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profile/ in chemi/try Svante August Arrhenius, Swedish Pioneer in Physical Chemistry George B. Kauffman California State University Fresna, CA 93740
Bernard Jaffe has referred to Svante Arrhenius (185919271, Wilhelm Ostwald (1853-1932), and Jacobus ~ e n r i c u s van't Hoff (1852-1911) as the three musketeers of the theorv of electrolykc dissociation ( I ) . The youngest member of thfs triumvirate, Svante August Arrhenius, the second son of Svante Gustav Arrhenius and Carolina Christina Arrhenius (n6e Thunherg), was horn a t Vik, Sweden, near Uppsala, on February 19, 1859 (2). Young Arrhenius' intellectual abilities manifested themselves early. He taught himself to read at the age of three. He acquired a fantastic arithmetic skill and a pictorial memory by observing his father adding columns of figures in his account books. Later in his scientific work, he was fond of discovering relationships and laws from masses of data. From 1867 to 1876 he attended the Cathedral School at Uppsala, where he distinguished himself in physics and mathematics. Arrhenius then entered the University of Uppsala, where he studied mathematics. chemistrv. ". and nhvsics. . . His orieinal intention was to major in chemistry, but he considered the Professor of Chemistry, Per Theodor Cleve (1840-1905), an authority on the rare earths and metal-ammines, an uninspiring teacher who neglected the theoretical side of his subject. In 1881 ~ r r h e n i i chose s physics as the main subject for his doctoral study, although the conditions for its study in Uppsala were poor. Since the Professor of Physics, Tobias Robert Thal6n (1827-1905), did not encourage independent work in his laboratory, Arrhenius left Uppsala for Stockholm in September 1881 to work in the laboratory of Erik Edlund, Professor of Physics at the Swedish Academy of Sciences. After assisting Edlund in his work on electromotive forces in the spark discharge, Arrhenius began his first independent research, on the decay of galvanic polarization with time. Learning from Cleve of the impossibility of determining the molecular weights of substances such as sugar, which could not be volatilized without decomposition,and being unaware of the work (beginning in 1882) of Franqois Marie Raoult (1830-1901) accomplishing this. Arrhenius measured the conductivities of solutions of electrolytes (acids, hases, and salts), hoping to calculate the molecular weight of added substances from their effects on the conductivity. He soon realized that the state of the conducting salt was a matter of primary importance. The theorv of electrolvsis and electrolvtic solutions was hypoth"in the air" at this time; rott thus' chains,~~lausius' esis on the continual momentary separation of ions, Hittorf s work on ionic migration, Helmholtz's conception of the atomic nature of electricity, and Kohlrausch's work on conductivity were all leading to some comprehensive theory, which was finally proposed by Arrhenius-the theory of electrolvtic dissociation. his ereatest contribution to science. which he submitted to the be dish Academy of Sciences on June 6,1883. I t was published in 1884 as "Recherches sur la conductibdit6 galvanique des 6lectrolytes" (Investigations on the Galvanic Conductivity of Electrolytes) (3). The two parts of this memoir were combined and served as Arrhenius' doctoral dissertation. Part I, "La conductihilit6 des solutions aqueuses extrhmement dilu6es" (The Conductivity of Extremely Dilute Aqueous Solutions), consisted of
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ROGER R FESTA Normeast Missouri Klrkswlle, stateMo university 63501
the ex~erimentalstudies made in Edlund's laboratorv alone with 19 theses. It described a new method for measurjng the resistance of electrolytic solutions by means of rapidly alternating currents produced by a depolarizer. Although Heinrich Lenz and Friedrich Kohlrausch had made similar measurements, they did not extend their work to the great dilutions used by Arrhenius. The main im~ortanceof Arrhenius' memoir liesnot in the experimental measurements or the 13 theses of Part I but in his development of general ideas, which contain the germ of his theory of electrolytic dissociation and which appeared in definitive form in 1887 (4). Part 11, "ThBorie chimique des Blectrolytes" (Chemical Theory of Electrolytes), consisting of 56 theses explaining the experimental results of Part I and which Arrbenius based on previous work by Alexander W. Williamson (1851) and Rudolf Clausius (1857), was summarized by him as follows (3): In the present part of this work we have first shown the probabilit y that electrolytes can assume two different forms, one active,
