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Home , Ytterby

Rediscovery of the Elements

Yttrium and

James L. Marshall, Beta Eta 1971, and Virginia R. Marshall, Beta Eta 2003, The Beginning of Department of Chemistry, University of i the Rare Earths North Texas, Denton,TX 76203-5070, 300 km -~. jimmaunt.edu A> The Beginning of the Rare Earths: 04 Turku Ytterby. (Figure 1). For centuries the Chinese were the masters of fine porcelain Ytterby ' manufacture. In 1708, Europe learned the art Stockholrrp when the two Germans, Johann Friedrich B6ttger (1682-1719) and Ehrenfried Walther Figure 1. The history of the rare earths begins with von Tschirnhaus (1651-1708), discovered how the Ytterby Mine, where the source mineral for to make quality chinaware from feldspar and was found; and Abo (now called by the quartz.' Swedish porcelain factories, such as Finnish name Turku), where Johan Gadolin dis- R6rstrand in in 1726, developed a covered yttrium in the Ytterby Mine specimen. great appetite for premium feldspar and quartz Ytterby, 20 km northeast of Stockholm, means available on Resar6 Island (Figure 2) in the "Outer village"in Swedish. Figure 3. The Ytterby Mine (N 59 25.60 E 18 Swedish archipelago 20 kilometers northeast of 21.21) can be reached directly from Ytterbyvagen 274 Stockholm.' On this island near the village of Qugen = road) on the eastern end of Resaro Ytterby, a mine was developed (Figure 3) which og erby Island. The slope leading up to the mine is littered could furnish this profitable raw material in with numerous interesting minerals. About the abundance (Figures 4, 5, 6). mine area are streets named Yttriunvagen~ In 1787, a Swedish artillery officer and ama- N <1 Terbiumvigen, Gadolinitvagen, Faltspatsvagen, teur geologist, Lieutenant Glimmnerviigen (glinnner= mica), Tantalvigen, (1757-1824), visited the Ytterby Mine"' and and Gruvv'gen (gruv = mine). noticed an unusual heavy black rock which occurred in narrow layers through the mineral the high activity of chemical research in Paris, quartz beds (Figure 7). He passed a specimen he never visited France, possibly because of his on to Bengt Reinhold Geijer (1758-1815), concern about the political climate there.' Inspector of Mines in Stockholm. A year later Figure2. The village of Ytterby on the island of Gadolin's important researches included Geijer announced' to the world the"heavy rock Resaro, historically could be reached only by boat. thermochemistry-he refined the values for the that my friend Arrhenius found ... in Ytterby It can now be accessed by road from Stockholm; heat of ice and showed it was identical to that three miles from Stockholm" (German Meile = public transportation(bus) is also available. of snow 1-and the theory of combustion-his 4.6 English miles). Geijer performed some pre- textbook was the first in Swedish to promote liminary tests, such as"Berlinblau," proving the was then called Abo, a part of Sweden). Johan the new antiphlogiston theory of Lavoisier. existence of iron (reaction with potassium fer- Gadolin, a native of Abo, had studied under His best known contribution, however, is his rocyanide to form the blue pigment "Prussian Torbern Bergman at Sweden's major university discovery of yttrium in the sample provided by blue"), and he speculated that perhaps the at Uppsala and written a dissertation on the Lieutenant Arrhenius. "Schwerstein," ("heavy rock") contained analysis of iron.' In addition to his native Even before the end of the phlogiston era, "Wolfram" (tungsten), recently discovered by Swedish, he also was fluent in Latin, German, the best analytical chemists of the late 1700s Scheele in 1781 in Koping, Sweden.; English, French, Russian, and Finnish." He trav- possessed a laboratory skill that was astonish- For a complete chemical analysis of his eled extensively through western Europe and ingly accurate. The most famous analytical "Schwerstein" Arrhenius turned to Johan visited universities and mines in England, chemists of the day were Louis Nicolas Gadolin (1760-1852), (Figure 8) a professor at Ireland, Holland, and Germany, finally return- Vauquelin (1763-1829) of Paris and Martin the University of Abo in Turku, Finland (the city ing to the University of Abo in 1797.' Despite Heinrich Klaproth (1743-1817) of Berlin. These

8 THE HEXAGON/SPRING 2008 -:-!_1'.r it' ,-"M : , :' ,

Figure 4. This was the original reason for the Ytterby Mine-high qualityfeldspar (left) and quartz (right) used in the porcelain industry. Feldspar (taken from German for"Feldspat," imea- ing'"field spar") is a general term for alkali and - alkaline earth alaninosilicatesand is the most conmion mineral in the earth's crust, comprising 60 percent. Quartz (SiO2) is the second most common mineral. Today the Ytterby area is still littered with large amounts of both minerals.

