Rediscovery of the Elements and

Sc Ti V Cr Mn Fe Co Ni Cu Zn (21) (22) (23) (24) (25) (26) (27) (28) (29) (30) Y Zr Nb Mo eka-Mn Ru Rh Pd Ag Cd (39) (40) (41) (42) (43) (44) (45) (46) (47) (48)

La Hf Ta W dvi-Mn Os Ir Pt Au Hg (57) (72) (73) (74) (75) (76) (77) (78) (79) (80)

Iigun' 1. Thb transition uctals of the Periodic ble had all /et'ni disuen'u'd /'iy /923 exapt fur the 'ka- manganeses (also known as "eka-"and"dvi-"Mn, "1 "and "2" in Sanskrit). Noddack and Tacke reasoned that these two elements might be found in platinum ores (where the shaded blue elements may be found as James L. Marshall, Beta Eta 1971, and impurities) and/or columbite (Fe,Mn)(Nb,Ta)206 (red shaded elements)." Their research showed that Virginia R, Marshall, Beta Eta 2003, element 75 (rheniuim) is actually most commonly associated with molybdenum in nature (see double headed arrow), correspondingto the "diagonal behavior"=,' occasionally obser-ud in the Periodic Table. Department of Chemistry, University of North Texas, Denton, TX 76203-5070, [email protected] Figum'e 2. Ida Tacke and Walter Noddack in their laboratory at the Physikalisch-Techische Reichsanstalt After the 1923 discovery of hafnium," only (PTR) in Berlin-Charlottenburg, two transition group elements were yet to be established in 1887, where rhenium discovered. These predicted elements (43 and t ~ was separated and characterized. 75) were homologues of manganese, the pre- Noddack is posing with his ever-pre- dicted "eka-manganeses" of Mendeleev" sent cigar and is wearing his stained (Figure 1). However, all attempts to find them laboratorycoat proving that indeed in crude manganese preparations ended in fail- he was a dedicated bench-chemist. ure. The problem of the missing elements was Photo, courtesy, Wesel Archives, addressed in a comprehensive research project Germany. by the husband-wife team of Walter Karl Friedrich Noddack (1893-1960) and Ida Eva Noddack-Tacke (1896-1978) (Figure 2). The "work-unit" of Noddack and Tacke." Ida Tacke was born in Lackhausen (a suburb Curie - some German journalists have called Walter Noddack was born in Berlin and educat- of Wesel), a town on the Rhine River 85 kilo- her "die deutsche Marie Curie."' The story is ed at that city's Friedrichs-Werdersche meters north of K/ln (Cologne). She was the told that when Walter passed away in 1960, it Oberrealschule. This was the same prestigious daughter of AdelbergTacke, the owner of a var- was because of an emotional heartbreak when institution where Friedrich Wbhler in 1828 dis- nish factory. Ida was educated at the Berlin he heard (incorrectly) that his wife, unreachable proved the theory of "vital force" in organic Hochschule, earning her doctorate in engineer- by telephone, had died during an illness in compounds by isomerizing ammonium iso- ing (Doktor-ingenieur) in 1921.' She special- Hamburg. cyanate into urea." Noddack then matriculated ized in organic chemistry, thinking that she at the University of Berlin and obtained his could improve the curing behavior of linseed oil The search for the missing elements. doctorate in 1920. His advisor was Walther in her father's business. After her graduation, Noddack and Tacke observed that odd-atomic Nernst (1864-1941; Nobel laureate in chem- however, she met Walter and was smitten by his number elements were less abundant than istry, 1920), who formulated the third law of quest for new elements. She joined the even-atomic number elements." Thus they real- thermodynamics. When Nernst left to accept Physikalisch-Technische Reichsanstalt in 1922 ized that the eka-manganeses might be partic- the presidency of the Physikalisch-Technische and they married four years later. The two ularly rare, and that a very meticulous and Reichsanstalt (Figure 3) in 1920, Noddack researchers formed, as she called it, the methodical search might be necessary to dis- moved with him. Three years later, Noddack Arbeitsgemeinschaft (work-unit)' that held them cover them. The team reasoned that since the became the new head of the Anstalt. It was here together through mutual research and love in a eka-manganeses had not been found in nature that he met Ida Tacke. manner reminiscent of Pierre and Marie with the parent element 25, they should search

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Figur 4. One of the more prolific sources of rhenium-bearing molybdenite is Knaben, Vest- Agder, Norway, where a historic mine is located (N58 39.55 E07 04.41). This mine provided strategic molybdenum used in steel armamentfor the WWII Nazi effort and was bombed twice by the allies in 1943. Note the snow in the foreground despite the summer date (June 30).