the other inactive, such that the active part is always, under the same exterior circumstances(temperatureand dilution),a certain fraction of the total quantity of the electrolyte. The active part conducts electricity, and is in reality the electrolyte, not so the inactive part. In the 1884 article (3) Arrhenius does not use the word "dissociation," in contrast to the 1887 article (4) in which the "active part" of the electrolyte is identified with free ions acting as separate entities in solution. Arrhenius' theory was accepted only slowly because it was generally believed that oppositely charged ions could not exist separately in solution. I t was accepted largely because of the efforts of Ostwald and van't Hoff, and it eventually found confirmation in the modern theory of atomic structure. In order to explain the nonconductance of solid salts and pure water when tested separately and the conductance of aqueous salt solutions, Arrhenius postulated that when a solid salt is dissolved in water its molecules dissociate or ionize into charged particles, which Michael Faraday (17911867) had called ions. While Faraday had assumed that ions are produced only during electrolysis, however, Arrhenius proposed that they are present in solution even without application of an electric current. Arrhenius' views have been shown to he correct for weak electrolytes (weak acids, weak hases, and other covalent substances), hut his ideas were later modified in the case of strong electrolytes (salts) by Peter Debye (1884-1966) and Erich Huckel (b. 1896) in their theory of interionic attraction (5). Arrhenius was bitterly disappointed when his dissertation was awarded only a fourth class (non sine laude approbatur-approved not without praise) and his defense a third class (cum laude approbatur-approved with praise), grades insufficient to qualify him for a docentship. He sent copies of the dissertation to Clausius, Lothar Meyer, Ostwald, and van't Hoff. In August 1884, Ostwald visited Arrhenius at Uppsala. Ostwald's offer of a docentship a t the Polytechnikum in Riga led to Arrhenius'appointment in November 1884 to a docentship in physical chemistry a t Uppsalathe first in Sweden for this new branch of science. Through Edlund's influence, Arrhenius received a travel grant from the Swedish Academy of Sciences, which allowed him to work with Ostwald in Riga (1886) and in Leipzig (188918901, Kohlrausch in Wurzburg (1886), Boltzmann in Graz (1887, 1890), and van't Hoff in Amsterdam (1888). During these Wanderjahre he developed his theory of electrolytic dissociation and worked on isohydric solutions (61, heat of Volume 65 Number 5
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Svante A w u s t Arrhenius (1859-1927). Coutlesty William 8. Jensen.
dissociation of electrolytes, the influence of temperature on the derree of dissociation (7).and eauilibrium between electrolyt& (8). He proved the influence of electrolytic dissociation on osmotic pressure, freezing-point depression, and hoiling-point evaluation for solutions containing electroIvtes. and he investieated the effect of temperature on reac;on ;elocity. He also determined the eleckolytic dissociation of salts by solubility experiments (9) and investigated the hydrolysis-of salts, weakacids, and weak bases (Id) and the alteration of the strength of weak acids by addition of salts (11). After 1887, Arrhenius was recognized abroad as one of the luminaries of physical chemistry, hut Edlund's death in 1888 deprived him of his stoutest champion at home and greatly reduced his chances of obtaininn academic emdovment in Sweden. In 1891 Arrhenius patriotically declined professorship offered hv the University of Giessen (Germany), and that same year he was appointed Lecturer in Physics, and, later (1895-19051, over strong objections, Professor of Physics at Stockholms Hogskola (Stockholm Technical University), of which he served as Rector (1896-1902). Although his laboratory was small and poorly equipped, his name attracted many foreign workers who helped give his ideas wider currency. In 1894 Arrhenius married his assistant and best pupil, Sofia Rudheck. hv whom he had one son, Olav Vilhelm, an agricultural botanist and soil scientist. One son and two dauehters resulted from his second marriage in 1905 to Maria .fohansson. That same year Arrhenius received an offer of a professorship in the Prussian Academy, hut since King Oscar I1 of Sweden had expressed the wish that he not he allowed to leave Sweden, the Swedish Academy of Sciences founded the Nohel Institute for Physical Chemistry in 1905, with Arrhenius as Director, a post which he held until his retirement in spring 1927. At the Nohel Institute he did little practical work. Instead, he wrote under ideal conditions on whatever problems pleased him, and he stimulated and encouraged others in their research. From being a scientific outcast in Sweden, he had become a scientific oracle. Arrhenius was elected an honorary member of, and re-
