Friedrich Wohler and Hi# Lifelong Interest in the Platinum Metals

Friedrich Wohler and Hi#Lifelong Interest in the Platinum Metals By Robin Keen Hainham Mark Grammar School, Kent

Friedrich Wohler was perhaps the last great a classical bias and he did well there while at all-rounder of chemistry (I). A skilful experi- the same time developing private hobbies. menter, he was above all a laboratory rather than During childhood he was an inveterate collector a theoretical chemist and he delighted in attack- of minerals and then as an eighteen year old his ing problems in inorganic or organic chemistry interest turned to their chemistry. We have at the workbench. New minerals and new ele- from letters he wrote to a schoolboy friend ments fascinated him. More than half a century Hermann von Meyer a blow by blow account of divides his first and last papers on platinum his youthful experiments, conducted in his metals (2, 3) and over the years he made several bedroom at home in Frankfurt (4). Oxygen pre- distinct contributions to their chemistry. paration, phosphorus extraction, and eventually He was born in 1800 at Escherheim, now a the isolation of potassium using a 100-plate suburb of Frankfurt-am-Main, to Auguste battery were all achieved in spite of phosphorus Wohler, one-time Master of the Horse to the burns and broken chlorine flasks. Meyer owned Elector of Hessen-Kassel but by then a wealthy a chemistry text-book by Ferdinand Wurzer farmer, and Katherina Schroder, the daughter (I765-1 844), Professor of Medicine at Marburg of a Professor of Philosophy. The Frankfurt University since 1804, which Wohler knew Gymnasium, which he attended from 1814,had almost by heart. Though there was no chemical

Friedrich Wohler 1800-1 882 One of the first German students to benefit from a period under Berzelius, Wohler became his life long friend and the translator of his works into German. While Professor of Chemistry at Kassel he investi- gated the separation of the platinum metals and devised a method of separating iridium and osmium that was used commercially. For many years afterwards he was professor of Chemistry at Gottingen, the Uni- versity founded by King George I1 of England, and his interest in the platinum metals continued

Platinum Metals Rev., 1985,29, (2), 81-85 81 instruction at Frankfurt Gymnasium Wohler or flexible tubing of any kind were available.) might have expected to find it on a medical Before leaving Sweden in September 1824 degree course at Marburg in 1820, but there Wohler toured with Berzelius, meeting Hisinger was none, so after a year he transferred to and Oersted, of whom Wohler wrote in 1875: Heidelberg. There Leopold Gmelin told him “he could not at that time have guessed what not to bother with the chemistry lectures but to epoch-making change would result from the work in his laboratory, and in I 822 Gmelin and major scientific discovery he had only recently Wohler published a joint paper on cyanide com- made” (6) (Oersted discovered electro- pounds, including the first preparation of the magnetism in I 820). double cyanides of platinum and palladium (2). Wohler Returns to Germany His Year with Berzelius Berzelius’s influence secured Wohler a post After graduation in medicine in 1823, and in Berlin which he held till 1831. By now his thanks to Gmelin, Wohler secured a year as Swedish was good enough for him to undertake assistant to Berzelius in Sweden. In a letter to the translation of Berzelius’s influential Meyer (5) we have a glimpse of Berzelius’s “Lehrbuch” (7) into German: successive edi- laboratory and life in Stockholm: tions of this and the magisterial reviews of chemistry (8) which Berzelius wrote each year “I lodge with the ship’s captain. . . . At 7 a.m. I eet UD and translate some exercises from the kept Wohler upto-date and provided him with Swedish. . . . At 8 a.m. I dress, cross the bridge the widest possible chemical education. German and walk (no skis for me, I prefer galoshes) to chemistry was in fact much influenced by the Berzelius’s house. There he sits at his table, availability of Berzelius’s writings and views. A which is covered with glass and platinum - his present work on fluorides can only be done in lively correspondence, sometimes about platinum. He wears a black coat - on which chemistry, but always full of personal warmth, several reactions can be studied. , . . I sit down at lasted till Berzelius’s death in I 848 (9). the table, look at my lithium salts crystallising Chemical mythology credits Wohler with from yesterday, and get on with an analysis of a cyanic salt compound which I had the misfortune being the first to prepare an organic compound, to discover and must now follow up. I carry on urea, from inorganic sources in 1828, an experi- with the analysis of lievrite which I have carried ment which was later widely believed to have out six times already but still have not finished because the results never agree. . . .” overturned the vitalistic view of the nature of organic compounds. He was not, however, the When he arrived in Stockholm Wohler had first, and the preparation did not have this been lent a platinum crucible, probably one result, but his admirers later in the century that Berzelius had from Wollaston in England claimed for him a number of doubtful but he now ordered his own from Frankfurt. priorities. Whether he or H. C. Oersted (or Berzelius’s accurate analytical results never indeed neither) first prepared a sample of cease to amaze the modern reader; before start- reasonably pure aluminium before 1827 is also ing an analysis Wohler had to purify by debatable (I0). But Wohler himself was not the recrystallisation all his reagents and he learned kind of man who bothered very much with in Stockholm the full discipline of Berzelius’s priorities and controversy. Unlike many of the methods. At the same time he met new major scientists of the nineteenth century apparatus and arranged for a spirit lamp Wohler was a modest, unpretentious, good- burner, which was unknown in Heidelberg, to humoured and well-loved man, who genuinely be sent to Gmelin. (Only 12 years later when enjoyed teaching the students who flocked to Wohler became Professor at Gottingen he his laboratory in Gottingen from many parts of found twenty-five platinum crucibles, a large the world. platinum retort, massive platinum tubes and H. C. Oersted’s work on aluminium consisted plenty of common apparatus but no spirit lamp of the preparation of aluminium chloride,

