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Page 1: Marcellin Berthelot (on 175th Anniversary of His Birthday) Pierre

1070-4272/02/7511-1889$27.00C2002 MAIK [Nauka/Interperiodica]

Russian Journal of Applied Chemistry, Vol. 75, No. 11, 2002, pp. 188931892. Translated from Zhurnal Prikladnoi Khimii, Vol. 75, No. 11,2002, pp. 1926 31929.Original Russian Text Copyright C 2002 by Morachevskii.

HISTORY OF CHEMISTRYÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ ÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ

AND CHEMICAL TECHNOLOGY

Marcellin Berthelot(on 175th Anniversary of His Birthday)

Pierre Eugene Marcellin Berthelot ranks among themost prominent chemists of the second half of theXIX century and early XX century. The great numberof his works include fundamental investigations in vir-tually all branches of chemistry of that time, originalstudies in physics, biology, history of science and art,archeology, philosophy, pedagogics, linguistics,ethics, and esthetics. Works of the French scientistmuch promoted the transformation of organic chemis-try into a separate kind of science, stimulated thedevelopment of the most important fields of physicalchemistry, and enriched the history of chemistry.

M. Berthelot was born on October 25, 1827, inParis into a doctor’s family. In 1846, he graduatedfrom a lyceum, having demonstrated substantial learn-ing capability both in natural sciences and in humani-ties. Berthelot was aided in his diverse scientific ac-tivities by his knowledge of foreign languages, in-cluding Grecian and Sanskrit. Soon after graduatingfrom the lyceum, he passed an examination to obtainbachelor’s degree in philosophy and history (es let-tres) and in mathematics and natural sciences (essciences). Following the example of his father,Berthelot started his higher education from medicineand simultaneously attended lectures in chemistry andphysics at College de France. In 1849, he obtained adegree of licentiate in physical sciences. By that time,the final choice of the main direction of research hadbeen made, and this was chemistry. Berthelot men-tioned among his teachers chemists J.B. Dumas(180031884), A.J. Balard (180231876), and T.J. Pe-louze (180731867), and especially a physicistH.V. Regnault (181031878). All of them were knownscientists and members of the Paris Academy ofSciences. In 1849, Berthelot started to work at Pe-louze’s private chemical laboratory, and in 1851, hebecame an assistant at Balard’s laboratory at Collegede France.

In 1854, Berthelot defended his doctoral disserta-tion. His study was concerned with the reaction ofglycerol with acids and artificial synthesis of naturalfats. In 1858, he passed examinations and becamea first-class pharmacist.

In 185931864, Berthelot was a professor at Ecolede Pharmacie in Paris. In 1863, the scientist waselected a member of the Academy of Medicine. From1865 till 1906, he was a professor at College deFrance. Professors of this institution are not bound byany curricula and are free from taking part in exami-nations. Every year a scientist chooses the subject ofhis lectures himself, commonly in correspondencewith the field of science he is currently interested in.In 1869, by proposition of J. Liebig (180331873),a known chemist, Berthelot was elected a member ofthe Bavarian Academy of Sciences. In 1873, he be-came a member of the Paris Academy of Sciences inphysics. By recommendation of a group of academi-cians, including A.M. Butlerov (182631880), Ber-thelot was elected in 1876 a foreign correspondingmember of the St. Petersburg Academy of Sciences.In 1877, the London Royal Society elected him aforeign member. Beginning in 1889, Berthelot wasa permanent secretary of the Paris Academy of

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Sciences; in the same year he was elected a memberof the French Academy of Literature and Fine Arts.

Together with being engaged in intensive anddiverse scientific activities, Berthelot held a numberof high state posts, he became a general supervisorof higher education in 1876 and was a minister ofpopular schooling in 188631887 and foreign ministerof France in 189531896.

Berthelot was elected an honorary member of theGerman chemical society in 1894 and an honorarymember of the French chemical society in 1900; in1866, 1875, 1882, 1889, and 1901 he was elected thepresident of the French chemical society.

