[In cyrillic:] Osnovy Khimii [Principles of Chemistry].
St. Petersburg: (Tovarishchestvo 'Obshchestvennaja Pol'za', for the author), 1869-1871. First edition, very rare, containing the first appearance of the periodic table of the elements. “Mendeleyev was a Russian chemist whose name will always be linked with his outstanding achievement, the development of the periodic table. He was the first chemist to understand that all elements are related members of a single ordered system. He converted what had hitherto been a highly fragmented and speculative branch of chemistry into a true, logical science … According to Mendeleyev the properties of the elements, as well as those of their compounds, are periodic functions of their atomic weights (relative atomic masses). In 1869, he stated that ‘the elements arranged according to the magnitude of atomic weights show a periodic change of properties’ …
Mendeleyev compiled the first true periodic table, listing all the 63 elements then known. Not all elements would ‘fit’ properly using the atomic weights of the time, so he altered iridium from 76 to 114 (modern value 114.8) and beryllium from 13.8 to 9.2 (modern value 9.013) … Also, in order to make the table work Mendeleyev had to leave gaps, and he predicted that further elements would eventually be discovered to fit them. These predictions provided the strongest endorsement of the periodic law … Far-sighted though Mendeleyev was, he had no notion that the periodic recurrences of similar properties in the list of elements reflected anything in the structure of their atoms. It was not until the 1920s that it was realized that the key parameter in the periodic system is not the atomic weight but the atomic number of the elements – a measure of the number of nuclear protons or electrons in the stable atom. Since then great progress has been made in explaining the periodic law in terms of the electronic structures of atoms and molecules” (Hutchinson’s DSB, pp. 475-7). “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’. Mendeleev's first report of his discovery 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’)” (DSB). This in fact is in Osnovy khimii, and is the heading to the periodic table that appears on p. [iv] of the preface, which is dated March 1869. Mendeleev had discovered the periodic arrangement on March 1 1869, and immediately sent his draft to the printers for inclusion in the first part of his textbook Osnovy khimii, which had been printed but not yet distributed. This appearance of the table is from the same setting of type as two single-sheet printings, with legends in French and Russian, which were printed at the same time for presentation to colleagues. Mendeleev then at a later date presented a slightly modified version, with a different title, to the Russian Chemical Society, in whose Journal it was published (this is the work cited by Horblit). The journal version utilises the same setting of type of the table itself (with minor variations due to locking up the type a second time), but with a different heading and additions to the text. It is therefore the second printing, with a revised text. Mendeleev himself makes clear, in the preface to the fifth edition of the Osnovy khimii, that he first published the periodic table in the first edition of this work. Not only does the Osnovy khimii contain the first appearance of the table, in its earliest version, but also Mendeleev’s expanded version of 1871, in which the periodic table assumes more or less its modern form (with the elements in the same group arranged vertically, instead of horizontally as in the first table), and his further researches into the 'periodicity' of the elements, including predictions of elements to be discovered based upon gaps in the table (including a whole series of rare earths). “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 Osnovv khimiii (‘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 … 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 Osnovy 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 … [This showed that] 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 … 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 … 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 discovery 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 finer points until 1907 … “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 employed 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 (1) sodium and potassium with monovalent (1) hydrogen … a formulation that may be seen as a confused premonition of the later rule of displacement” (DSB). Kaji gives a detailed chronology of the discovery of the period law. “In May or June 1868, Mendeleev published the first volume [of Principles] (Chapters 1-11). On February 17, 1869, he compiled the first periodic table, titled ‘An Attempt at a System of the Elements Based on Their Atomic Weight and Chemical Affinity’. On March 6, N. A. Menshutkin (1842-1907), the secretary of the recently established Russian Chemical Society, read Mendeleev’s first paper on his discovery, ‘The Correlation of the Properties and Atomic Weights of the Elements’, at a meeting of the society. At almost the same time, Mendeleev published the second volume of Principles, Chapters 12-22. At the end of February or early in March 1870, the third volume, which comprises Chapters 1-8 of Part 2, appeared. Finally, the last volumes (the fourth and fifth), which include Chapters 9-23, were published in February 1871 … This chronology makes it clear that Mendeleev discovered the periodic law in the middle of writing Principles” (Kaji, pp. 8-9). “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 few 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 … 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” (DSB). Dibner 48 (citing the German translation of 1891); Horblit 74 (citing the journal appearance); Parkinson p. 373. Kaji, ‘D. I. Mendeleev’s concept of chemical elements and the Principles of Chemistry,’ Bulletin of the History of Chemistry 27 (2002), pp. 4-16.
5 parts in 2 vols., 8vo (179 x 111 mm), pp. [ii], [i-] iii [-iv, with the periodic table], 816; [iv], 951, [1], with large folding table in vol. II and numerous wood-engraved illustrations in text. Bound in two very fine pastiche bindings with cyrillic spine lettering.
Item #5950
Price: $80,000.00