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,ip ABOVE: Figure 3. The chemistry building (Chemie Gebdude) of the PTR is now used for administrationpurposes. The name of the PTR was changed to the Physikalisch-Technische Bundesanstalt (Physics-TechnicalFederal Institute) in 1945. Presently, among other responsibilities, the Bundesanstalt is ~r~4 accountable 7 for atomic clock standards in Germany. Inset: The Waffen (icon) as it appears at the entrance of the Anstalt, Abbestrafe (2-12, N52 30.98 E13 19.26), Charlottenburg,West Berlin. -~. : RIGHT: Figure 5. The talus scattered about at Knaben, Norway- 900-million-year-oldPrecambrian granitic gneiss - is profuse with molybdenite that looks like splashes of solder. The molybdenite is rich in rhenium, with concentrations as high as 7.5 ppm. Vr Historically, molybdenite, native lead, and graphite were all con- t4 fused with one another; Scheele distinguished the three in 1779. &I Y 2 Molybdenum is named after the Greek word for lead (molybdos). I in platinum and columbite ores, in which many ic number, they identified lines from elements confirmed element 75 (rhenium)." Rhenium low-concentration elements had already been 43 and 75. They claimed the discovery of two was the last naturally-occurring element to be observed (Figure 1). Ida took a full year's sab- new elements,6 which they named masurimn discovered (Note 1). batical to conduct a thorough literature search (Ma) and rhenium (Re), respectively (after Unfortunately, the Noddacks could not to develop a complete repertoire of chemical regions in Prussia and the Rhineland). So far reproduce the results for element 43 (masuri- separation procedures to help them in their they could not obtain either element in weigh- um). Unknown to them, element 43 has no sta- quest. able quantities. ble isotopes, and its discovery had to await Working with a variety of platinum and After their marriage, Noddack and Tacke nuclear synthetic procedures (vide infra). columbite samples, in 1925 they obtained a traveled to Scandinavia to find richer sources of In 1935, the Noddacks moved from Berlin to white sublimate (Re207). Collaborating with rhenium; they procured ore samples from 124 Freiburg, then in 1941 to Strassburg after Otto Berg (1873-1939) of Siemens & mines in Sweden and Norway. An analysis of Germany annexed the region (Strassbourg in Halske"- whose laboratories were conve- these indicated relatively large amounts of rhe- French), and finally the University of Bamberg niently located only 400 meters north - Tacke nium in molybdenite (MoS,) in several of the in 1946, where he founded the Staatliches recorded the X-ray spectra of their prepara- Norwegian sites' (Figures 4, 5). In two years Forschungsinstitut fir Geochemie (State tions. Based on the work of Moseley"' which they were able to isolate 1 gram of rhenium Research Institute for Geochemistry) (Note 2). predicted the X-ray frequencies based on atom- from 660 kg of molybdenite, whose X-ray lines As an outgrowth of their search for the eka-

