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Yttrium and Johan Gadolin

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Yttrium and Johan Gadolin Rediscovery of the Elements Yttrium and Johan Gadolin 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 yttrium was found; and Abo (now called by the quartz.' Swedish porcelain factories, such as Finnish name Turku), where Johan Gadolin dis- R6rstrand in Stockholm 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 Carl Axel Arrhenius 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 holmium, scandium, 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.
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