Vladimir Vasilevich Markovnikov

Born Dec. 13 (25), 1837, in the city of Kniaginin in present-day Gorky Oblast; died Jan 29 (Feb. 11), 1904, in Moscow. Russian chemist. Student of A. M. Butlerov.

Markovnikov graduated from the University of Kazan in 1860, where he became a lecturer in 1862 and a professor in 1869. In 1871 he and a group of other leading scientists left the university to protest the dismissal of Professor P. F. Lesgaft. Subsequently, Markovnikov held a professorship at the University of Novorossiia in Odessa (until 1873). He was appointed professor at Moscow University in 1873.

Markovnikov’s main works deal with the development of the theory of chemical structure and with the study of petroleum and alicyclic hydrocarbons (naphthenes). Using butyric acid (normal structure) and isobutyric acid, he demonstrated the existence of isomerism in fatty acids in 1865. He discussed the history of the theory of isomerism and presented a critical analysis of its status in his master’s dissertation, “On the Isomerism of Organic Compounds” (1865). Drawing on views set forth by A. M. Butlerov and extensive experimental data, he established a number of the laws governing chemical substitution, addition, and breakdown (in particular, what is now called the Markovnikov rule) in his doctoral dissertation, “Material on the Interaction of Atoms in Chemical Compounds” (1869). The inferences drawn by him played an important role in the development of the theory of atomic interaction based on the concept of the electron.

During the 1870’s, Markovnikov obtained all of the isomeric dibasic acids of the general formula C3H6(CO2H)2 predicted by the structure theory. In the early 1880’s, he began a systematic investigation of the petroleum of the Caucasus. He discovered and studied a new class of hydrocarbons, which he called naphthenes. He isolated aromatic hydrocarbons from petroleum and discovered their ability to form azeotropic mixtures with other classes of hydrocarbons. Markovnikov was the first to investigate naphthylenes (tricyclenes). He discovered that naphthenes (cycloparaffins) are converted into aromatic hydrocarbons upon the catalytic action of aluminum bromide. He was the first to synthesize a number of naphthenes and paraffins with branched carbon chains. Markovnikov studied the density of hydrocarbons as a function of temperature, and he proposed a method of determining the purity of a hydrocarbon by noting the deviation from its freezing point.

Markovnikov was the first to obtain compounds with sevenmembered and eight-membered rings. He studied the reaction mechanism of esterification and the oxidation of substituted cyclic ketones. He also conducted research on the salt lakes of Russia.

Markovnikov worked for the development of a domestic chemical industry, for the dissemination of scientific knowledge, and for close ties between science and industry. He credited A. M. Butlerov with the formulation of the chemical structure theory. The Lomonosov Collection, which deals with the history of chemistry in Russia, was published in 1901 on Markovnikov’s initiative.

Markovnikov was one of the founders of the Russian Chemical Society (1868). His students included many eminent scientists, such as N. Ia. Dem’ianov, M. I. Konovalov, N. M. Kizhner, and I. A. Kablukov.