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Figurcte 6.bill Rad atintihaioi1 atlh mc (yi California-Berkeley housed the 27-inch cyclotron invented by Figure 6. This bronze bust of Ida Noddack-Tkc Lawrence (later modified to a 37-inch instrument). This laboratory stands in her hometown of Wesel on Ida- was put into operation in 1931, refurbished the Civil Engineering 0 from Noddack-Stra e (N51 40.70 E06 37.96). Testing Laboratory, built in 1885 (N37 52.40 W122" 15.37). The This two-meter monument, erected in 2006, was building was demolished in 1959 and replaced by Latimer Hall. constructed by Andreas Krdmimic'r F-r oteir Segr was co-discoverer of technetium (1937) and sr Natrsc2 aid -a). Figure 7. Emilio later at Berkeley was co-discoverer of the antiproton in 1955 with P Owen Chamberlain (1920-2006), with whom he shared the Nobel manganeses, Ida and Walter Noddack originat- Prize in Physics in 1958. Segrb moved permanently to the United r ed the concept of "elemental abundances" in States in 1938, followed the next year by his wife Elfriede nke Spiro. the earth's crust ("Die Hdufigkeit der chemis- Segr played a critical role in the Manhattan project, solving problems chen Elementen")' and produced estimates for involving plutonium in atomic bonbs. the occurrence of all known elements. Walter retired in 1956. The Noddacks were nominated several (1879-1968) of Ida's suggestions regarding and "masurium."" Unbeknownst to chemical times for the Nobel Prize, but unlike the Curies nuclear fission, Hahn would abruptly dismiss explorers, this element did not exist in the were not successful. It is suggested that the the idea with "Ein Fehler reicht" ("One mistake earth's crust in appreciable quantities.The most 98 inability to verify masurium contributed to their is enough"!),"" referring to the Noddacks' stable isotope of element 43 is 43Tc with a failure to win this prize." It is ironic that Enrico masurium research. It is sobering to reflect on half-life of 4.2 x 106 years - and any primor- Fermi (1901-1954) was awarded the 1938 the possible outcome of Germany's WWII cam- dial element 43 should be long gone since the Nobel Prize in Physics for "new radioactive ele- paign if Hahn, winner of the 1944 Nobel Prize creation of the earth 4.6 x 109 years ago. Hence, ments"" as Ida Noddack-Tacke (Figure 6) was in Chemistry for"his discovery of the fission of the discovery of technetium was not possible correctly challenging the Italian scientist's con- heavy nuclei"'5 at the Kaiser Wilhelm Institut, until the advent of the artificially produced ele- clusions. Refusing to accept the general con- had not ignored Tacke's early suggestions. It ments. sensus that neutron bombardment of uranium was 30 years later, during a radio broadcast in While the Noddacks were isolating their first was creating transuranium elements in Fermi's 1966, Hahn finally admitted, ".. . und die Ida gram of rhenium, Emilio Gino Segre laboratory, she suggested smaller atomic frag- hatte doch Recht." ("... and Ida was right after (1905-1989) was beginning his studies with ments would be created and one should first all"!)4' Fermi at the University of Rome. Segre (Figure check the product mixture for all known ele- 7) was born in Tivoli, 26 km east of Rome. After ments.'" In her article "Ober das Element 93," The discovery of element 43 - tech- a short stint in the military, Segre became pro- she actually proposed the concept of nuclear netium." Many historic claims for "the ele- fessor of physics at the University of Rome fission'' five years before the dramatic ment between molybdenum and ruthenium" (1932), where he joined the "Via Panispema announcement of Hahn, Strassman, Meitner, have been proposed, including "polinium," boys," a group of scientists under the guidance and Fritsch." During the period 1935-1938, "ilmenium," "pelopium," "davyum," "lucium," of Fermi who were pioneering the field of whenever Walter would remind Otto Hahn "nipponium," "neomolybdenum,""moselium," nuclear reactions involving slow neutrons. In

86 THE HEXAGON/WINTER 2013 V Ii,U ABOVE: Figure 10. The magnet used for the 27-inch cyclotron (opera- tional 1932), then modified to the 37-inch cyclotron (operationalfive years later), is now standing outside the Lawrence Hall of Science. The Figure 9. Ernest Orlando Lawrence (1901-1958; Nobel Prize in Physics in 1939) magnet, originally built for power communication between the U.S. and invented the cyclotron in 1931, and improved its design and size through the coming Europe in World War I, was acquired by Lawrence as war surplus. years. A museum devoted to him-the Lawrence Hall of Science-is the best place to be introduced to the extraordinary history of nuclear chemistry at Berkeley. This BELOW: Figure 11. On Via Archirafi 36, Palermo, Sicily, Italy, is the old museum is on Centennial Drive in the Berkeley Hills (N37 52.77 W122 14.80) Experimental Physics Building (N38 06.61 E13 22.39), where tech- overlooking the University of California at Berkeley. The museum was establishedin netium was discovered. The first two floors housed physics, and the top 1982 by Glenn Theodore Seaborg (1912-1999; Nobel Prize in Chemistry 1951; AX-' floor housed mineralogy. The building is now used for library resources, - Beta Gamma '35, John R. Kuebler Award, 1978). storage, and the Mineralogy Department. (The modern science buildings are at the new campus on Viale Delle Scienze, 2.2 kni to the west.)