A lot of the credit for the development of variousbranches of chemistry and chemical technology mustgo to Berthelot; he made the most prominent contribu-tion to the development of organic synthesis. This isquite understandable since organic chemistry domi-nated the development of chemistry in the middle ofthe XIX century.

Voluminous literature has been concerned withBerthelot’s life and scientific activities; his workshave been studied in detail. A prominent contributionto studies of this kind performed in Russia wasmade by Yu.S. Musabekov (191031970), a knownhistorian of chemistry [1, 2]. Rather detailed remi-niscences about his French colleague were publishedby K.A. Timiryazev (184331920), an outstandingnatural scientist [3] who was well-acquainted withBerthelot and worked at his laboratory (186831870).In 1927, a collection of articles was published in con-nection with the centennial anniversary of Berthelot’sbirthday. The collection presented evidence aboutscientist’s life (D.P. Konovalov) and his works inthermal chemistry (I.A. Kablukov), technology ofexplosives (S.P. Vukolov), and history of chemistry(B.N. Menshutkin). Materials on Berthelot can befound in numerous reference publications [538].

Berthelot was the first to synthesize by originalmethods from elements and simple substances a greatnumber of new and known natural compounds. Ber-thelot’s contribution to the development of the syn-thetic direction in organic chemistry was analyzed in[9311]. In 185331854, the scientist was dealing withsynthesis of fats by heating glycerol with palmitic,stearic, and oleic acids in sealed ampules. Berthelotproved that the substances synthesized by him formthe basis of animal and vegetable fats and are com-posed of a combination of three parts of acids and onepart of glycerol, with liberation of three parts of water.In 1855, he synthesized ethanol from ethylene and

water mixed with sulfuric acid, and later (1882) ob-tained formic acid from carbon monoxide and water inan alkaline medium. Already in 1861, Berthelot wrotea two-volume book Organic Chemistry Based on Syn-thesis, which made its author famous.

Much later, in a three-volume publication Hydro-carbons, Experimental Investigations, 185131901,Berthelot summarized the results of an enormousnumber of syntheses of hydrocarbons and their deriva-tives from simple substances or elements.

He synthesized acetylene from carbon and hydro-gen in an arc furnace, and acetylene could then beconverted into quite a number of compounds: ben-zene, styrene, naphthalene, anthracene, etc. Berthelotthen passed from acetylene to ethylene, methane, andother compounds of the aliphatic series, to numerousoxygen- and nitrogen-containing substances. The partplayed by acetylene in classical Berthelot’s synthesesand the influence exerted by works of the Frenchscientist on the subsequent development of the chem-istry of acetylene were analyzed in detail in [12].Berthelot proposed a versatile method for reduction oforganic compounds with hydrogen iodide. This tech-nique had been widely used before the discovery ofthe catalytic hydrogenation method.

Together with problems of organic synthesis, Ber-thelot had been intensively studying for more than40 years, beginning in 1865, thermal chemistry andwas, together with a Russian scientist G.I. Hess(180231850) and Danish physical chemist J. Thomsen(182631909), one of its founders. As noted by So-lov’ev [13], Berthelot published in the field of thermalchemistry 152 works of his own, and 63, togetherwith his numerous disciples. In particular, V.F. Lugi-nin (183431911), a Russian physical chemist whoorganized at Moscow University the first Russiancalorimetric laboratory (1892), took part in Berthelot’scalorimetric studies. Berthelot paid much attentionto improvement of techniques for calorimetric meas-urements. The manual of thermal chemistry, writtenby him, was translated in Russia (Odessa, 1894). Asfar back as 1881, Berthelot was the first to designa calorimetric bomb for determining the heat of for-mation of organic compounds. The bomb later foundwide use in thermochemical laboratories all over theworld. The advance in calorimetric measurements wasmuch promoted by the invention by H. Le-Chatelier(185031936) of the platinum3rhodium thermocouple.

