professor vladimir fedorovich alekseev (on 150th anniversary of his birthday)

1070-4272/02/7509-1541$27.00C2002 MAIK [Nauka/Interperiodica]

Russian Journal of Applied Chemistry, Vol. 75, No. 9, 2002, pp. 154131542. Translated from Zhurnal Prikladnoi Khimii, Vol. 75, No. 9,2002, pp. 1576 31577.Original Russian Text Copyright C 2002 by Morachevskii.

HISTORY OF CHEMISTRYÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ ÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ

AND CHEMICAL TECHNOLOGY

Professor Vladimir Fedorovich Alekseev(on 150th Anniversary of His Birthday)

Vladimir Fedorovich Alekseev, a prominent Rus-sian physical chemist of the end of the XIX century,carried out a number of classical experimental in-vestigations in the theory of solutions and heterogene-ous equilibria involving liquid phases.

V.F. Alekseev was born on October 12, 1852, inSt. Petersburg. He received secondary education at theSecond St. Petersburg Military College. In 1867, heentered the Mining Institute and graduated from theinstitute as a mining engineer in 1873. Alekseevstarted his studies in chemistry already when beinga student, under supervision of Prof. K.I. Lisenko(183631903), a known scientist working in the fieldof technical chemistry. In 187331877, Alekseevworked as laboratory assistant at the chemical labora-tory of the Mining Institute and conducted researchin preparative organic chemistry and mutual solubilityof liquids. In 187731879, he held the position of as-sistant assayer at the Mint, without terminating hisstudies of solutions. In 1879, Vladimir Fedorovichdefended his dissertation On Mutual Solubility ofLiquids at the Mining Institute and became an adjunctat the chair of chemistry of the same institute. Thiswas the beginning of the twenty years of Alekseev’spedagogical activities at the Mining Institute.

During his work on the dissertation, the youngscientist established for the first time the existence ofa temperature at which two liquid layers mix witheach other in any proportion to form a homogeneousmixture. The author proposed a rather simple andoriginal optical method for determining the mutualsolubility of liquids.

The first Russian chemist to become interested inthe mutual solubility of liquids was D.N. Abashev(182931880), a graduate from St. Petersburg Univer-sity (1851) and, later, a professor of Kiev and Novo-rossiya (Odessa) Universities. In 1858, he defendedhis master’s dissertation Studies of Mutual Solubilityof Liquids. Abashev’s experiments became the startingpoint for extensive investigations carried out in thisfield by Alekseev. Using the method developed byhim, he obtained systematic data on the mutual solu-bility of a wide variety of liquids, with many of thesedata still found in reference books. As noted by

N.S. Kurnakov (186031941), [V.F. Alekseev was thefirst to present the facts for constructing full solubilitydiagrams for binary systems characterized by forma-tion of two liquid layers] [1]. Alekseev was also thefirst to present experimental data on the mutual solu-bility in the form of graphical phase diagrams, pub-lished first geometric images of phase diagrams forliquid systems, and indicated the homogeneity andphase separation regions.

One more thing is associated with Alekseev’sname, the [rectilinear diameter rule,] according towhich the arithmetic mean of the composition (pre-sented in wt %) of equilibrium liquid phases varieslinearly with temperature, and the point of intersectionof the straight line expressing this dependence withthe boundary of the phase separation region (binodalcurve) corresponds to the critical solution temperature,which is a critical point [2, 3]. A detailed analysis ofthe history of this discovery and the evidence of Alek-seev’s priority have been presented [4] by S.A. Pogo-

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 75 No. 9 2002

1542 MORACHEVSKII

din, a known physical chemist and historian of chem-istry.

Alekseev’s active investigations into various prop-erties of solutions and heterogeneous equilibria in-volving such solutions were carried out since 1875until 1886. During this period of time, he published17 papers and made 31 reports at meetings of theRussian Physicochemical Society. To elucidate thenature of solutions, the scientist studied a wide varietyof their properties: specific heat, heats of mixing,saturated vapor pressure, and surface tension. In con-trast to the standpoint of D.I. Mendeleev (183431907), Alekseev believed that chemical interaction isnot a necessary condition for dissolution. Later,I.F. Shreder (185831918), also a professor of theSt. Petersburg Mining Institute, considered solutionswith the minimum extent of chemical interactionbetween their components as a special group of solu-tions. Alekseev believed that the fundamental aspectsof behavior are the same for widely diverse classes ofsolutions, including metal alloys. However, alloyswere the subject of only a single Alekseev’s paperconcerned with the mutual solubility of bismuth andmercury. A detailed analysis of Alekseev’s works inthe field of mutual solubility of liquids and solutionproperties can be found in a paper by Ya.I. Gerasimov[5] and monograph by A.Ya. Kipnis [6].