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ceived medals from, numerous scientific societies (121, and he was awarded honorary degrees from many universities. His overdue election to the Swedish Academy of Sciences did not take place until 1901, and even then with strong opposition. His receipt of the Nobel Prize in Chemistry in 1903 ("in recognition of the extraordinary services he has rendered to the advancement of chemistrv hv his electrolvtic theory of dissociation"), the first swedeto-win this honor, marked the triumohant end of the battle for his theorv (13). After his theory b a s accepted by the entire scientificworld. Arrhenius turned his attention to other tooics. He became interested in the widest application of the fkdamental theorv of chemical reactions. In 1902 he heean to apolv the laws oftheoretical chemistry to physiologica~proble~,kspecially those of serum therapy (14). He found that organismic changes follow the same laws as ordinary chemical reactions and that no essential difference exists between reactions in the test tube and those in the human body. Arrhenius hecame active in the fields of astronomy and cosmic physics; he proposed a new theory of the birth of the solar system by the collision of stars (15) and used the ability of radiation oressure to transoort cosmic material to explain comets, the corona, the aurora borealis, and zodiacal iight. He also hvoothesized that spores of living matter are transported hiiadiation pressure from planetto planet with the resultant spread of life throughout interstellar space. He developed a theory to explain the ice ages and other profound climatic changes undergone by the earth's surface. He reflected upon the world's energy supply and the conservation of natural resources and was an early prophet of today's energy crisis (16). There was hardly a field of science to which he did not make original, if not universally accepted, contributions. During his last vears he wrote several textbooks and many hooks of apop;lar nature, in which he made it a point to indicate what was still to he done in the fields under discussion (17). He had a healthy constitution, hut he made great demands upon himself in order to maintain his extraordinary productivity. After a brief attack of acute intestinal catarrh in September 1927, Arrhenius died on October 2 and was buried in Uppsala. Literature Cited 1. Jaffe, B. In Crucibles: The Story o/ Chrmislry, /?om Ancient Alchemy to Nucieor Fisrion.4thed.: Dover: New York. 1976: pp 164-180. 2. Ostwald. W. 2. p h y i k . Chem. 1909. 69, V: Walker, J. J. Chrm. Sor, 1928, 1380: Palmaar. W. In Dcr Rurh d r r p r o r r ~ nChcmiker; Buggo, G., Ed.: Verlag Chemie: WeinheimiRergatrasse. 1929, 1965 Yol 2. pp 443.482; Riosonfeld, E. H. Ber. 1930, 6 3 4 1; Panington.J. R. A Hirtwy n/ Chamktry; St. Martin's: New York, 1964; Val 4, pp67268L: Sndderr, H. A. M. In Dicrionaryoiscirnlifir Biogmphy:Glllkpie. C. C., Ed.; Scribner's: New Yo&. 1970: Vol 1. pp 296.302: Kauffman, G. B. Eneyc1op~din n/ World Rinsrophy: McGraw-Hill: New York, 1973: Vsl 1, pp253-254 e V~tmskapr-AkodemiensHondlingsr 3. Arrhenius. S. Bihong till K o n ~ i i ~Suenska 1884.8 (13, 14); partial Engl tranal. by 0. Ladge inBrit. Asm. Reports 1886 1887, 310,357: tranal. and reprinted as Unlarauchungen vber die galvonirche Leil/tihisT O~twsld'sKlss~ikerder exakten Wisenehaften No. 160: Enkeil ~ P Ebktmlyte; gelmsnn: Leipzig, 1907. 4. Alrhcnius.S.Z,physik. Cham. 1887,1.631; translandreprinted as''0n theDissociatian of Substances in Aqueous Solution" In The Foundalionr of the Theory a/ Dilufr Solutions; Alembic Club Reprint No. 19 Livingsfone: Edinburgh. 1961: pp 4347. 5. Debye. P.: HOekel. E. Physik. 2.1923.24. 185. 305. 6. Arrheniu~,S. Ofuarslgl a/Kunaligo V ~ t ~ w k a p r o k o d r m i s nForhandlingor s 1888.233: /- ohusik. IR1R 2 284 ,~Chem .~~ ~-~~ ~. 7. Arrheniu%S. Zphysik. Cham. 1889.4.98. 8. Amheniur. S. O/mrsigt 1889,619Z.physik. Chem. 1890,5.1. 9. Arrhenius, S. O/wisiel 1892,481:Z.phyrik. Chem 1893.11,391. 10. Arrheniur.S. Zphysih. Chem. 1894. 1.7407. 11. Arrheniu8.S. Z.physik. Cham. 1899,31. 197. 12. in 1911 Arrheniusuirited theunited StatesforeeeivethefirstWillardGibb~Medslof the American Chemical Society's Chicago Senlon and presented the Sillirnsn Lect u r e at Yale Univerrity. published as Arrhenius. S. Theorirs o/ Solution: Yale Univemity: NPW Haven, CT, 1912. 13. Alrhenius. S. "Development of the Theory 01 Electrolytic Dibrociation": in Nobel Foundation Nobel Lectures. Chemistry. 1901-1921; Elsevier: Amsterdam, 1966: pp 45-61. 11. Arrhenius,S.;Madron,T. Z.physik. Chrm. 1903,44,7:Arrheniur,S. lmmunochem~rtry: Mecmillan: New York, 1907: Quontiinliue Laus in Bialoglenl Chsmirlry; Bell: London. 19L5. 15. Amhenius. S. Lahrbueh d s r kosmisrhm Phyrik; Hirzel: Leiprig, 1803: 2 vds. 16. Mosdey, C. G. J. Cham. Bduc 1978.51, 193. 17. Arrheniur,S. Vtirldornos Lllurckling: Cober:Storkholm, 1 9 W Ger. translLDas W e r ~ d m der Welten; Akad~miacheVedag6gesellsrhaft: Leiprig, 1907: Engl. transl.. Worlds in the Mokinp: Harper: New York. 1908; Dia Chrmie und dar modeme I,~b~n:AksdemischeVerlagsgerell~chaft: Lebzig. 1922: E q l trans1,Chemistryin Modern Life: Van Nostrand: New York. 1925.
