who preceded him in his work as well as those who later contributed to the development of the law, and dealt with both the history and what might be called the prehistory of it. During the same visit to London Mendeleev was also invited to lecture before the Royal Institution of Great Britain. In this speech, “An Attempt at the Application to Chemistry of one of Newton’s Principles,” he sought to oppose the concept of chemical structure to the hypothesis that the mutual influence of atoms within the molecule is in concord with Newton’s third law of motion. In both these lectures (which he published in 1889 as Dva Londonskikh chtenia [“Two London Lectures”]), Mendeleev did not confine himself to chemistry, but went on to draw philosophical generalities that embraced the whole of the natural sciences.

Even while he was working toward the periodic law and its proofs, Mendeleev was also concerned with the problem of the liquefaction of gases. As early as 1870 he discussed the necessity of intensive cooling in the process, while in December 1871 he suddenly turned to purely physical research on permanent gases and their compressibility. In initiating this investigation, he hoped to find the hypothetical “universal ether,” which he believed to be an extraordinarily thin gas that must, in his system, occupy the place above hydrogen. Although his primary goal was unreachable, in the course of his studies Mendeleev discovered a number of deviations of gases from the Boyle-Mariotte law, and gave a more precise equation for the state of real gases. His work then assumed a more practical slant, and he turned to aeronautical research; giving a general form to his experiments on the temperature of the upper layers of the atmosphere (1875) in the report “Ob opytakh nad uprugostyu gazov” (“On Experiments on the Elasticity of Gases”), published in 1881. In 1887 Mendeleev made a solo balloon ascension from Klin, for the purpose of observing a solar eclipse.

After 1884, Mendeleev concerned himself with the expansion of liquids and in particular with the specific weights of aqueous solutions of various substances. He was able to conclude that in such solutions discontinuous relationships exist between the solvent and the solute, attesting to the existence of determinate chemical relationships—a necessary condition, according to chemical atomic theory. Mendeleev thus arrived at a chemical theory of solutions, which he opposed to the theory of electrolytic dissociation of dilute aqueous solutions set forth by Arrhenius. Mendeleev stated his theory both in his Issledovanie vodnykh rastvorov po udelnomuvesu (“Research on Aqueous Solutions According to Their Specific Weight”) of 1887 and in the fifth edition of Osnovy khimii.

From the last years of the 1870’s Mendeleev was also concerned with the production of petroleum. In 1876 he visited the United States; in the resultant book, Neftyanaya promyshlennost v Severo-amerikanskom shtate Pensilvanii i na Kavkaze (“Petroleum Production in the North American State of Pennsylvania and in the Caucasus”), he advanced a theory of the inorganic origin of petroleum. Mendeleev traveled to Baku, too, to study oilfields. He did further research on the uses of petroleum, including its medical applications; in 1878 he employed petroleum as a self-treatment for pleurisy. In 1880–1881, Mendeleev wrote a series of reports of the results of his Caucasian journeys, and thus became engaged in a dispute with Nobel over the proper location of petroleum refineries. In 1883, with Po voprosy o nefti (“On a Question of Petroleum”), he entered into a discussion with Markovnikov; in the same year and the one following he wrote a series of works on the refining of both Baku and American oil. In an article of 1889 he denied recurrent rumors of the exhaustion of the Baku fields.

By the end of the 1880’s Mendeleev had added an investigation of the coal industry to his practical concerns; he visited the Donets Basin to study mining and wrote Budushchaya sila, pokoyushchayasya na beregakh Dontsa (“Future Power Lying on the Banks of the Donets”; 1888). None of his efforts toward the development of domestic industry was successful, however; the czarist government chose to dismiss his remarkable ideas and projects as “professorial dreams.”

The decades of the 1870’s and 1880’s marked a major transitional period in Mendeleev’s life. The law that he had discovered was developed and confirmed, and he had turned to more commercial matters in the interest of the national economy; he had also left his family and entered into a second marriage, in 1882, with a young artist, Anna Ivanova Popova, by whom he had two sons and two daughters. He became increasingly concerned with philosophical matters, of which he wrote, “Much in me was changing; at that time I read much on religion, on sects, and philosophy, economic articles,” His writings on philosophical themes included the articles “Ob ediniyse” (“On Unity”; 1870), “Pered kartinoyu A. I. Kuindzhi” (“Before a Picture of A. I. Kuindzhi; 1880), “O edinstve veshchestva” (“On the Unity of Matter”: 1886), and, most importantly, the book Materialy dlya suzhdenia o spiritizma (“Material for an Opinion on Spiritism” 1876), which embodied the results of the work of a special commission of the Physical Society of St. Petersburg. Of the last, Mendeleev later wrote, “I tried to fight against superstition…it took professors to act against the authority of professors. The result was right, spiritism was rejected.”

