Rediscovery of the Elements Germanium: Freiberg, Germany James L. Marshall Beta Eta '71 and after his death.' Agricola lived most of Virginia R. Marshall his life in Saxony and Bohemia; he Department of Chemistry, University of was born in Glauchau, Saxony; worked in Sankt Joachimsthal, North Texas, Denton TX 76203-5070; Bohemia; and later became Burger- / Berlin. jimm@unt. edu; meister of Chemnitz, Saxony (Note 1). U Computer Technology, Denton ISD, De Re Metallica, translated from the Freiberg Denton TX 76201 original Latin into English by Herbert and Lou Henry Hoover,' not only con- Half a millennium ago, alchemy was tains full textual descriptions of the construction of mines and the assay Germany maturing into chemistry by advancing on and smelting of metals, but also two fronts: medicine and mining. In abounds with detailed woodcut fig- Munchen medicine, Paracelsus (Phillipus Aureolus ures. Agricola was one of the first to Theophrastus Bombastus von Hohenheim, differentiate among bismuth, antimo- 1493-1541) was promoting the use of chemical ny, tin, and lead. preparations and preached that a medicine The rich mining tradition of this .. 200 k possessed a quintessence that could be extract- Saxony-Bohemia region carries on to ed and used to combat disease. In mining, this day and centers about Freiberg, Georgius Agricola (Georg Bauer, 1494-1555) Germany (Figure 1). Annual festivals Figure 1. Freibergis the focus of mining activity in the was preparing classic treatises on mining and and parades are held with the miners Saxon area and boasts the major mining university in the 2 y metallurgy. The most famous work of Agricola in their uniforms with the classic region the Technisches Institut Bergakademie (the technical was De Re Metallica, which appeared a year crossed hammers (Figure 2). The uni- instit te and mining academy). forms are worn with pride, as they commemorate a centuries-old guild tradition that gifted the miners with rank and famous Mineralogical Museum at the 7 respect. The crossed hammers, known as"Eisen Bergakademie is named after him. und Schagel" originated in the thirteenth cen- Of the hundreds of mines about the region, tury near Kremnica, Bohemia, and are now the one particularly rich mine named the universal symbol of mining throughout eastern Himmelsfirst Mine in St. Michaelis (about 15 Germany and the western Czech Republic. Not kilometers south of Freiberg) yielded an unusu- only can visitors to the region attend these fes- tivities, but they can also roam through scores of mines which in past centuries have delivered silver, gold, nickel, tin, bismuth, tungsten, and copper, and which today are open to the public T + as"museums." One of the famous mining institutes in this region is the Technisches Institut Bergakademie (Mining Academy) in Freiberg, founded in 1765. Freiberg had become the economic and scientific center of the Saxony Erzgebirge region, where silver ore had been discovered in Argyrod it 1168. During the early days of the GRUBE HIMMELSFURST Figure 2. Frequent festivities are held celebrating Bergakademie, chemistry and mining had not the mining tradition. On the hat of this musician yet separated into different disciplines. The best are the famous "crossed hammers" ("Eisen und known mineralogist of this time, Abraham G. Figure3. Argyrodite, AgsGeS6, collected from Schlugel"), the symbol of the miners in the Saxony Werner (1749-1817) of the Bergakademie, was the Himmelsfirst Mine south of Freiberg, and and Bohemia regions. Inset: close-up of pewter a proponent of the Neptunian hypothesis, displayed in the Werner Mineralogical Museum. chalice with "crossed hammers"and the miner's which held that geological structures were laid Argyrodite was the source of the germanium dis- greeting"Gluck aufi" down by water deposition." Indeed, the present covered by Winkler "Grube"translatesas "mine." 20 THE HEXAGON VIP ? ,,,, ,,. l tt i t iiu1 [ItPIORIil I ' I "Al Kt J WMEQ1J~~~ 3Y ,,, iUTt.. AMtt/ 11o'11 V4( 1iUI41 as xw i Figure 5. The last page of a four-page letter from I Mendeleez's 1886 letter to Winkler, where the r famous Russian speculates on exactly what Winkler I s Figure 4. WVinkler's laboratory on 5 Brennhausgasse. has discovered. His conjectures rangefrom -a new This small museum may be visited by appointment element between antimony and bismuth-to "eka- Figure 7. Mn delee ' earlier L'riodic lable, in through the university. silicon." This latter guess turned out to be correct, Russian, on the wall inside Winkler's laboratory. i.e., directly below silicon on the Periodic Table. This This Periodic Table dated from before Mendeleev's letter is written in excellent formal German, and predicted elements. al mineral called "argyrodite" (named from the Mendeleev's signature can easily be discerned at Greek "silver-bearing;" see Figure 3). From this the bottom of the page. mineral Clemens A. Winkler (1838-1904), a