1936, Segre became professor and director of the Department of Physics at the University of Palermo. During a visit to Berkeley in 1936, he became curious about the possibilities of trans- mutations occurring in the cyclotron (Figure 8) invented by E. O. Lawrence (Figure 9). He returned to Palermo with scrap metal pieces which had been radiated from which he isolat- ed several radioactive elements, including sul- -iXE _ fur-32. In February 1937 in Palermo, he received from Berkeley a radioactive strip of molybde- num foil used as a deflector plate in the 37-inch E . - - } cyclotron (Figure 10). Since the molybdenum had been bombarded with deuterons (1H), Segre "suspected at once that it might contain element 43," next to molybdenum in the ~~7 Periodic Table. Segre needed chemical expertise, and he was fortunate that his university building (Figure 11) housed the institutes of both physics and mineralogy. The head of mineralo- gy was Carlo Perrier (1886-1948) (Figure 12), an Italian mineralogist well versed in the classical ammonia to remove the surface impurities, were individually isolated, but none showed analytical procedures in chemistry. In their sep- where the nuclear reactions would have radioactivity. To the remaining radioactive aration procedures, Segre and Perrier followed occurred. Because of the anticipated small solution they added a rhenium (75) carrier 18 the radioactive material in their separations amounts of product (less than 10-10 gram, ) to which was precipitated by H2 S. This radioactive using the manner pioneered by the Curies the extracted solution, they added various carri- rhenium (sulfide) carrier was converted to the when they first separated polonium and radi- ers - zirconium (at. no. 40), niobium (41), oxide with hydrogen peroxide and distilled to um." First, they reacted the Mo foil with boiling molybdenum (42), and manganese (25). These remove the volatile rhenium oxide, which

WINTER 2013/THE HEXAGON 87 LEFT: Figure 12. Carlo Perrier; head of the Mineralogy Institute, worked out the chemistry of technetium"-' which allowed its isolation. Despite the impor- tance of his work which allowed the dis- covery of the first artificially produced element , Perrier never received the Nobel Prize. RIGHT: Figure 13. Prof Arturo Russo, of the Dipartimento di Fisica e Tecnologie Relative, Universith di Palermo, was the host of the authors during their visit to Palenno. Dr. Russo is interested in the science history of his university. From forgotten storage items he has found the - old equipment used by Emilio Segr'. Russo is holding the ionization chamber constructed bi Segri'.