Platinum Metals Rev., 1985,29, (2) 82 which he then decomposed by potassium occurs at red heat and the hydrogen is released. amalgam to leave “aluminium” after distillation Carbon dioxide he showed to be unreactive to (I I). Wohler in his paper (I 2) gave full credit to palladium at all temperatures. He described Oersted but reported that he had been unable to how palladium absorbs hydrogen at low produce any metal from the chloride in this temperatures and releases it at higher way. Instead, for the second stage he heated temperatures; cool palladium with absorbed aluminium chloride with potassium metal in a hydrogen became red hot in air as the hydrogen platinum crucible, causing a very energetic burned away. reaction “but the metal of the crucible was not International fame came to Wohler in 1832 affected in any way”. Soon afterwards he used when he and Liebig published an outstanding the same technique to obtain beryllium and paper on oil of bitter almonds (benzaldehyde) what he believed, probably erroneously, to be and the benzoyl radical (18). By this time he yttrium (I 3). was Professor at Kassel and in 1835 he visited In 1855 Henri Sainte-Claire Deville Paris for three weeks, meeting for the first time (I8 I 8-1 88 I) published a method for extracting Gay-Lussac, ThCnard, Arago, Chevreul and aluminium, on a larger scale, from sodium Dumas, a galaxy of talent which he described in aluminium chloride, NaAlCl 4. Napoleon I11 letters to Berzelius. The wealth and social honoured both Deville and Wohler and a medal standing of the French chemists, the formality was struck, zocm in diameter, from Deville’s of their meetings and the quality of much of first ingot, bearing Napoleon’s head on one side their work impressed him. Dumas, almost an and on the other Wohler’s name and the date exact contemporary of Wohler, gave him to 1827. Unfortunately this medal seems now to take home a pound of platinum residues, a be lost (14).Wohler later published with Deville black solid left behind when platinum ore had two joint papers on compounds of silicon and been digested in aqua regia. Writing to Liebig three on boron (I 5). (19): Between 1821 and 1880 over 300 papers “Dumas was most hospitable and personally arranged a demonstration of his vapour density appeared in Wohler’s name, 23 with Liebig as method. He also gave me a large portion of co-author but only 19 with any other platinum residues and this has encouraged me to collaborators. He did not believe in adding his work out a very practical method of separation. If name to students’ work carried out under his you mix the residues with salt and heat the mixture in a stream of damp chlorine gas the supervision. The span of time involved is iron-titanium is left behind while soluble illustrated by the opening of a paper (3) by chlorides of osmium and iridium sublime.” Wohler published in 1877: “Already, a long time ago, in 1824, I have observed that The Separation of Iridium palladium.. . when left in an alcohol flame and Osmium slowly becomes covered with a layer of carbon”. Besides the private letter to Liebig there was He had also observed that the palladium was another to Pelouze in Paris which was left as a brittle fine skeleton and at that time he published in Annales de Chimie (20). Berzelius believed that palladium had an affinity for had just sent him for translation in manuscript carbon (I 6). After Graham’s work (I 7) on occlu- a chapter on platinum for the Textbook, and sion he now accepted that the phenomena were then further material on what seemed to be a due to the absorption of hydrogen. Still compound of iridium and osmium. Wohler interested in the subject, he obtained, through carried on with his own work and published a Liebig’s influence, twenty ounces of palladium full account in 1834 (21). The first stage from the large amount that Wollaston had described above was now attributed to Berzelius bequeathed to the Royal Society and carried out but was worked out in more detail. By careful experiments with ethylene, finding no reaction temperature control most of the osmium can be at IOO~C,though decomposition of the ethylene made to sublime while the iridium stays in the