Michaelis (Figure 8). In contrast to other mines professor at the Bergakademie, discovered ger- which still exist intact (for example, the Fata manium in 1886. He first performed detailed main Akademie building with a monument to Baii Mine in Romania"'), the Himmelsfurst blowpipe analysis (Note 2) and ascertained the Winkler erected nearby. Mine region is disappointingly barren-the mineral held 75% silver and 18% sulfur, hence The Himmelsfirst Mine can be reached in mine has been closed, the shafts have been a loss of 7%. Searching for the unaccounted one-half hour by driving from Freiberg to St. filled in, the area has been cleaned of talus and material, Winkler fused a sample with sodium carbonate and sulfur, separated the aqueous fil- trate from the black silver sulfide, and added concentrated hydrochloric acid, which threw down a new flaky, white sulfide. He isolated the new element by passing hydrogen over this sul- fide." Argyrodite is now known' by the formula Ag 8GeS 6. Winkler's laboratory still exists in the univer- sity and is one of the very few famous chemical laboratories of the nineteenth century that have not been torn down (Figure 4). This laboratory is a private museum and can be visited by appointment through the Freiberg Tourist Bureau (Freiberg Fremdenverhekrsampt). In one corner of the museum is a letter (Figure 5) from Mendeleev to Winkler (Figure 6), congrat- ulating him on filling a void in Mendeleev's periodic table. In this letter, dated 1886, Mendeleev prematurely predicts that the new element will be inserted between "antimony and bismuth"-but later corrects the identifica- tion of the new element as his predicted "eka- silicon" between silicon and tin. On a wall hangs one of Mendeleev's earlier Periodic Tables, in Russian (Figure 7). Freiberg Institute, proud of its heritage and famous chemists (Note 3) has not only preserved the original Figure6. Dmitri I. Mendeleev and Clemens A. Winkler. This famous pose of Mendeleev, 1834-1907, and laboratory but also built a museum within the Winkler, 1838-1904, (left and right, respectively) was taken in Berlin in 1900. SUMMER 2001 21 debris, and only abandoned, tom-down stone 4. Historically, a typical greeting among city folk ruins may be occasionally found (Figure 9). An was "Glck zu [Sie]," i.e., "Luck to you." The occasional tourist sign marks the site of a previ- country folk (miners) distinguished themselves ous shaft (Figure 10). with a play on words by using "auf" ("on") ^4 Ml' For visitors interested in an active mine, per- a ~ o9d0 Des Yy instead of "zu" ("off"). The expression "Glick haps the most interesting, and certainly the A auf" has stuck ever since, and can be found on (;rschachftes most convenient, is the Himmelfahrt rraescha,tReearyer buildings, signs and documents. The famous Fundegrube Mine which produces silver to this A'uspehV derang aaf ter Er*gang Werner Museum has such a greeting on its 'Verhergen fracher" day on the outskirts of the city. Other important .za Nffmre/s4-findg4,begehae'd stone edifice. sites which may be reached by day trips in a rented automobile include St. Joachimsthal Literature Cited (Jchymov, Czech Republic), whence the J. R. Partington, A History of Chemistry, Vol. 2, Curie's radium ore originated, and pp 115-151, Macmillan & Co., Ltd, London, Johanngeorgenstadt, the source of Klaproth's 1961. uranium ore-but descriptions of these will Figure 10. Historicalpost identifying an old shaft. 2 Ref 1, pp 42-62. have to wait until a future installment of The shafts have long been filled in and little evi- ' Agricola, G. (Latinized from Bauer, G), De re Rediscovery of the Elements. To the interested dence remains except for a few talus piles and metallica, Frobenius, Basel, Switzerland, 1556. tourist who wishes to visit mines and mining stone ruins. 4 Hoover, Herbert, translator of 1556 edition museums, a most informative brochure has of Agricola,G., De re metallica, Dover Publica- been developed by the Tourist Bureau." Visitors Woman's University, Denton, TX, who helped tions, NewYork,1956. to the Erzgebirge are greeted with a friendly the authors with the German translations and ' Heriko, I. I. Mineralogical Record, 1988, "Gluck Auf!"-the historic standard miner etymologies. 19(1), Jan-Feb, pp 7-8. greeting (Note 4)-as they visit mines, muse- Caswell, L. R. The Southwest Retort, 2000, 53, ums, hotels, and restaurants in this very beauti- Notes Dec., pp 5-9. ful and scenic region of the world. 0 ' Weber, W. Mineralogical Record, 1992, 23(3) 1. Saxony is present-day Eastern Germany and May-June, p 255. Bohemia is the Czech Republic. Joachimsthal is Acknowledgments " Weeks, M. E., Discovery of the Elements, the etymological source of"thaler" and "dollar," Gratitude is extended to Dr. Siegfried H. 7th ed., Journal of Chemical Education, 1968, St. Joachimsthal is now known by its Czech Richter of the Technische Universitat pp 655-662.