Si ,IIe - I he thri-! lmue is now hea ilIy olTrroWl' with tras and otherteetation. it A( \ ( .n'ecan chemists' exquisite skill allowed them to deter- Society of Metals) International has erected a sign recognizing the site as a historical landmark, the "birth- and to dis- mine the composition of minerals place"of the rare earth elements. cover several new elements-long before mod- ern techniques such as spectroscopic analysis. Gadolin was an accomplished analytical chemist as well, and his research allowed him discover in 1794 the first rare earth, yttrium; to 'N, A centuries-old method for assaying ores began with the digestion of an ore in concen trated nitric acid. When Gadolin"' used this pro HAI DESIGNA1ED cedure on "Schwerstein," an insoluble portion AN HETRCAL LANDMiARK was separated and identified as silica by its cal cination with sodium carbonate to obtain a clear glass. The remaining soluble portion was treated with sodium carbonate to give a hydroxide precipitate, which proved to be iron by its positive"Berlinblau" reaction, corroborat figure o. T111 "1% sign tolls us that"Ytterbnt was Figure 7. The Ytterby Min' was special because the ing Geijer's conclusion. The remaining solution the physical and etymological source for four ele- rocks there were formed by slow cooling, allowing was treated with ammonia to give additional ments. This mine also furnished minerals for the the formation of pegmatites (mixtures of quartz, hydroxide precipitate. Further treatment of the discovery of , , and tantalum. feldspar, and dark minerals with large crystals). solution with KOH gave no further precipitate, Unusual minerals such as gadolinite indicating that there was no calcium, magne- (Y FeBe Si20 ) separated out in wide bands in sium or tungsten (these cations precipitate in Anders Gustaf Ekeberg (1767-1813), a pro- 2 2 10 the special geochemical cooling process. Johan KOH but not in ammonia)-disproving fessor of chemistry at the University of Uppsala Gadolin analyzed gadolinite and found all compo- Geijer's guess that tungsten was present. When (who in 1802 was to discover tantalum in nents in this mineral-yttrium, iron, beryllium, treated with excess KOH, a minor portion of yttrotantalite, Y2TaO4, also collected at the and silicate-but the beryllium, which had not yet the gray hydroxide precipitate redissolved, Ytterby Mine,"'), procured a larger, purer sam- been discovered (in 1798 by Vauquelin in Paris), identified as aluminum because of its ampho- ple of the Arrhenius "black stone from Ytterby" was mistaken by Gadolin for aluminum. teric nature." The remaining precipitate of yttri- uncontaminated with feldspar. He confirmed um hydroxide was characterized by Gadolin and refined Gadolin's results in 1797, giving a with reactions with various acids and with the composition of 25 parts of silica, 18 parts of iron Beryllium was discovered a year later by 2 blow pipe. He concluded he had a new earth:2 ' oxide, 41/2 parts of aluminum oxide, and 47 1/2 Vauquelin1 who was studying beryl and emer- "These properties suggest that this earth has parts of the new earth." He gave the name alds'" upon the suggestion of Ren6-Just Ha6y of similarities with alum and with lime, but also "Ytterjord" (Swedish for "Ytter earth") or the Ecole des mines in Paris, who had suggest- dissimilarities from both of these, as well as "Yttria" (Latin) to the new earth, and ed that these two minerals, with the same crys- 2 other known earths, whence it should be "Ytterstein"(ytterbite) to the source mineral. talline form, might be chemically identical.' included among the simple earths..."He thus Unfortunately, Gadolin and Ekeberg did not Vauquelin was fortunate that beryl/emerald proposed the composition of the mineral to be know that their "aluminum" was a new ele- contained only four elements (Be 3Al 2Si 60 18), 31 parts silica, 19 parts aluminum oxide, 12 ment-beryllium, not yet discovered! This over- allowing simple distinction between aluminum parts iron oxide, and 38 parts of an unknown sight was understandable, because their atten- and beryllium not confounded by the presence earth ("unbekannte Erdart"). tion was concentrated on the new earth, yttria. of other metallic ions. In the laboratory

