In August 1869, only five months after his announcement of his periodic law, Dmitri Mendeleev (1834-1907) gave a paper entitled "On the Atomic Volumes of Simple Bodies" at the Second Congress of Russian Scientists, held that year in Moscow.  The proceedings of the Congress, which were published early in 1870, contain Mendeleev's 10 page paper along with contributions from other Russian scientists, including the chemists Beilstein, Zaitsev, and Butlerov.  Mendeleev's paper on atomic volumes is the second that he wrote on his periodic law, and as such it gives valuable insights into his early thinking.  Its Russian text, which has never been translated into any Western language, has remained largely unexamined since it was printed.  Atomic volumes (and the related concept of molar volumes) are easily calculated by dividing the atomic or molecular weight (g/mol) of a substance by the density (g/cm<sup>3</sup>) of a solid sample of the substance; they therefore have units of cubic centimeters per mole.  Shortly after the concept of atomic volume was defined by Le Royer and Dumas in 1821, Polydore Boullay and Amedeo Avogadro noticed that atomic volumes were correlated with certain aspects of chemical reactivity such as cohesive ability and electronegativity.  Atomic and molar volumes also formed an important role in Mendeleev's own chemical education: his master's thesis of 1856, which was exclusively devoted to the topic, showed that molar volumes exhibited consistent mathematical regularities.   He pointed out, for example, that the molar volume of potassium hydroxide (KOH) is approximately equal to the average of the molar volumes of potassium oxide (K2O) and water (H2O). Moreover, the tables in his master's thesis often list the elements according to what eventually would be groups in the periodic table: the alkali metals Li, Na, K are immediately followed by the alkaline earths Be, Mg, Ca, Sr, Ba; and sulfur and selenium are listed one after the other.  Of course atomic volumes were crucial to Lothar Meyer's own independent development of the periodic law.  The present talk will describe Mendeleev’s 1869 paper on atomic volumes, and his discussion about how their mathematical regularities supported his newly devised periodic law.

Atomic volumes and Mendeleev's development of the periodic table

256th National Meeting (2018)

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