The same period also saw a change in Mendeleev’s academic status. In 1876 he was elected a corresponding member of the St. Petersburg Academy of Sciences; in 1880 he was defeated in an election for extraordinary membership by the reactionary majority of members of the physics and mathematics section, who had come to fear his democratic tendencies. In the course of the protests that followed this event, Butlerov published an article entitled “Russkaya ili tolko Imperatorskaya Akademia Nauk v S.-Peterburge” (“The Russian or Only an Imperial Academy of Sciences in St. Petersburg”) and some twenty other scientific institutions elected Mendeleev an honorary member. In 1890 disorders broke out among the students at the University of St. Petersburg and Mendeleev underlook to deliver a student petition to the ministry of education. He was given a rude and insulting answer, tantamount to a demand for his personal resignation; he thus left the university, where he had taught for more than thirty years. On 3 April 1890 Mendeleev gave his last lecture to the students of the general chemistry course.

His teaching career at an end, Mendeleev decided to publish a newspaper in support of the protectionist policies that his investigations of petroleum and coal production had convinced him were the “sole means of saving Russia.” Before he could begin this project, however, he received a commission from the naval ministry to conduct large-scale laboratory research on the production of smokeless powder—a secret project that took high priority. From 1890 to 1892, he also participated in a study of the tariff structure, at the invitation of the ministry of finance: this resulted in his Tolkovy tarif (“Comprehensive Tariff”), which was published in 1891–1892. The government was appreciative of his services, and Mendeleev rose rapidly in the bureaucracy, being appointed privy counciltor in 1891.

From 1892 on. Mendeleev was concerned in the regulation of the system of weights and measures in Russia, a task that he discharged “with enthusiasm, since here the purely scientific was closely interwoven with the practical.” In 1893 he was named director of the newly created Central Board of Weights and Measures, a post that he held until his death, and in connection with which he frequently traveled abroad. In the 1890’s Mendeleev was also actively involved in problems of shipbuilding and the development of shipping routes. He participated in the design of the icebreaker Ermak (launched in 1899) and wrote on the progress of research in the northern Arctic Ocean (1901). He simultaneously studied the development of heavy industry in Russia, traveled to the Urals and to Siberia to observe the production of iron, began to publish a series entitled Biblioteka Promyshlennykh Znany (“Library of Industrial Knowledge”)—for which he also compiled a curriculum—and wrote, in addition to several related books and articles, Uchenie o promyshlennosti (“Theory of Industry”; 1901), which contained a number of ideas that he later developed in his Zaventye mysli (“Private Thoughts”; 1903–1905).

Nor was Mendeleev unconcerned with theoretical chemistry during these years. A sixth edition of Osnovy khimii was published in 1895; in it he expressed some skepticism about the discoveries (in 1894 and 1895, respectively) of the first inert gases, argon and helium. After Ramsay’s 1898 discovery of their three analogues (which Ramsay had himself predicted), and after the determination of the place of the whole group as a zero valence group within the periodic system (1900), Mendeleev reconsidered his position and not only accepted the new elements but also grouped Ramsay among the “reinforcers of the periodic law.”

Mendeleev denied the discovery of the electron, however, and in particular the explanation of radioactivity as the disintegration of atoms and the transformation of elements, thinking that these discoveries destroyed the very foundations of the periodic law. He disputed the transmutation of elements in his article “Zoloto iz serebra (“Gold From Silver”) of 1898; while in Popytkakhimicheskogo ponimania mirovogo efira (“An Attempt at a Chemical Conception of the Universal Ether”) of 1902, he introduced the erroneous notion that the universal ether is similar in nature to a very light inert gas and that it takes part in radioactive processes. In 1902 he visited the Paris laboratories of the Curies and Becquerel to study radioactivity further. He dealt with these questions in the seventh and eighth editions (1903 and 1906) of his textbook.