exhibited no radioactivity. The remaining pute as to whether or not the Noddacks ever radioactive solution was concluded to contain could have detected element 43 in their prepa- element 43 -but without weighable amounts rations. The short half-life of technetium pre- isolated and without an X-ray spectrum'" cludes its presence on earth except in radioac- (Figure 13). tive ores where secondary processes have Segre promptly visited the Noddacks, now occurred since the creation of the earth.,' A in Freiburg (September 1937). Segre, who subsequent careful analysis has shown that the the Russian muraled Periodic Table, while "Il" spoke excellent German, wished to give credit low concentration of uranium in the remains. One might suspect political reasons where it was due. He wanted to establish Noddacks' material would not have produced are responsible for this removal of "Ma," since unequivocally whether he had simply con- detectable amounts of technetium by their X- the Battle of the Masurian Lakes in World War I firmed the existence of "masurium,"or whether ray analysis." was a victory for Germany over Russia. Some he was actually the first to observe element 43." The struggle for priority of the discovery of believed the Noddacks chose the name for According to Segre's account' Walter was non- the elements has often been contentious. In a nationalistic reasons, despite the Noddacks' committal and could not produce the X-ray 1947 editorial by Friedrich Adolph Paneth insistence it was done in recognition of his plates of masurium, which he said "had acci- (1887-1958) in Nature, this "speaker of father's homeland (East Poland, then dentally been broken." Obtaining no definitive authority"" wryly noted, "... the slowness of Prussia)."' information, Segre concluded that at the very chemists in taking the obvious action of aban- In defiance of the general rejection of least, the Noddacks had "no clear-cut results" doning suggested names is due to the failure of masurium by the scientific community, a plaque and that if their claims were indeed lacking, the claimants to withdraw their statements, on Ida's old homestead in Wesel (Note 3) bold- they would probably "fall of their own although during years of intensive effort they ly proclaims [translated] "... This worldwide weight."" Two weeks later, the Noddacks and had been unable to substantiate them. In the famous woman chemist discovered and colleagues, outfitted in uniforms with case of masurium, W. Noddack even went so far described in 1925, together with her husband, swastikas,"' appeared at Segre's laboratory in ... as to complain to the convener of a chemical rhenium and masurium (today known as tech- Palermo; Segre showed them his results and meeting in Kinigsberg for not having invited netium ... )." Q they left without comment. No more personal him to speak on this element, as ... he would contact occurred between Segre and the have been in a position to disclose the whole Acknowledgements. Noddacks. chemistry of masurium ... but no communica- The authors are indebted to Dr. Hans Subsequent work with the cyclotron at tion has ever appeared on this work. ""' Georg Tilgner of Wesel, Germany, local expert Berkeley allowed material to be produced Despite the lack of further proof of masuri- on the Noddacks and author' of Forschen, whose X-ray spectrum confirmed element 43. um, the most"up-to-date" Periodic Table in the Suche und Sucht [Research, Quest, and By the early 1940s, it was generally agreed that late 1920s and early 1930s was the Antropoff 2 Obsession], for his generous help of informa- element 43 is"missing from our earth" " (tech- Periodic Table (highlighted in the previous issue tion and photographs regarding the discovery netium has since been detected in the spectra of of The HEXAGON") which proudly proclaimed of rhenium, particularly that dealing with the stars') and in five years a protocol was suggest- "Ma" as element 43. The "largest Periodic Table hometown heroine Ida Tacke. ed for the naming of artificial elements. 2" In in the world,"constructed in 1935 on the wall of 1947, a publication appeared in Nature dubbing the Metrology Institute in St. Petersburg," Notes. the first artificial element, atomic number 43, as included not only masurium (43) but also illini- technetiumn. 2 um (61), both spurious elements which at that NOTE 1. A claim was made in 1908 for a new element nipponiunF found in thorianite (ThO,) Could the Noddacks have observed tech- time were erroneously "firmly rooted in text- 2 by a Japanese chemist, Masataka Ogawa netium? Ever since Perrier and Segre's books and tables." "' It is interesting to note (1865-1930), in the research group of Sir announcement in 1947, there has been a dis- that the original tiled "Ma"has been scraped off