The basic idea in Berthelot’s works, and also ininvestigations by Hess and Thomsen, was the conceptof the heat effect of a chemical reaction as a measureof affinity of the reactants. In the final form, Berthelot

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MARCELLIN BERTHELOT 1891

formulated the principle of maximum work as follows(1875): [Any chemical transformation occurring with-out any influence of a foreign external energy tendsto produce bodies or systems of bodies whose forma-tion is accompanied by liberation of the maximumamount of heat.] In the subsequent years, the approp-riateness of application of the maximum work prin-ciple was discussed by quite a number of scientists[13315]. In particular, D.I. Mendeleev wrote in thefourth edition of Osnovy khimii (Fundamentals ofChemistry) (St. Petersburg, 1881, part 1): [...Al-though the principle of maximum work can well beapplied to experimental data in numerous cases, itcan be considered neither firmly established norbeing in agreement with the whole body of chemicalevidence.]

The development of chemical thermodynamics inthe end of the XIX century affected Berthelot’s viewsand, as noted in [15], this principle is already notdominant in the two-volume publication of the Frenchscientist, Thermal Chemistry, Quantities and Numeri-cal Laws (1897). A constructive criticism of theBerthelot3Thomsen principle can be found in worksby A.L. Potylitsyn (184531905), a Russian chemist,Mendeleev’s disciple [15, 16].

Berthelot also worked in the field of chemical ki-netics. Together with L. Pean de Saint-Gilles, hestudied the rates of the reversible esterification3saponification and demonstrated that, at any given in-stant of time, the rate of ester formation is propor-tional to a product of reactant masses and describedmathematically the reaction of acetic acid with ethan-ol. Having mentioned the relatively slow course ofreactions of this kind, the authors predetermined fordecades their being chosen as model reactions instudying the main kinetic laws. Berthelot was one ofthe first to pay attention in his book Studies of Chemi-cal Mechanics (1879) to the role of time in the courseof chemical reactions. Experimental studies by Ber-thelot and Saint-Gilles, carried out in 186231863,preceded classical works in chemical kinetics, per-formed in 186431867 by Norwegian scientistsC.M. Guldberg (183631902) and P. Waage (183331900).

A prominent place in Berthelot’s investigationswas occupied by inflammation and explosion. Accord-ing to Berthelot, two kinds of waves are generated inexplosion: blast wave and sound wave. Berthelot wasconcerned with problems of explosion and chemistryand technology of explosives till the end of his life.This aspect of the activities of the French scientistwas considered in detail by Vukolov [4]. The results

obtained by Berthelot in studying explosives and ex-plosions have been used for military purposes andin mining.

Much attention was paid by Berthelot to meth-odological and scientific-historical problems. Thephilosophical concepts of the scientist were sum-marized in quite a number of monographs: Scienceand Philosophy (1886), Science and Morals (1887),Science and Education (1901), and Science and FreeThinking (1905), and also in his correspondence withE. Renan (1898). E. Renan (182331892), professor ofancient Oriental languages at College de France,author of the multivolume publication History of theOrigin of Christianity, was on very friendly termswith Berthelot from his teens till the end of his life.Berthelot imagined the beginning of the XXI centuryas the time of unprecedented flourishing and leadingrole of chemistry. Simultaneously, he suggestedevolution of means of transportation, energetics, andcommunication. Unfortunately, Berthelot’s predic-tions, and in the first place those concerning the struc-ture of society and its morals and manners, proved tobe unrealizable.

In 1869, Berthelot visited, as a member of theFrench delegation, Egypt in connection with the open-ing of the Suez channel. This trip much stimulatedBerthelot’s interest in the ancient culture of thiscountry, and also in alchemy and astronomy. Hestudied the composition of ancient coins, decorationarticles, and arms. Berthelot wrote 10 volumes direct-ly concerned with history of chemistry, and he can berightfully considered one of founders of archeologicalchemistry.

Marcellin Berthelot died on March 18, 1907, at theage of 79, several hours after his wife passed away.He was buried in the Pantheon, near other outstandingsons of France. As an exception, his wife was buriednearby.