The fifth and later editions of the Osnovy khimiiwere translated into the western European languages. In addition, from 1892 Mendeleev took an active part in the preparation of the great Brockhaus encyclopedia, which provided another vehicle for the dissemination of his ideas in western Europe. He introduced a section on chemistry and the production of chemicals and wrote the articles on matter, the periodic regularity of the chemical elements, and technology, among a number of other topics. His work as a whole amounted to more than 400 books and articles, as well as a large number of manuscripts, which are preserved in the D. I. Mendeleev MuseumArchive, Leningrad State University.

In 1894 Mendeleev was awarded the doctorate by both Oxford and Cambridge; his seventieth birthday was widely observed in 1904, as was the fiftieth anniversary of his scientific career the following year. In 1905 he attended the commemorative session of the Royal Society of London, and was awarded the Copley Medal; he was also a member of many Russian and foreign scientific societies. He held several czarist orders and the French government made him a member of the Legion of Honor. Following his death from heart failure, students followed his funeral to the Volkov Cemetery in St. Petersburg. They carried the periodic table of the elements high above the procession as the fitting emblem of Mendeleev’s career.

BIBLIOGRAPHY

I. Original Works. Mendeleev’s works were published in Russian during his lifetime in the form of monographs and magazine and encyclopedia articles, many of which were translated into English, French, and German. For Mendeleev’s own annotated bibliography of his works (1899) see Sochinenia, XXV, 686–776. After his death Osnovy khimii was reprinted many times, collections of his work appeared in the series Klassiki Nauki (“Classics of Science”), his archival material was published, and his complete works were published as Sochinenia (“Works”), 25 vols. (Leningrad, 1934–1952); a supp. vol. contains a detailed index.

Osnovy khimii (“Principles of Chemistry”), Mendeleev’s main work, went through eight eds. during his lifetime: 1868–1871; 1872–1873; 1877; 1881–1882; 1889; 1895; 1903; 1906. The 1st ed., in 4 pts., was published in two vols. Starting with the 5th ed. the book was no longer divided into parts. In the 8th ed. all notes were placed at the end of the book as special appendixes. The periodic law is the focus of the work; beginning with the 3rd ed. (after the discovery of gallium in 1875) it is more prominent because it had been verified experimentally. Mendeleev rewrote each ed., including all new scientific data—particularly confirmations of the periodic law—and reanalyzing difficulties that had arisen to hinder its confirmation (inert gases, radioactivity, radioactive and rare-earth elements). He also expanded the sections on the chemical industry and on philosophy and methodology. To update the posthumous 9th (1928) and 10th (1931) eds. a section by G. V. Wulff et al. was added on new trends in the construction of chemical principles. This new section was omitted from the 11th to 13th eds. (1932–1947).

The first English trans., The Principles of Chemistry (London, 1891), was made from the 5th ed. The 2nd (London, 1897) and 3rd (London, 1905; repr. New York, 1969) eds. were based on the 6th and 7th Russian eds., respectively. A German version, Grundlagen der Chemie (St. Petersburg, 1890), was based on the 5th ed. and a French trans., Principes de chimie (Paris, 1895), on the 6th ed. Several articles from Periodichesky zakon (“Periodic Law”), B. M. Kedrov, ed., in the series Klassiki Nauki (Moscow, 1958), were published in other languages. Those in English are “The Periodic Law of the Chemical Elements” (written in 1871), in Chemical News and Journal of Physical (Industrial) Science, 40 , nos. 1042–1048 (1879); 41 nos. 1049–1060 (1880), reviewed by W. Crookes, “The Chemistry of the Future,” in Quarterly Journal of Science, no. 55 (July 1877), also published separately, George Kamensky, trans., as An Attempt Towards a Chemical Conception of the Ether (London, 1904); “An Attempt to Apply to Chemistry One of the Principles of Newton’s Natural philosophy,” in Chemical News, 60 , no. 1545 (1889), 1–4; no. 1546, pp. 15–17; no. 1547, pp. 30–32, also published separately under the same title (Loudon, 1889); and “The Periodic Law of the Chemical Elements (Faraday Lecture),” in Journal of the Chemical Society, 55 (1889), 634–656, repr. in Faraday Lectures 1869–1928 (London, 1928). See also “The Relations Between the Properties and Atomic Weights of the Elements,” in Henry M. Leicester and Herbert S. Klickstein, eds., A Source Book in Chemistry 1400–1900 (New York, 1952), 438–444.