Together with studying various solutions, Alekseevpaid much attention to general problems of the chemi-cal thermodynamics of that time. In 1884, he pub-lished an interesting [Treatise of the Present State ofChemical Mechanics] [Gornyi Zhurnal (Journal ofMining), 1884] devoted to the theory of chemicalequilibrium. The treatise, in particular, read: [Chemi-cal mechanics plays an exceedingly important role inapplied chemistry, and clear understanding of at leastsuch fundamental processes as, e.g., the evergreenBessemer process and blast-furnace melting is impos-sible without it] [7]. Here, the works of H. Saint-ClairDeville (181831881), a French chemist, in the field ofthermal dissociation and theory of chemical equilibri-um are meant in the first place. The same treatisepresented, for the first time in the Russian chemicalliterature, the notion of entropy and also gave an ac-count of J. Gibbs’ (183931903) equilibrium principle.

In 1886, Alekseev ceased studies of solutions anddevoted himself entirely to problems of applied chem-istry. In Kurnakov’s opinion [1], [... the reason whythis occurred is V.F.’s passionate and not always bal-anced temper, a financial position that became com-plicated, and changes in his social standpoint under

the influence of Leo Tolstoy’s concepts.] Alekseevstarted to study coals and peat and developed methodsfor testing these. In 1895, he published his funda-mental work [Fossil Coals of the Russian Empire andTheir Composition] (St. Petersburg, 1895). To achievean efficient use of peat deposits in northern regions ofRussia, Alekseev founded a special laboratory inSt. Petersburg and a peat plant in Tver Province.

After 25 years of service at State institutions, Alek-seev ceased teaching at the Mining Institute and re-tired. Beginning in 1901, he lived at his Sosno manorin the Vyshni Volochek District of Tver Province,where he did farming, studied problems of peatery,and was engaged in social activities. He died on Sep-tember 12, 1919. The obituary written by Academi-cian Kurnakov read: [The general chemistry and itsnew field, physicochemical analysis, lost in V.F. Alek-seev’s person an outstanding researcher, whose workswill undoubtedly grow in importance for the under-standing of the fundamental properties of equilibriumsystems with the development of science] [1]. Later(in 1928), he noted: [Three chemists, V.F. Alekseev,D.P. Konovalov, and I.F. Shreder, originating fromthe chemical laboratory of the Mining Institute, hadgreat impact on the development of such a field ofgeneral chemistry as physicochemical analysis] [8].

REFERENCES

1. Kurnakov, N.S., Izv. Inst. Fiz.-Khim. Anal., 1922,vol. 2, pp. 134.

2. Gerasimov, Ya.I., Dreving, V.P., Eremin, E.N., et al.,Kurs fizicheskoi khimii (A Course of Physical Chemis-try), Moscow: Goskhimizdat, 1963, vol. 1.

3. Anosov, V.Ya., Ozerova, M.I., and Fialkov, Yu.Ya.,Osnovy fiziko-khimicheskogo analiza (Fundamentals ofPhysicochemical Analysis), Moscow: Nauka, 1978.

4. Pogodin, S.A., Usp. Khim., 1950, vol. 19, no. 1,pp. 1253127.

5. Gerasimov, Ya.I., Materialy po istorii otechestvennoikhimii (Materials on the History of Domestic Chemis-try), Moscow: Akad. Nauk SSSR, 1950, pp. 52362.

6. Kipnis, A.Ya., Razvitie khimicheskoi termodinamiki vRossii (The Development of Chemical Thermo-dynamics in Russia), Moscow: Nauka, 1964.

7. Solov’ev, Yu.I., Ocherki po istorii fizicheskoi khimii(Studies of the History of Physical Chemistry), Mos-cow: Nauka, 1964.

8. Solov’ev, Yu.I., Nikolai Semenovich Kurnakov: 186031941, Moscow: Nauka, 1986.

A. G. Morachevskii