SPRING 2008/THE HEXAGON 9 C

Figure 9. The predominant language in Turku is Figure 10. This is the appearance of the unwu'rsny now Finnish; in Gadolin's time the city was ('Akademitorget i Abo"or"Academy Square in known by its Swedish name Abo. Key sites in Abo") before the Great Fire of 1827, and where Turku are: (A) Turku Cathedral (Tuomiokirkko), Gadolin made his discovery of yttrium in 1794 N 600 27.15 E 220 16.66. (B) FirstAcademy ("B"of Figure 9). The ground floor of the front Building, where Gadolin discovered yttrium, now right building housed the first chemical laboratory occupied by Vanha Akatemiatalo (Old Academy of the Academy (1764-1804). A glimpse of Building)-Rothoviuksenkatu 2, N 600 27.11 E Vdrdberget (see Figure 13), the hill where Gadolin Figurc Gadolin, professor at S. Johan of chemistry 220 16.77. (C) Modern chemistry building had his garden and private laboratory, can be seen the University of Abo (Turku, Finland) and the "Gadolinia,"Porthanskatu(Porthansgatan) 3, N in the background at left. The top of the cathedral discoverer of yttrium. Even though Gadolin lived 600 27.25 E 220 16.77. (D) The origin of the 1827 spire can be seen behind the building; hence, the to the age of 92, this is the only known portrait of fire, in Puutorisquare, historicallya public toilet, view is southwest along the present Hiimeenkatu, him, made when he was a student at the now a restaurantPuutorin Vessa ("Public Toilet the main street of Turku. University of Uppsala, Sweden, at the age of 19. Pub"), N 600 27.30 E 220 16.12. Plaques are in the east side of the square,flush with the side- age of 62. He spent his last years in Mynamaki walk, Aninkaisenkatu 9, N 600 27.32 E 220 16.20. (Wirmo), 30 kilometers to the northwest, where Vauquelin fused beryl with caustic potash (E) Observatory Hill, Vartiovuori ("vuori"= "hill"), he lived on a manor until the age of 92. (KOH); the resulting mass could be completely N 600 26.92 E 220 16.65, blocked the historicfire dissolved in muriatic acid (hydrochloric acid). Gadolin's legacy. Until the discovery of the from spreadingfurther south. (F) Handicraft Upon incomplete transuranium elements, Gadolin shared with evaporation, silex (silica) pre- Museum (survived the 1827 fire), on Samarsky (Vasili Evgrafovich Samarsky- cipitated and was separated out. The filtrate, Luostarinmuki (LuostarinHill), N 600 26.83 E Bykhovets 1803-1870, chief of the Russian containing only aluminum and beryllium 22 16.60, a "living historicpark"where guides in Mining Engineering Corps 1861-1870) the cations, was treated with caustic potash to pre- costume show how people lived in the early 19th honor of being the only person after whom an cipitate the hydroxides. In excess KOH he then century. (G) Gadolin plaques, on wall in front of element was named-gadolinium and samari- redissolved the amphoteric' aluminum/berylli- fish restaurant, KalaravintolaKaskenahde, which um, respectively. Gadolin's discovery of yttrium um hydroxide mixture. The observant Vauquelin was the site of Gadolin'sformer home, 6A, was the beginning of a long line of rare noticed that a fraction of the hydroxides did not Kaskenkatu, N 600 26.80 E 220 16.37; in back is earths, no less than 17. Mosander (Berzelius' assistant) seem to be quite as soluble. This fraction he the orphanage, site of Gadolin's laboratory, 5 later in Stockholm from yttrium separated separated and showed to have chemical behav- Luostarinkatu, N 600 26.80 E 22 16.46. (H) "Old and , which in turn led to dis- ior distinct from that of aluminum using a few plantation,"where Gadolin raised his crops, now covery of more of the key experiments," viz., beryllium's solubility in the site of Surutoin restaurant, where formerly "heavy" rare earths which were ammonium carbonate, its reprecipitation in "Gadolin dishes"were served, Kaskenkatu 12, N separated out-while Berzelius' subse- boiling KOH, its inability to form an alum, and quent discovery of cerium" led to the discovery 600 26.69 E 220 16.51. (1) Site of 1823 painter's 2 the solubility of its oxalate or tartrate salts." location (see Figure 11), Kerttulinmuki (Kertulin of the "light" rare earths ' (Note 2). Berzelius later exclaimed (1843), "What a scoop it would Vauquelin called the element glucinium Hill), N 60 27.02 E 220 17.03. NOT SHOWN: have been if he [Gadolin] had been able to sep- because of the sweet taste of its salts-chemists Gadolin's grave at Myndmdki, 30 km northwest of 0 arate them!". then routinely reported taste and smell of new Turku, N 60 40.76 E 21 59.39, in the village he 0 substances-but Klaproth preferred"Beryllerde" retired (then known by the Swedish name ("beryl earth") and the name stuck."' (Note 1) Wirmo). Notes. After Vauquelin's discovery of beryllium, Note i. Klaproth suggested glucinium be called Ekeberg realized his "Ytterbite" contained beryllium, because "yttrium salts also were beryllium instead of aluminum.'"). His refined ratory where Gadolin performed his yttria sweet."" We suspect this was an error, due to analysis gave 23 parts of silica, 55.5 parts of research (Figure 10) no longer exists; it was the beryllium component in the gadolinite. yttria, 4.5 parts of beryllium, and 16.5 parts of destroyed in the Great Fire of 1827 which raced Modern literature (including MSDS and Merck iron. Klaproth, who also analyzed the mineral, down the hill from a bakery to the center of information) does not include taste data for named it "gadolinite," the name by which we town (Figure 11). The laboratory was beside the yttrium salts (except for redactions of know it today."' By the latter 1800s the formu- cathedral, which itself was badly damaged in Klaproth's initial comments). We conducted a la" was determined, Y2FeBe 2Si 2O 10 . the fire (Figure 12). In 1797, Gadolin had private sommelier session with yttrium chloride Rediscovering Turku. Today Abo is known moved to his Turku home atVardberget (Figure and can report the salt to possess a pleasant tart by its Finnish name Turku (Figure 9). The labo- 13), where he lived until his retirement at the taste, but not sweet.