French translations include “Remarques à propos de la découverte du gallium,” in Comptes rendus … de I’ Académie des sciences, 81 (1875), 969–972; “La loi périodique des éléments chimiques (Faraday Lecture),” in Moniteur scientifique, 3rd sei., 9 (1879), 691 ff; “La toi périodique des éléments chimiques,” ibid., 4th ser., 3 , pt. 2, no. 572 (1889), 899–904; and “Comment j’ai trouvé le système périodique des éléments,” in Revue générale de chimie pure et appliquée, 1 (1899), 210 ff., 510 ff.,—here, repr. under another title, is “Periodicheskaya zakonnost khimicheskikh elementov” (“Periodic Law of Chemical Elements”), from Brockhaus and Efron’s Entsiklopedichesky stovar (“Encyclopedic Dictionary”).

For German translations, see “Zur Frage über das System der chemischen Elemente,” in Berichte der Deutschen chemischen Gesellschaft, 4 (1871), 348–352; “Die periodische Gesetzmässigkeit der chemischen Elemente,” in Justus Liebigs Annalen der Chemie, supp. 8 , no. 2 (1871), 133–229, repr. in Ostwald’s Klassiker, no. 68 (Leipzig, 1913), pp. 41–118; “Ueber die Stellung des Ceriums im System der Elemente,” in Bulletin de l’ Académie des sciences de St. Petersbourg, 16 (1871), 45–50; “Ueber die Anwendbarkeit des periodischen Gesetzes bei die Cerit metallen,” in Justus Liebigs Annalen der Chemie, 168 , no. 1 (1873), 45–63; “zur Geschichte des periodischen Gesetzes,” in Berichte det Deutschen Chemischen Gesellschaft, 8 (1875), 1796–1804; and “Das natürliche System dor chemischen Elemente,” in Ostwald’s klassiker, no. 68 (Leipzig, 1913), pp. 20–40.

Publications from Mendeleev’s scientific archives include Novye materialy po istorii otkrytia periodicheskogo zakona (“New Material on the History of the Discovery of the Periodic Law”), B. M. kedrov, ed. (Moscow, 1950); Nauchny arkhiv (“Scientific Archive”), I, Periodichesky znkon (“The Periodic Law”), compiled and edited by B. M. kedrov (Moscow, 1953), which includes theoretical material from 1869–1871. Notes on experiments related to the periodic law during this period will appear in vol. II, Eksperimentalnye raboty (“Experimental Works”). Material preceding the periodic law and directed toward it will be in vol. III, Podgolovlenie otkrytia (“Preparation for the Discovery”), and that which followed ihe discovers will be in vol. IV, Razrabotka otkrytia (“Development of the Discovers”); Rastvory (“Solutions”), k. P. Mishchenko, ed., in the series klassiki Nauki (Leningrad, 1959); Nauchny arkhiv. Osvoenie kraynego Severa (“Scientific Archive. The Conquest of the Far North”), I, Vysokie shiroty Severnogo Ledovitogo okeana (“High Latitudes of the Northern Arctic Ocean”), A. I. Dubravin, ed. (Moscow—Leningrad, 1960); Nauchny arkhiv, Rastvory (“Scientific Aichive, Solutions”), compiled by R. B. Dobrotin (Moscow—Leningrad, 1960); and Izbrannye lektsii po khimii (“Selected Lectures in Chemistry”), compiled by A. A. Makarenya et al (Moscow, 1968), Mendeleev’s chemistry lectures from 1864, 1870–1871, and 1889–1890.

For autobiographical Source material, see D. I. Mendeleev. Literaturnoe naslecdstvo. I, zametki i materialy D. I. Mendeleeva biograficheskogo kharaktera (Leningrad, 1938). a collection of biographical notes and material; Arkhiv D. I. Mendeleeva, I, Avtobiograficheskie materialy. Sbornik dokumentov (Leningrad, 1951), with Mendeleev’s bibliography of his works, pp. 39–130, as well as diary notes, chronology, a catatog of Mendeleev’s personal library, and a list of the contents of his scientific archives; and M. D. Mendeleeva. ed., Nauchnoe nasledstvo (“Scientific Heritage”), Natural Science Sen., II (Moscow–Leningrad, 1951): see pp. 111–256 for Mendeleev’s diaries for 1861–1862, and pp. 257–294 for his letters concerning his work on smokeless powder, P. M. Lukyanov, ed.

