As regards history, rhenium had an undoubted advantage over hafnium: nobody had ever questioned the fact that element No. 75 had to be an analogue of manganese, or tri-manganese in Mendeleev’s terminology. However, in all other respects there was no certainty.
Let us perform an experiment. If we select at random a few monographs and textbooks where rhenium is discussed we shall see that the authors agree on some things while sharply disagreeing on others. They all agree that rhenium was discovered in 1925 but when it comes to the source from which rhenium was extracted, they disagree. Among minerals mentioned as sources of rhenium are columbite and platinum ore, native platinum and tantalite, niobite and wolframite, alvite and gadolinite. Even an experienced geochemist will be at a difficulty finding his way among so varied a group of minerals.
After these introductory remarks, we may name the discoverers of rhenium: V. Noddack, I. Takke (who later married V. Noddack), and the spectroscopist O. Berg. Their authorship was never contested by anybody. This may be the only case when engineers became interested in the yet undiscovered element. They were aware of the uses of the periodic system. Since tungsten was widely used in electrical engineering, there was every reason to believe that element No. 75 would possess properties even more valuable for this industry. It is highly probable that the first attempts of the Noddacks to find this element were prompted by practical needs.
In 1922, after thorough preparations they set to work. First of all, they collected all reports on the discovery of manganese analogues. Since these discoveries remained unconfirmed, it was tempting to check them. The scientists drew up an extensive program of research: they were going to look for two elements at once since unknown manganese analogues included not only element No. 75 but also its lighter predecessor–element No. 43 with an unusual fate (see p. 200). The periodic table made it possible to predict many of their properties. We can now compare the Noddacks’ predictions on rhenium with the actual properties of the element.
Prediction Modern data
Atomic mass 187-188 186.2
Density 21 20.5
Melting point 3300 K 3 323 K
The higher oxide formula X2O7 Re2O7
Melting point of the higher
Oxide 400-500oC 220oC
The agreement is, indeed, excellent. Only the melting pint of the oxide proved to be much lower that
the expected one whereas on the whole Mendeleev’s classical method of prediction was fully confirmed. In other words the Noddacks had a perfectly good idea about what element No. 75 (and element No. 43) was going to be. Thus, the history of rhenium was closely related to the history of its light analogue.
But where to search for these element? Predicting the geochemical behavior of rhenium the Noddacks used to the full the capacity of theoretical geochemistry of that time; They even knew that it had to be a very rare element. They could not know, however, that it was a trace element and that, therefore, what seemed unquestionable to them was in effect open to doubt.
The scientists planned to investigate two groups of minerals: platinum ores and so called columbites (tantalites). Four years (from 1921–1925) were spent in searching for the wanted elements but in vain. Then a communication appeared about the discovery of hafnium whose existence in nature was proved by X-ray spectroscopy. Undoubtedly, this event gave the Noddacks the idea to use the same method in order to prove the existence of manganese analogues and they turned for help to O. Berg, a specialist in X-ray spectroscopy.
In June 1925, V. Noddacks, I. Takke, and O. Berg published an article about the discovery of two missing elements, Masurium (No. 43) and rhenium (No. 75). They were found in columbite and in the Uralian platinum and named after two German provinces. The elements X-ray spectra provided the main confirmation of their existence; but there was no question of extracting the elements and the reasoning of the German scientists was, in general, too involved. However, the article attracted attention and other scientists tried to reproduce the results.
However, no such reproduction followed. A year passed and the Soviet scientist O. E. Zvyagintsev and his colleagues proved irrefutably that the Uralian platinum ore contained no new elements. After that the German scientists continued to study columbites which varied considerably in composition but, according to the predictions, had to contain mysterious manganese analogues. They subjective the minerals to complex chemical treatment in order to concentrate the unknown elements and performed X-ray spectral analysis. The data obtained were reassuring but definite conclusions would have been premature: the scientists could not obtain any noticeable amounts of elements No. 43 and No. 75 and experimentally determine their properties.
Nobody could reproduce the results obtained by the Noddacks. Their compatriot W. Prandtl even sent his assistant. A Grimm to the Noddacks’ laboratory to watch them prepare manganese analogues Back home, A. Grimm reproduced the entire procedure, perfected it and…, we do not know the extent of his distress about the wasted time. The English scientists F. Loring and the Czechs Ya. Geirovskii and Y. Druce also doubted the Noddacks’ results. Later, Loring, Geirovskii, and druce claimed the priority of discovering element No. 75 by other methods and from other sources. History has retained their names but not as discoverers of rhenium.
The two German scientists believed to have also isolated element No. 43 (known later as technetium). Now we know that they by no means could detect the presence of technetium at the time but, nevertheless, the Noddacks were more sure of its discovery than of the discovery of rhenium (the fact which is hardly a feather in their cap). As time passed, the Noddacks became convinced that the range of the minerals for analysis had to be considerably enlarged. The previous geochemical prediction did not, apparently, come true. In the summer of 1926 and in 1927 the Noddacks went to Norway to collect minerals among which were: tantalite, gadolinite, alvite, fergusonite, and molybdenite. In the early 1928 the scientists, analysing the minerals, isolated about 120 mg of rhenium mainly from molybdenite (molybdenum sulphide). Earlier it had never been considered as a possible source of manganese analogues.
Thus, rhenium became, at last, a reality. An end was put to doubts and the symbol Re occupied forever box No. 75 in the periodic table; masurium, however, remained an enigma for a long time.
Hence, 1928 is the date of the reliable discovery of rhenium, the final step in the long process of search. As regards the widely accepted date, 1925, it is only a landmark in the prehistory of the element.
Having planned the directions of research, the Noddacks assembled all publications of supposed discoveries of eka-manganese. Their notes were lost during the second World War but, undoubtedly, the name of the Russian Scientists S. F Kern and the name of the element “devium” were mentioned in them. This may be the most reliable discovery of a new element of all unreliable discoveries. And it is equally possible that the history of element No.75 could have begun 50 years earlier.
The events were as follows. In 1877 reports appeared about the discovery of a new metal “devium” named after H. Davy. The reports aroused great interest and Mendeleev suggested inviting S. F.Kern to report to a session of the Russian Chemical Society. The scientists of Bunsen’s laboratory in Heidelberg decided to check Kern’s result carefully. Later his results were confirmed by two or three other scientists the most interesting fact was that some chemical reactions proved to be identical to those found later for rhenium. Does not it point to the identity of devium and rhenium?
For some reason or other S. F Kern lost interest in his discovery and never returned to the problem after 1878. He had extracted the element from platinum ores, which seems impossible from modern point of view (recall Zvyagintsev’s work in 1926). The fact is, however, that platinum ores have a complex and varied composition. The Uralian ore does not contain rhenium but its presence as traces in ores of other deposits has been proven.
- F. Kern studied a very rare sample of platinum ore from Borneo where by that time mines had already been abandoned. At the beginning of the 20th century the Russian chemist G. Chernik worked on the island. Analyzing platinum ores he found a constant mass loss in all samples and tried to explain it by the presence of an unknown element. This element- could well be Kern’s “devium”.
In 1950 Y. Druce devoted a large article to devium. He wrote that if rhenium would be discovered in platinum minerals, this would confirm Kern’s discovery. Samples of platinum ores from Borneo can be found now only in a few mineralogical museums of the world. It would be of interest to analyse them thoroughly. This is a case when the history of a chemical element could be partially changed.