After graduating from the gymnasium classes of the institute in 1856, he entered the cameral department of the law faculty of Kazan Imperial University; in the process of studying, he moved to the natural department of the university, where he listened to the lectures of A. M. Butlerov, according to which, in 1860, after completing a university course, he was left to prepare for a professorship and was appointed laboratory assistant at a chemical laboratory. In 1864 he defended his master's thesis. In the spring of 1869, he defended his doctoral dissertation.
After graduating from the gymnasium classes of the institute in 1856, he entered the cameral department of the law faculty of Kazan Imperial University; in the process of studying, he moved to the natural department of the university, where he listened to the lectures of A. M. Butlerov, according to which, in 1860, after completing a university course, he was left to prepare for a professorship and was appointed laboratory assistant at a chemical laboratory. In 1864 he defended his master's thesis. In the spring of 1869, he defended his doctoral dissertation.
Vladimir Vasilyevich Markovnikov Russian organic chemist. He contributed to the structural theory and to the understanding of the ionic addition (Markovnikov addition) of hydrogen halides to the carbon-carbon double bond of alkenes.
Background
Vladimir Markovnikov was born on December 22, 1838, in Chernorechye near Nizhny Novgorod, Russian Empire (now Dzerzhinsk, Nizhny Novgorod Oblast, Russian Federation) where at that time lodged the Belevsky Jaeger Regiment in which his father, Lieutenant Vasily Markovnikov, served. Soon after the birth of Markovnikov, his father retired and settled in a family estate received as a dowry for his wife, in the village of Ivanovo, Knyagininsky district of the Nizhny Novgorod province, where the future scientist spent his early childhood.
Education
At the age of ten Markovnikov was sent to the Nizhny Novgorod Nobility Institute. After graduating from the gymnasium classes of the institute in 1856, he entered the cameral department of the law faculty of Kazan Imperial University; in the process of studying, he moved to the natural department of the university, where he listened to the lectures of A. M. Butlerov, according to which, in 1860, after completing a university course, he was left to prepare for a professorship and was appointed laboratory assistant at a chemical laboratory. In 1864 he defended his master's thesis. In the spring of 1869, he defended his doctoral dissertation.
After graduating from the university in 1860 Markovnikov became Butlerov’s assistant in teaching inorganic and analytical chemistry. From 1865 to 1867 he was in Germany, spending most of his time in the laboratories of Erlenmeyer at Heidelberg and of Kolbe at Leipzig. After his return, he became assistant to and then succeeded, Butlerov in the chair of chemistry at Kazan University. In 1871, however, protesting the arbitrariness of the administration, he resigned. Markovnikov was immediately invited to the University of Odessa, and in 1873 to Moscow University. There he improved the teaching of chemistry, set up a new chemical laboratory according to his own plans, and created his own school of chemists.
An important turning point in Markovnikov’s scientific career occurred in Moscow: he shifted his attention mainly to practical chemical research, and thus was reproached for betraying pure science. He devoted almost twenty-five years to the study of the hydrocarbons of Caucasian petroleum and to the chemistry of alicyclic hydrocarbons - “naphthenes,” as he called them. But the range of Markovnikov’s research also included the composition of the salts of the southern Russian bitter-salt lakes and the Caucasian sources of mineral waters and methods and materials for testing railroad ties.
Markovnikov also studied the history of chemistry. He took the initiative in the publication of the Lomonosovskogo sbornika (“Lomonosov Collection”; Moscow, 1901), which included material on the history of Russian chemical laboratories; and he himself wrote a detailed sketch of the laboratories of Moscow University.
The most important results which Markovnikov obtained in his work on the theory of structure and the chemistry of petroleum and alicyclic compounds were the following. He tested certain conclusions, important in the first stage of structural theory, concerning the existence of isomers in a series of fatty acids (for example, butyric and isobutyric acid, the identity of “acetone” acid, obtained by G. Städeler in 1859 from “the mixture of acetone, hydrogen cyanide, and diluted hydrochloric acid,” with isobutyric acid). Developing Butlerov’s theory of the mutual influence of atoms, Markovnikov introduced certain “rules.”
The rule for the substitution reaction in its general form states that with an unsymmetrical olefin, where two possible modes of addition are open, the reaction ordinarily follows a course such that the hydrogen becomes attached to the carbon atom of the olefin that already has the greater number of hydrogen atoms.
Markovnikov recognized that tertiary hydrogen atoms and hydrogen atoms in the α position to a carboxyl group are more active than hydrogen atoms in other positions. This also indicated to him at what point in a molecule destructive oxidation would take place. Markovnikov also first stated the rule that when molecules of water or hydrogen halide are obtained from alcohols or alkylhalides, the separation occurs between them and the two neighboring atoms of hydrogen.
This rule, as Markovnikov showed, can be used to determine the structure of unsaturated compounds. The formation of compounds of the hydrogen halides or water with an unsymmetrical olefin occurs so that the halogen or hydroxyl radical adds to the carbon of the ethylenic bond with the lesser number of hydrogen atoms while the hydrogen adds to the carbon with the larger number of hydrogen atoms. This is known in textbooks as the Markovnikov rule. Markovnikov explained the mechanism of the reactions of isomerization, similar to the transition of isobutyl alcohol to tertiary isobutyl alcohol by reference to such reactions of separation and addition. He also stated rules relating to monomolecular isomerization and certain other reactions, stressing their dependence on the conditions.
In 1872, two years before van Hoff’s stereochemical representation (tetrahedral) of the carbon atom, Markovnikov showed the necessity of developing a theory of chemical structure by studying the relation between chemical interaction and the “physical position” of atoms in space; and in 1876 he stated that “the relative distribution of atoms in a molecule should be expressed by chemical formulas.”
Markovnikov and his colleagues showed, contrary to the current opinion, that oil from the Caucasus contained derivatives of cyclopentane and aromatic hydrocarbons along with derivatives of cyclohexane. He discovered the existence of azeotropic mixtures of both these types of hydrocarbons. Markovnikov proposed a method for obtaining aromatic nitro derivatives by means of direct nitration of petroleum fractions.
Markovnikov was one of the first to understand the importance of studying the composition of petroleum hydrocarbons for practical uses. For example, he and his colleagues showed, contrary to the current opinion, that oil from the Caucasus contained derivatives of cyclopentane and aromatic hydrocarbons along with derivatives of cyclohexane. He discovered the existence of azeotropic mixtures of both these types of hydrocarbons. Markovnikov proposed a method for obtaining aromatic nitro derivatives by means of direct nitration of petroleum fractions.
Achievements
Markovnikov is best known for Markovnikov's rule, a discovery that was as named to honor his name. He later received the Professor Pavel Ilyenkov Prize as well as a Gold Medal from the International Oil Congress for "Investigating the Oil of the Caucasus."
