Chemical Education Today
Letters Some Footnotes on the History of Masurium I was very pleased to read the recent article by R. Zingales (1) about the history of element 43 which in notable parts comprises the twisted story of masurium from the announcement of its discovery (2) to its final acceptance more than seven decades later (3). Nonetheless, I felt that some additional comments might be appropriate. Somewhat unfortunately, J. Newton Friend’s vitriolic remarks about the choice of the name “masurium” were only partly cited in ref 1 and the primary source was not given. Friend’s verdict in fact originates from the year 1941 (4) and thus should to some extent be judged as a result of wartime emotions. Such harsh and inequitable comments clearly became more frequent as an aftermath of World War II, but they should not be considered as commonplace—least of all in earlier years. They cannot be found in preceding comparable reviews (5–8) and were even absent in a contemporaneous one (9). Particularly impressive is the comparison of Friend’s extreme criticism with the subtle reservation at the end of ref 5. It might be noted in passing that the review by Weeks (8) contains a factual error [also committed elsewhere (10)]. The names masurium and rhenium cannot be associated with any territories lost by Germany as a result of World War I. In any case, the diverse attempts to associate the element names masurium and rhenium with World War I events should always be contrasted with the far more prosaic version (1, 11, 12) that these names were chosen according to the respective regions where Walter Noddack’s and Ida Tacke’s families originated from. That rhenium had been named for her home region at the Lower Rhine was, incidentally, already pointed out by Ida Noddack-Tacke herself (13). A minor error in ref 1 concerning these matters should also be corrected. Walter Noddack indeed was of East Prussian ancestry, but his birthplace was Berlin (14). Another comment regards the anecdote about the Noddacks’ use of the symbol “Ma” for masurium on a wall chart of the periodic system. As it may not be completely obvious from ref 1, it seems advisable to point out that the symbol “Ma” was quite firmly established in the chemical literature of the 1940s. To give some arbitrarily chosen examples from English-speaking countries, see ref 9, 15, 16, or the 1941 periodic chart reproduced in ref 17. F. A. Paneth strongly dissented from this widespread practice and held the Noddacks’ adherence to their results responsible for it. It was this context in which he introduced the above-mentioned anecdote (18). It is also apparent from ref 18 that personal animosities may have played a certain role. A final remark is concerned with the Noddacks’ political standpoint. While it is surely legitimate to characterize it
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as a decidedly national one, the straightforward allegation of positive attitudes toward National Socialism should be regarded as a matter of dispute. It was, in particular, forcefully rebutted by H.-J. Eichhoff, who had worked together with the Noddacks from 1936 (11). As is so often the case, the truth most probably lies somewhere in-between these antagonistic positions. Some additional material about this controversial issue can be found in ref 12. Literature Cited 1. Zingales, R. J. Chem. Educ. 2005, 82, 221–227. 2. Noddack, W.; Tacke, I.; Berg, O. Naturwiss. 1925, 13, 567– 574; Sitzungsber. Preuß. Akad. Wiss. Phys.-Math. Kl. 1925, 400–409. 3. de Laeter, J. R.; Böhlke, J. K.; De Bièvre, P.; Hidaka, H.; Peiser, H. S.; Rosman, K. J. R.; Taylor, P. D. P. Pure Appl. Chem. 2003, 75, 683–800; p 763. 4. Friend, J. N. Chem. Ind. 1941, 691–695. 5. Nature 1925, 116, 54–55. 6. Bligh, N. M. Sci. Progress 1926, 21, 109–114. 7. Druce, J. G. F. Sci. Progress 1933, 27, 687–689. 8. Weeks, M. E. J. Chem. Educ. 1933, 10, 161–170. 9. Druce, J. G. F. Chem. Ind. 1941, 729–730. 10. Smith, D. D. J. Chem. Educ. 1978, 55, 49. This note is extremely error-ridden. The word “masurium” is misspelled throughout and element 75 (rhenium) is completely confused with element 72 (hafnium). 11. Van Assche, P. Nuclear Europe 1988, Issue 6–7, 24–25. 12. Sime, R. L. Lise Meitner: A Life in Physics; University of California Press: Berkeley, Los Angeles, 1996; p 465 (see also p 273). Particularly noteworthy is the quotation of E. Segrè’s grotesquely exaggerated version of J. N. Friend’s criticism. 13. Noddack-Tacke, I. In Sto let periodicheskogo zakona khimicheskikh elementov; Izdatelstvo “Nauka”: Moscow, 1969; pp 99–102. 14. Engel, M. In Neue Deutsche Biographie, Vol. 19; Duncker & Humblot: Berlin, 1999; pp 307–308. 15. Moelwyn-Hughes, E. A. Physical Chemistry; University Press: Cambridge, 1947; p 230. 16. Glasstone, S. Textbook of Physical Chemistry, 2nd ed. (British reissue); Macmillan: London, 1948; p 89. 17. Trimble, R. F. J. Chem. Educ. 1975, 52, 585. 18. Paneth, F. A. Nature 1947, 159, 8–10. H. J. Wagner Theoretische Physik Universität Paderborn Pohlweg 55 33098 Paderborn, Germany
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Chemical Education Today