88 THE HEXAGON/WINTER 2013 William Ramsay (1852-1916, Nobel laureate in 10. M. F. Rayner-Canham and G. W. Rayner- 20. F. A. Paneth, Nature, (a) 1942, 149, 565-568; Chemistry, discoverer of the noble gases.") Canham, ed., A Devotion to their Science. (b) 1947, 159, 8-10. Ogawa placed the element between molybde- Pioneer Women of Radioactivity, 1997, 21. B. T. Kenna, J. Chem. Ed., 1962, 39(9), num and ruthenium in the Periodic Table, i.e., "Ida Tacke Noddack,"F. Habashi, 217-225, 436-442. element 43, or present-day technetium. Upon Chemical Heritage Foundation, and E. Segre, 1947, 159, returning to Japan, Ogawa isolated what he Philadelphia. 22. C. Perrier Nature, 24. This article, dealing with the naming of thought to be the same element from Japanese 11. http://www.nobelprize.org/nobel-prizes/ is immediately followed by molybdenite. H. KenjiYoshihara (1929-)" long technetium, ph ysics/laureates/1938/ the announcement of element 85 astatine, after Noddacks'work, suggested that Ogawa in produced by treating bismuth with alpha fact had rhenium,'" ,= which probably was true 12. (a) I. Noddack, Angewandte Chemie, 1934, with the new 60-inch cyclotron based on an analysis of the Noddacks' world- 47, 653-656. (b) An excellent review of particles (D. R. Corson, K. R. Mackenzie, and E. wide analyses' which showed Japanese molyb- "the detours leading to the discovery of denite to be the richest they ever studied (9.8 nuclear fission"is laid out in K. Starke, Segre, idein). ppm Re). J. Chem. Ed., 1979, 56(12), 771-775. 23. A. M. Hayashi, Scientific American, 2000, 13. Hahn 282(2), 18. NOTE 2. A plaque devoted to Walter Noddack O. and F. Strassman, Natunissenschaften, 1939, 27(1), 11-15; resides at Kinstlerhaus, Villa Concordia, 24. (a) F. Habashi, J. Chem. Ed., 2006, 83(2), Concordiastrage 28, Bamberg (N49 53.28 E10 L. Meitner and O. R. Frisch, Nature, 1939, 213; (b) R. Zingales, letter, iden. 143(3615), 239-240. 53.31), in honor of his accomplishments in geo- 25. H. K.Yoshihara, Spectrochimica Acta, Part B, chemistry. 14. R. L. Sime, Lise Meitner A Life in Physics, 2004, 59, 1305-1310; Proc. Jpn. Acad., Ser. B, 1997, U. of California Press (a) 271-273; NOTE 3. The old Tacke home in Wesel ("Haus 2008, 84, 232-245. (b) 464. Wohlgemuth") is located at Bruner Landstrage 26. For a full discussion of nipponium, see http://www.nobelprize.org/nobel-prizes/ 301 (N51 41.04 E06 39.12), beside the Bruner 15. M. Fontani, M. Costa, and M.V. Orna, Lackhauser Farben (paint store), on the site of chemistry/laureates/1944/hahn-bio.html The Lost Elements: Errors, Retractions, and the original varnish factory established in 1867. 16. R. Zingales, J. Chem. Ed., 2005. 82(2), Dead Ends in the Creation of the Periodic A plaque was erected in 2006, which describes 221-227. This is arguably the best article Table, 2014, (in press). her major accomplishments, notably the dis- technetium, and is the on the discovery of 27. E. Scerri, A Tale of 7 Elements, 2013, Oxford, covery of rhenium and masurium, and her 1934 source for most of the information herein. 109-114. idea of the splitting of the uranium atom by 17. E. Segre: A Mind Always in Motion. neutron bombardment. 28. E. Scerri, The Periodic Table. Its Story and its The Autobiography of Emilio Segr,1993, Significance, 2007, Oxford, "Diagonal U. of California Press, 112-117. References. Behavior" 265-267. 18. E. Segre, Nature, 1939, 143, 460-461. 1. J. L. Marshall and V. R. Marshall, 29. C. Perrier and E. Segre, Rend. Lincei, The HEXAGON of Alpha Chi Sigma, (a) 2004, 19. C. Perrier and E. Segre, J. Chem. Phys., 6th ser., 1937, 25, 723-730; 27, 579-581. 95(3), 46-50; (b) 2005, 96(1), 8-13; (c) 2007, 1937, 5, 712-716; 1939, 7, 155-156. 98(2), 23-29; (d) 2010, 101(1), 6-11; (e) 2010, 101(3), 42-47; (f) 2011, 102(3), 36-41; (g) 2012, 103(3), 36-41; (h) 2013, 104(3), 46-51; (i) 2013, 104(3), 65-66, 69. 2. L. C. Hurd, .Chem. Ed.,1933, 1010), 605-608. 3. A. Lykknes, D. L. Opitz, B.Van Tiggelen, ed., For Better or For Worse? Collaborative Couples in the Sciences, 2012, Birkhsuser, 103-123. 4. H. G.Tilgner, Forschen, Suche nd Sucht, 1999, Libri Books; (a) p 216. 5. Schubert, Fritz, Die"deutsche Marie Curie"; Rheinischen Post, Beruhmte Niederrheiner, 36. Jg., Dusseldorf, 15. August 2009, S. B 6. 6. W. Noddack, I. Tacke, and O. Berg, Naturwissenschaften,1925, 13 (26), 567-574; [English summary] Nature, 1925, 116, 54-55.

7. I. and W. Noddack, Das Rhenium, 1933, Leopold Voss, Leipzig. 8. I. and W. Noddack, Z. anor . algein. Chem., 1929, 183, 353-375. 9. I. and W. Noddack, Die Naturwissenschaftcm, 1930,18,757-764.

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