10 THE HEXAGON/SPRING 2008 classic amphoteric hydroxides - aluminum Puutori square and beryllium-will neutralize either an acid or a base. Hence, these hydroxides are Observatory Cathedral insoluble in water but soluble in acids or Laboratory bases, e.g., Al(OH)3(s) + 3H+ - A13 +(aq) + 3H20; and Al(OH)3(s) + KOH KAl(OH)4(aq). 't 10. Dana's New Mineralogy, 8th Ed., John Wiley & Sons, N.Y. 1997. 11. A. G. Ekeberg, Kungl. Vetensk. Akad. Handle. [Trans. Roy. Acad. Sci. Stockholm], 1797, 18, 156-164; Chem. Ann. [Creel's Annalen], II, 63-73. Figiur I. Iesttin/ &lete Ae/\1'& mIum, C__ 1799, four years before the Great Fire, with important 12. Marshall, op. cit., 2004, 95(2), 24-28. sites identified. This overall view emphasizes the Ann. Chim., 1798, 26, s- - ^ "A 1- - - 13. L.-N.Vauquelin, hilly terrain of Abo (present Turku). The view is 155-177, 259-265. westward front Kerttulinmuki (Kertulin Hill). The 14. C. L. Parsons, The Chemistry and Literature cathedral ('A"of Figure 9) and Observatory Hill Figure 12. The proeminent Turku Cathedral of Beryllium, 1909, Chemical Publishing Co., (Vartiovuori) with its old observatory ("E"of (Tuomiokirkko) wais originally built of wood in the Easton, PA, 1-2. Figure 9) are the prominent features. The road is 1200s and augme 'ited with stone 1500-1700. 15. M. Klaproth, Beitrage Zur Kentniss der the old Humeentie (today Hiimeenkatu), the his- The cathedral ("A' (a), p 52; (b), p 78. toric main road out of Abo and the present main historic Turku. Just to the right (out of sight) was Mineralkbrper,18oo, 3. street of Turku. Disappointingly, the old Gadolin located the chemis try laboratory where Gadolin 16. A. G. Ekeberg, Kungl. Vetensk. Akad. Handl. laboratory ("B"ofFigure 9) cannot be clearly dis- discovered yttriumi, now occupied by a modern [Trans. Roy. Acad. Sci. Stockholm], 1802, 23, cerned, although its position can be marked. The "Old Academic Building"("Vanha Akatemiatalo.") 68-83. Great Fire of 1827 started in Puutori square ("D" The view is east ard. 17. G.W. Petersson, Geol. Fren i Stockholm of Figure 9) and swept relentlessly down the hill Forh., 1890, 12, 275-347. past the cathedral and the university, but it 18. Marshall, op. cit., 2007, 98(4), 70-76. stopped at Observatory Hill. After the fire, the References. 19. D. M.Yost, H. Russell, Jr., and C. S. Garner, university continued in the observatory for several 1. D. Lundberg, Doctor Thesis, 2006, ISSN The Rare-Earth Elements and Their months, before it moved to Helsinki the following 1652-6880, Swedish Society of Agricultural Compounds, 1947, Wiley, NY. year. The observatory was at sea level 7000 years Sciences, SLU Service/Repro, Uppsala, ago! (Scandinavia, because of geological isostasy, Sweden. is lifting as the global ice melts.) 