Letters More on Element 43 In his masterly account of the search for Element 43, “From Masurium to Trinacrium: The Troubled Story of Element 43” (1), Roberto Zingales has detailed in historical context the quest for the long-sought eka-manganese, whose existence had been predicted by Dmitrii Ivanovich Mendeleev as early as 1872. When I was a graduate student at the University of Florida more than half a century ago, one of the unsubstantiated claims for the discovery of this elusive element involved local professor of chemistry Fred Harvey Heath (1883–1952) (2, 3), who had died shortly after I arrived on the Gainesville campus. While at the University of Washington, sometime between 1917 and 1923, Heath and electric engineer J. D. Ross claimed to have prepared compounds of a hitherto unknown element from ores that they had obtained from British Columbia (4, 5). They submitted their results to the Journal of the American Chemical Society, whose editor, Arthur Becket Lamb (1880– 1952) (6), requested X-ray spectra as proof of their discovery. Because at that time the necessary equipment was unavailable to them, their report was not published. Since technetium occurs in only infinitesimal amounts in nature (7) and since Heath and Ross had isolated salts in weighable quantities, it is extremely improbable that the element that they had reported was technetium (element 43). However, it might have been rhenium (element 75), in which case they would still have antedated Noddack, Tacke, and Berg’s discovery (8). On the other hand, because the chemical literature contains many unsubstantiated claims to the discovery of element 43, as Professor Zingales has noted (1), their “substance” might have been a mixture. At any rate, their claim constitutes an interesting and little known footnote in the annals of the history of chemistry. Literature Cited 1. Zingales, R. J. Chem. Educ. 2005, 82, 221–227. 2. Kauffman, G. B. In American Chemists and Chemical Engineers; Miles, W. D., Ed.; American Chemical Society: Washington, DC, 1976; pp 207–208. 3. Kauffman, G. B. In American National Biography; Garraty, J. A., Carnes, M. C., Eds.; Oxford University Press: New York, NY, 1999; Vol. 10, pp 471–472. 4. Kauffman, G. B. Florida Acad. Sci. Quart. J. March 1963, 26 (1), 1–3. 5. Kauffman, G. B. Educ. Chem. July 1993, 30 (4), 94. 6. Kauffman, G. B. Hexagon Spring 2001, 92 (1), 3. 7. Kenna, B. T.; Kuroda, P. K. J. Inorg. Nucl. Chem. 1961, 23, 142. 8. Noddack, W.; Tacke, I.; Berg, O. Naturwiss. 1925, 13, 567.
An Improved Preparation of 2,4-Dinitrophenylhydrazine Reagent In the analysis of aldehydes and ketones (both for characterizing the functional group and identifying such compounds by the melting points of their derivatives), 2,4dinitrophenylhydrazine reagent is often used. Of the several formulations of this reagent, the most popular uses sulfuric acid. The method involves making a paste of 2,4-dinitrophenylhydrazine in concentrated sulfuric acid, dispersion of the paste in ethanol, addition of water, and the filtration of the reagent (1). This improvement uses milder conditions, which may obviate the need for the final filtration. Those responsible for preparation of stock reagent solutions for classes should note that this method facilitates scaling up the preparation. To a clean, dry 125-mL Erlenmeyer flask and magnetic stir bar, add 3 grams of 2,4-dintrophenylhydrazine, 20 mL of water and 70 mL of 95% ethanol. Place the flask in an ice bath in a beaker. Stir and allow the mixture to cool. When the temperature reaches 10 °C, with continued rapid stirring, begin the slow addition of 15 mL concentrated sulfuric acid, trying to avoid boiling. If the temperature goes above 20 °C, stop addition until the temperature goes back to 10 °C. When the sulfuric acid has been added, turn off the stirrer, remove the ice-bath and place the flask on a stirrer-hotplate. Stir and warm the flask until the 2,4-dintrophenylhydrazine stops dissolving or the temperature reaches 60 °C, whichever comes first, then continue stirring without heating. When the solution has cooled, filter through a fritted funnel, if necessary. Hazards 2,4-Dinitrophenylhydrazine [119-26-6] is a flammable solid, which must be kept moist and is harmful if swallowed, inhaled, or absorbed through the skin. Concentrated sulfuric acid [7664-93-9] is poisonous and corrosive. Its mist can cause severe burns to all body tissue. It may be fatal if swallowed or by skin contact. It is harmful if inhaled and may cause cancer. Ethanol [64-17-5] is flammable and should be kept from ignition sources. Eye and face protection, protective clothing, and gloves must be worn. Literature Cited 1. Linstromberg, W. W.; Baumgarten, H. E. Organic Experiments, 6th ed.; Houghton Mifflin: Boston, 2002; p 175. Shriner, R. L.; Hermann, C. K. F.; Morrill, T. C.; Curtin, D. Y.; Fuson, R. C. The Systematic Identification of Organic Compounds, 8th ed.; Wiley; Hoboken, NJ, 2004; pp 278–279.
George B. Kauffman
Ben Ruekberg* and Eric Rossoni
Department of Chemistry California State University, Fresno Fresno, CA 93740-8034
[email protected] University of Rhode Island Chemistry Department Kingston, RI 02881 *
[email protected] 1310
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