Platinum Metals Rev., 1985,29, (2) 83 tube. After the heating the tube contents were Liebig’s Annalen from 1838 till 1882, the extracted with water, the insoluble titanium publication developing from a vehicle for and iron compounds filtered away, then the Liebig’s polemics to a very sober journal of solution evaporated to dryness and roasted - impersonal record. more osmium left at this stage severely irritat- ing the eyes. Sodium carbonate was fused with A Lasting Influence on the the remaining solid and the residue extracted Platinum Industry with water. Finally the insoluble iridium ses- Two of Wohler’s German students made quioxide was reduced in hydrogen to the metal. important technical and commercial contribu- This method was used by platinum refiners tions to the platinum industry. Wilhelm Carl until the twentieth century. In his letter to Heraeus trained as a pharmacist and then as a Berzelius (22) Wohler noted that there seemed chemist at Gottingen, while Heinrich Rossler to be quite a high percentage of gold in the obtained a doctorate with work on double residues and wondered if it would be worth cyanides of platinum and palladium at Gott- trying to buy platinum residues in bulk to ingen in 1866 (28). When the young Wilhelm extract the gold! Carl returned to the family pharmaceutical In 1839 the method was used to show that business he engaged, additionally, in chemical black speck impurities in a gold sample sent to preparation and the refining of precious metal him by a goldsmith were composed of osmium scraps. This led him to establish in I 85 I the W. and iridium (23). A quarter of a century later C. Heraeus Platinum Refinery, the forerunner Wohler published a paper describing the of the Heraeus company which continues to various colours osmium salts exhibit with this day as one of the major refiners and certain reagents and compared the reactions fabricators of platinum. Heinrich also returned with those of ruthenium (24). to run, with his brother Hector, a family Iridium ammonium chloride and several business which was later formed into the mixed salts of iridium and platinum were pre- limited company known as the Deutsche Gold- pared and described in 1857 (25). Just as und Silber-Scheideanstalt vormals Roessler. In Berzelius had received samples of minerals from time the name was simplified to DEGUSSA and all over the world and given them to students this international enterprise also remains for analysis, Wohler became recognised as an among the leaders in the platinum industry. expert in his turn. A sample of a mineral from Another student, an American named Edgar Borneo caught his attention in 1866 and the Fahs Smith, discovered from a fellow student same mineral was sent to him from Oregon, that at the Ph.D. oral examination Wohler had U.S.A., in I 869 (26). He noticed that these were a standard question on the separation of the the first known examples of a natural sulphide platinum metals, so he learned 12 pages of of a platinum-type metal: in this case Wohler’s text book by heart. Wohler con- ruthenium with some osmium. An early gratulated him not only on his chemistry but on American student (Ph.D 1847), Charles A. Joy the perfection of his language! Smith was in (I 823-1 89 I), re-visited Gottingen in I 857 with Gottingen in 1874 and he describes Wohler as his wife Laura and Wohler named the mineral an energetic teacher (29). In I 880 four hundred Laurite in appreciation of his friendship with of Wohler’s students subscribed to give him a the Joys: they stayed in correspondence for gold medal: 75 of these were American. many years. Wohler enjoyed a healthy old age, dying in his In a seven-line paper Wohler described in lodgings at the Gottingen chemistry building. I 874 the spontaneous reduction of palladium Just before the end of his life he gave away to a oxide in hydrogen (27), an excellent lecture friend a long-treasured relic of his period in experiment. Stockholm, Berzelius’s own platinum spatula. Wohler’s name appeared on the title page of He had lived to see Napoleon I occupy

Platinum Metals Rev., 1985,29, (2) 84 Frankfurt in 1814and to remark in a letter to during the second half of the nineteenth century. Liebig after the Franco-Prussian war that the The anonymous obituary for Chemical News French eagles captured in 1870 were made of in I 88 I could not have been written for many gdded aluminium. He was given many honours, of his contemporaries. It concludes: including the Royal Society Copley Medal on his seventieth birthday. “As a colleague, a teacher, and in every rela- tion of private life, Wohler was esteemed and When he died his early achievements seemed beloved for his kindliness and geniality of his so remote in time that they were hard to assess. disposition, his modesty and uprightness. Many In retrospect he can be seen above all as a great successive generations of students, now dispersed disseminator of chemical principles and over the world, can bear witness to his readiness to perceive and aid merit. He gave his pupils his practice, part the German scientific of own ideas, aided them in carrying out the educational system which underpinned the great necessary investigations and kept his share in the technological leap forward which took place work a secret” (30).