II. Secondary Literature. Biographical works on Mendeleev include N. A. Figurovsky, Dmitry Ivanovich Mendeleev (Moscow, 1961); B. kedrov and T. Chentsova, Brauner—spodvizhnik Mendeleeva (Moscow, 1960), written by Mendeleev’s associate, with their correspondence and material on their elaboration of the periodic law; A. A. Makarenya et al., eds., D. I. Mendeleev v vospominaniakh sovremennikon (“Mendeleev Recalled by His Contemporaries” Moscow, 1969), with recollections of his friends, students, acquaintances, and relatives; A. I. Mendeleeva, Mendeleev v zhizni (“Mendeleev in Life”; Moscow, 1928), written by Mendeleev’s second wife; M. N. Mladentsev and V. E. Tishchenko, Mendeleev, ego zhizn i deyatelnost (“Mendeleev, His Life and Work”), I (Moscow-Leningrad, 1938)—Tishchenko was Mendeleev’s laboratory assistant and the biography goes as far as 1861; O. N. Pisarzhessky, Dmitry lvanovich Mendeleev (Moscow, 1959); and Semeynaya khronika (“Family Chronicle”; St. Petersburg, 1908), letters from his relatives and recollections by his niece, N. Y. Gubkinaya.

On the history of the discovery and development of the periodic law, see L. A. Chugaev, Periodicheskaya sistema khimicheskikh elementov (“The Periodic System of the Chemical Elements”; St. Petersburg, 1913); K. Danzer, Dmitri I. Mendelejew und Lothar Meyer. Die Schöpfer des Periodensystems der chemischen Elemente (Leipzig, 1971); B. M. kedrov, Razvitie ponyatia elementa of Mendeleeva do nashikh dney (“The Development of the Concept of the Element From Mendeleev to Our Times”; Moscow–Leningrad, 1948), pp. 24–71, 220–239; Evolyutsia ponyatia elementa v khimii (“The Evolution of the Concept of the Element in Chemistry”; Moscow, 1956), pp. 137–161, 188–294; Den odnogo velikogo otkrytia (The Day of One Great Discovery”; Moscow, 1958), also translated into French as “Le l^er mars 1869; jour de la découverte de la loi périodique par D. I. Mendeléev,” in Cahiers d’histoire mondiale, VI, 3, 644–656, gives the history of the discovery of the periodic law on 1 Mar. 1869 and includes many archival documents; Filosofsky analiz pervykh trudov D. I. Mendeleeva o periodicheskom zakone (1869–1871) (“A Philosophical Analysis of the First Works of D. I. Mendeleev on the Periodic Law [1869–1871]”; Moscow, 1959), a continuation of the preceding work; Tri aspekta atomistiki (“Three Aspects of Atomic Theory”), III, Zakon Mendeleeva. Lagiko-istorichesky aspekt (“Mendeleev’s Law. Logical-Historical Aspect”; Moscow, 1969); Mikroanatomia velikogo otkrytia. K 100-letiyu zakona Mendeleeva (“Microanatomy of the Great Discovery. For the 100th Anniversary of Mendeleev’s Discovery”; Moscow, 1970); B. M. kedrov and D. N. Trifonov, Zakon periadichnosti i khimicheskie elementy. Otkrytia i khronologia (“The Law of Periodicity and the Chemical Elements. Discoveries and Chronology”; Moscow, 1969); Paul kotodkine, Dmitri Mendeleiv et la loi périodique (Paris, 1963); V. A. krotikov, “The Mendeleev Archives and Museum of the Leningrad University,” in Journal of Chemical Education, 37 (1960), 625–628; V. Y. Kurbatov, Zakon D. I. Mendeleeva (“D. I. Mendeleev’s Law”; Leningrad, 1925); Henry M. Leicester, “Dmitrii Ivanovich Mendeleev,” in Eduard Farber, ed., Great Chemists (New York, 1961), 719–732; A. A. Makarenya, D. I. Mendeleev o radioaktivnosti i slozhnosti elementov (“D. I. Mendeleev on Radioactivity and the Complexity of