2. Episodes from the History of the Rare Earth Elements, C. H. Evans, ed., 1996, Kluwer. (a) Note 2. Yttrium, discovered in gadolinite in P. Pykk6 and 0. Orama,"What did Johan 1794, was found over several decades to be a Gadolin actually do?" 1-12. (b) J. Trofast, mixture of rare earths, yielding a series of other "The Discovery of Cerium-a Fascinating so-called "heavy rare earths" including erbium, Story," 13-36. (c) L. Tansj6,"Carl Gustaf terbium, , holmium, , ytter- Mosander and his Research on Rare bium, scandium, and lutetium. Because of the Earths," 50. contraction, the "heavy rare earths" 3. Johan Gadolin 1760-1852 in Memoriam, 191o possess a smaller atomic radius, similar to that pub. by E. Hjelt and R. Tigerstedt, Druckerei of the lighter yttrium, and they occur with it in der Finnischen Literaturgesellschaft, nature.'" Cerium, discovered by Berzelius and Helsingfors [Helsinki]. Hisinger in 1803,'" tends to harbor in nature the 4. B. R. Geijer, Chem. Ann. [Creel's Annalen], Figure 13. Gadolin's home and laboratoryat his "light rare earths"which are larger: lanthanum, 1788, I, 229-230. Turku plantation on Vdrdberget ("Fire Signal praseodymium, neodymium, samarium, Mountain") 1797-1814 is now occupied by a fish gadolinium, and europium."" 5. J. L. Marshall and V. R. Marshall, The HEXAGON of Alpha Chi Signia, 2005, restaurant ("G"of Figure 9). His laboratory was in 96(1), 8-13. back of the restaurant, a building which still exists Acknowledgments. and which is used as an orphanage (not shown). 6. P. B. Dean and K. I. Dean, Acad. Radiol, His home was not touched by the Great Fire, and The authors are indebted to Pekko Pykk6, 1996, 3, 165-168. professor of chemistry at the University of his records were preserved. Two corroded copper 7. J. R. Partington, A History of Chemistry, Helsinki, who furnished a large amount of the plaques (on the stone wall above sidewalk) in both 1961,Vol. III, Macmillan, London, 235-236. information regarding Turku and Gadolin Finnish and Swedish translate "On this site at (including Figure 10). Professor Pykko actually 8. J. Gadolin, Kungl. Vetensk. Akad. Handl. house number 161 in the Cloister Quarter the lived at Kaskankatu 6, the site of the home of [Trans. Roy. Acad. Sci. Stockholm], 1794, 15, professor of chemistry at Abo Akademi Johan Gadolin, during the mid-1970s, and thus has a 137-155; Chem. Ann. [Creel's Annalen], Gadolin had his laboratory 1797-1814." personal connection with the history of 1796, I, 313-329. (Luostarinkatu, the address of his laboratory, Gadolin. The home is now gone and has been 9. F. P. Treadwell, Analytical Chemistry, 1937, translates into Swedish as Klostergatan, meaning supplanted by a condominium. Vol. 1, 9th English Edition, Wiley, N.Y. The "Cloister Street.")

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