References

I There are several reviews of Wohler’s life includ- 13 F. Wohler, Ann. Phys. (Poggendm, 1828, 13, ing: 577 (a) R. Keen, in “Dictionary of Scientific Biogra- 14 An account of Deville’s work and the medal is phy”, ed. C. C. Gillispie, Scribner’s Sons, New given in: J. Richards, “Aluminium: its History, York, Vol. XIV, 1976, pp. 474-479; also Ph.D. Occurrence, Properties, Metallurgy and Applica- thesis, Univ. London, “The Life and Work of tions”, London, I 890 Friedrich Wohler, 1800-1882”,1976 15 On silicon: H. St.-C. Deville and F. Wohler, (b) A. W. Hofmann, Berichte, 1882, I& Annalen, and On 3 127-3290. A comprehensive but uncritical 1857,104,256; 1859,110,248. obituary notice. boron 1857,101, 113; and 1857,101, 347; and (c) J. Valentin, “Friedrich Wohler”, Stuttgart, 1858,105567 Wohler, Ann. Phys. (Poggendorff), I949 16 F. 1824,I, 231 2 L. Gmelin and F. Wohler, J. fiir Chem. I 7 T. Graham, Proc. Roy. SOC.,I 868/9, 17, 2 I 2 and (Schweiggm), I 822,36,230 500 3 F. Wohler, Annalen 1877,184,128 18 J. Liebig, and F. Wohler, Annalen, 1832,3,249 4 A. W. Kahlbaum, “Friedrich Wohler, ein 19 A. W. Hofmann, ed. “Aus Justus Liebig’s und Jugendbildnis in Briefen an Hermann von Friedrich Wohler’s Briefwechsel I 829-1 873”, Meyer”, Leipzig, I Braunschweig, 1888,2 vols. (This is in fact a poor 900 digest of the original letters, largely preserved in 5 Ibid.,p. 90 the Bayerische Staatsbibliothek in Munchen.) 6 F. Wohler, Berichre, 1875~8,838 11, P. 77 7 J. J. Berzelius, “Larbok i Kemien”, 1st Edn., 20 F. Wohler, Lettre A M. Pelouze sur l’extraction Stockholm, 1808-1 830, 6 vols. Wohler revised de I’iridium et de l’osmium du rCsidu noir de the first two volumes and translated the rest, platine, Ann. Chim., 1833~54~317 then saw two further editions - not published in 2 I F. Wohler, Annalen, I 834,9, 149 Swedish - through the press by I 841 8 J. J. Berzelius, “Jahres-Bericht uber die 22 0. Wallach, “Briefwechsel zwischen J. Berzelius Fortschritte der physischen Wissenschaft”, Tub- and F. Wohler”, Wiesbaden, I 90I ,2 vols., p. 544 ingen, 27 vols., 1822-48; Vols. 4-20, 1836-41, 23 F. Wohler, Annalen, 1839~29,336 bear Wohler’s name as translator 24 F. Wohler, Annalen, 1866,140, 253 9 0. Wallach, “Briefwechsel zwischen J. Berzelius 25 A. Muckle and F. Wohler, Annalen, 1857,104, and F. Wohler”, 2 vols.. Wiesbaden, 1901.A 368 scholarly edition with extensive footnotes F. Wohler, Annalen, 1866, illuminating the history of this period 26 139, 116;1869, 151, 374 10 K. Goldshmidt,Z. angew. Chem., 1925,38, 1057; 27 Wohler, Annalen, 1874,174, 199 I. Fogh, Kgl. Dan. Vidensk. Math. Fys., 1921,3. F. These set out the opposing claims 28 An account of W. C. Heraeus and Heinrich Rossler is to be found in D. McDonald and L. B. I I H. C. Oersted, “Scientific Papers”, ed. Frau K. Hunt, “A History of Platinum and its Allied Meyer, Copenhagen, 1920,Vol. I, p. cxxiii; the most accessible version. Original papers in Metals”, Johnson Matthey, London, 198% p. 326 Danish were not fully translated in foreign 29 H. S. Van Klooster, J. Chem. Educ., 1944, 5, journals of the time 158;C. A. Browne,J. Chem. Educ., 1930,7,502 I 2 F. Wohler, Ann. Phys. (Poggenm, I 827, I I, I 46 30 Chem. News, 1882,46,183

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