the Elements”), 2nd ed, (Moscow, 1965); and D. I. Mendeleev i fiziko-khimicheskie nauki (“D. I. Mendeleev and the Physicochemical Sciences”; Moscow, 1972), an attempt at a scientific biography; F. A. Paneth, “Radioactivity and the Completion of the Periodic System,” in Nature, 149 (23 May 1942), 565– 568; Periodichesky zakon D. I. Mendeleeva i ego filosofskoe znachenie (“Periodic Law of D. I. Mendeleev and Its Philosophical Significance”; Moscow, 1947), a collection of articles by A. N. Bakh, A. F. Joffe, A. E. Fersmann, A. V. Rakovsky, B. M. kedrov, G. S. Vasetsky, and B. N. Vyropaev; Periodichesky zakon i stroenie atoma (“The Periodic Law and Atomic Structure”; Moscow, 1971), a collection of articles; O. V Pisarzhevsky, Dmitrii Ivanovich Mendeleev. His Life and work (Moscow, 1959); Daniel Posin, Mendeleyev, the Story of a Great Scientist (New York, 1948); E. Rabinowitsch and E. Thito, Periodisches System. Geschichte und Theorie (Stuttgart, 1930), trans. into Russian as periodicheskaya sistema elementov. Istorich i teria (Moscow-Leningrad, 1933), pt. 1, esp. ch. 5; N. N. Semenov, ed., Sto let periodicheskogo zakona khimicheskikh elementov (“A Hundred Years of the Periodic Law of the Chemical Elements”) (Moscow, 1969); 75 let periodicheskogo zakona D. I. Mendeleeva i Russkogo khimicheskogo obshchestva (“A Hundred Years of the leev’s Periodic Law and the Russian Chemical Society”; Moscow-Leningrad, 1947), a collection of articles with a bibliography on pp. 261–265; T. E. Thorpe, Essay in Historical Chemistry (London, 1911), 483–499; W. A. Tildon, Famous Chemists (London, 1921), 241–258; D. N. Trifonov, O kolichestvennoy interpretatsii periodichnosti (“On the Quantitative Interpretation of Periodicity”; Moscow, 1971), pp. 16–31; Voprosy estestvoznania i tekhniki (“Questions of Natural Science and Technology”), no. 4 (29) (Moscow, 1969), a collection commemorating the centenary of the periodic law; Alexander Vucinich, “Mendeleev’s Views on Science and Society.”),in Isis, 58 (1967), 342–351; and Science in Russian Culture (Stanford, Calif., 1970), 147–165; and Yubileynomu Mendeleeveskomu sezdu v oznamenovanie 100-letney godovshchiny so dnya rozhdenia D. I. Mendeleeva. Varianty periodicheskoy sistemy (“Mendeleev Anniversary Congress in Recognition of the Centenary of D.I. Mendeleeve’s Birth. Variants of the Periodic System”), collected by M. A. Blokh (Leningrad, 1934).

On other aspects of Mendeleev’s life and work, see V. P. Barzakovsky and R. B. Dobrotin, Trudy D. I. Mendeleeva v oblasti khimii silikatov i stektoobraznogo sostoyania (“Mendeleev’s Works on the Chemistry of Silicates and Glass-Making”; Moscow, 1960); T. S. kudryavtseva and M. E. Shekhter, Mendeleev i ugolnaya promyshlennost Rossii (“Mendeleev and the Russian Coal Industry”; Moscow, 1952); A. A. Makarenya and I. N. Filimonova, D.I. Meedeleev i Peterburgsky universitet (“Mendeleev and St. Petersburg University”; Leningrad, 1969); V. E. Parkhomenko,D. I. Mendeleev i russkoe neftyanoe delo (“Mendeleev and the Russian Petroleum Industry”; Moscow, 1957); S. I. Volfkovich et al., eds., D. I Mendeleev. Raboty po seltkomu khozyaystvu i lesovodstvu (“Mendeleev. Works on Agriculture and Forestry; Moscow, 1954); and G. A. Zabrodsky, Mirovozzrenie D. I. Mendeleeva (“Mendeleev’s World View”; Moscow, 1957), issued to commemorate the fiftieth anniversary of his death.

B. M. Kedrov