Academician N.N. Beketov (182731911), a promi-nent Russian physical chemist, spoke of his Frenchcolleague as follows: [Markings of his activities willremain indelible in the intellectual development of themankind.] W. Nernst (186431941), an outstandingGerman physicist and physical chemist and NobelPrize winner, named Berthelot [...one of the mostprominent scientists of all times.] And this is no over-statement. The already mentioned Timiryazev’s remi-niscences were named [Lavoisier of the XIX Century(Marcellin Berthelot, 192731907).]

In 1927, the centennial anniversary of MarcellinBerthelot’s birthday was celebrated in France. A rather

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representative Russian delegation, headed by A.V. Lu-nacharskii (187531933), a known statesman andpublic figure, people’s commissar of education of theRussian Soviet Federative Socialistic Republic, tookpart in the celebration. Reminiscences of this celebra-tion were published by V.E. Tishchenko [17] andKablukov [18], members of this delegation.

REFERENCES

1. Musabekov, Yu.S., Marcellin Berthelot, 182731907,Moscow: Nauka, 1965.

2. Musabekov, Yu.S., Sb. Nauchn. Tr. Yaroslav. Tekhnol.Inst., 1972, vol. 22, no. 2, pp. 3317.

3. Timiryazev, K.A., Sochineniya (Works), Moscow:Sel’khozgiz, 1939, vol. 8.

4. M. Berthelot, 182731927, Sbornik statei (M. Ber-thelot, 182731927, Coll. of Works), Leningrad: Izd.Akad. Nauk SSSR, 1927.

5. Blokh, M.A., Biograficheskii spravochnik (BiographicBook of Reference), Leningrad: Nauchnoe Khimiko-Tekhnol. Izd., 1929, vol. 1.

6. Musabekov, Yu.S. and Chernyak, A.Ya., Vydayu-shchiesya khimiki mira: Bibliograficheskii ukazatel’(Outstanding Chemists of the World: BiographicGuide), Moscow: Kniga, 1971.

7. Tuchs, G., Heinig, K., Kertscher, G., et al., Bio-graphien bedeutender Chemiker, Berlin: Volk undWissen Volkseigener Verlag, 1977.

8. Crosland, M.P., Dictionary of Scientific Biography,

Gillespie, Ch.C., Ed., New York: Charles Scrilner’s,1980, vol. 1, pp. 63372.

9. Giua, M., Storia della Chimica, Torino: Union Tipo-grafico-Editrige Torinese, 1962.

10. Bykov, G.V., Istoriya organicheskoi khimii: Otkrytievazhneishikh organicheskikh soedinenii (History ofOrganic Chemistry: Discovery of the Most ImportantOrganic Compounds), Moscow: Nauka, 1978.

11. Nikulina, E.P., Ocherki po istorii organicheskoi khimii(Essays on the History of Organic Chemistry), Mos-cow: Nauka, 1977, pp. 21363.

12. Shmulevich, L.A., Glavy iz istorii organicheskoi khi-mii (Selected Chapters of the History of OrganicChemistry), Moscow: Nauka, 1975, pp. 283121.

13. Solov’ev, Yu.I., Ocherki iz istorii fizicheskoi khimii(Essays on the History of Physical Chemistry), Mos-cow: Nauka, 1964.

14. Kipnis, A.Ya., Razvitie khimicheskoi termodinamikiv Rossii (The Development of Chemical Thermo-dynamics in Russia), Moscow: Nauka, 1964.

15. Istoriya ucheniya o khimicheskom protsesse: Vseob-shchaya istoriya khimii (History of the Concept ofthe Chemical Process: General History of Chemistry),Moscow: Nauka, 1981.

16. Solov’ev, Yu.I., Istoriya khimii v Rossii (History ofChemistry in Russia), Moscow: Nauka, 1985.

17. Tishchenko, V.E., Zh. Prikl. Khim., 1928, vol. 1,no. 1, pp. 57359.

18. Kablukov, I.A., Nauch. Rabotn., 1928, no. 1, pp. 67375.

A. G. Morachevskii