Element 61—Promethium

Author(s):  
Eric Scerri

The last of our seven elements to be isolated was element 61, which is also the only rare earth among the seven. The problem with rare earths, which are 15 or even 17 in number depending on precisely how they are counted, is that they are extremely similar to each other and as a result are very difficult to separate. When the periodic table was first discovered in the 1860s only two or three rare earths even existed. As more of them turned up it became increasingly difficult to place them in the periodic system. Just like with all the other seven elements in our story, there were many false claims to its discovery. Moreover, the early claims must have seemed very plausible at the time because they appeared to draw support from X-ray evidence and Moseley’s law. Just like the priority dispute involving hafnium that took place in the early 1920s, the case of element 61 also involved an international controversy. This time one cannot entirely blame the aftermath of the Great War, as the two opponents consisted of Italians and Americans, with much of the scientific chicanery taking place, as was usual for the time, in the pages of London’s Nature magazine. But even though both sides of the priority dispute appealed to X-ray data and Moseley’s law, it turned out that neither side was right. In their own way, each side was working in complete delusion, since element 61 is highly radioactive and unstable, does not occur naturally on Earth, and could only be isolated in minute quantities by artificial means when such methods became sufficiently developed in the 1940s. Let us start at the beginning. In 1902, the Bohemian rare earth chemist Bohuslav Brauner was the first to suggest that an element lying precisely between neodymium and samarium remained to be discovered. He gave talks in his native Bohemia and published articles in some fairly obscure journals, all of which meant that few chemists in the wider arena became aware of his work.

Author(s):  
Eric Scerri

The story concerning the discovery and isolation of element 72 bears all the characteristics of controversy and nationalistic overtones that seems to characterize many of our seven elements. On one hand, it seems odd that there should be so much controversy associated with these elements given that Moseley’s method had apparently provided an unequivocal means through which elements could be identified as well as a way of knowing just how many elements remained to be discovered. On the other hand, perhaps it was precisely because the problem of the missing elements became so clearly focused on a few elements, with known atomic numbers, that the stakes became higher than they would have been if the number of elements remaining to be discovered had been uncertain, as they were in pre-Moseley times. Element 72 (fig. 4.1) was clearly anticipated, although not as such, even in Mendeleev’s earliest table of 1869. As fig. 4.2 shows, Mendeleev considered that an as yet undiscovered element with an atomic weight of 180 should be a homologue of zirconium (The modern accepted value is 178.50). This fact may not seem very significant and yet we will see, as the story of this chapter unfolds, that it amounts to Mendeleev predicting that this element would be a transition metal rather than a rare earth. But Mendeleev was not really in a position to make such a statement since the nature and number of rare earth elements was unknown in his day. Indeed, the problem of the rare earths was one of the most acute challenges to his periodic system and one that he personally never resolved. Sometime later, Julius Thomsen, a chemistry professor at the University of Copenhagen and incidentally the chemistry instructor to the physicist Niels Bohr, published a periodic table in which he too included a missing element that was a homologue of zirconium (fi g. 4.3). Suffice it to say that there was a general consensus among chemists that on the basis of the periodic table there should exist an element before tantalum that would be a homologue of zirconium.


About 20 years ago v. Kupffer (85) described in the embryos of Petromyzon an epithelial structure extending, between the ectoderm and the somatic plate of the mesoderm, from the head to the posterior boundary of the branchial region, and described it under the name of the neurodermis; subsequently, he bestowed on it the name branchiodermis. Seventeen years later the same structure was again discovered by Koltzoff (02), who identified it with the mesectoderm which was described by Miss Piatt (94) in Necturus embryos. Subsequently, so far as Petromyzon is concerned, nothing was published until last year, when a paper by Sehalk (13) appeared, although the corresponding layer of cells was described by A. Dohrn (02) in Selachii and by Brauer (04) in Gymnophiona. For a long time the origin and fate of the layer in question engaged my attention. Last summer I was able to re-examine my sections and to confirm observations which I had previously published in a paper entitled “Die Bildungsweise und erste Differenzierung des Mesoderms beim Neunauge ( Lampetra mitsukurii , Hatta),” in which, the origin and differentiation of the so-called mesectoderm are described and illustrated by a series of microphotographs. To my regret the paper, which was ready for press when the great war broke out, could not be sent to the editor of a certain scientific journal in Belgium, who had promised to publish it in his journal. The present note is an attempt to communicate some of the principal points of that paper which relate to the mesectoderm. The other organs dealt with in the above-mentioned paper have already been described in preliminary notes or in my previous papers.


Materials ◽  
2019 ◽  
Vol 12 (5) ◽  
pp. 713 ◽  
Author(s):  
Nejc Rozman ◽  
David Tobaldi ◽  
Uroš Cvelbar ◽  
Harinarayanan Puliyalil ◽  
João Labrincha ◽  
...  

In order to expand the use of titania indoor as well as to increase its overall performance, narrowing the band gap is one of the possibilities to achieve this. Modifying with rare earths (REs) has been relatively unexplored, especially the modification of rutile with rare earth cations. The aim of this study was to find the influence of the modification of TiO2 with rare earths on its structural, optical, morphological, and photocatalytic properties. Titania was synthesized using TiOSO4 as the source of titanium via hydrothermal synthesis procedure at low temperature (200 °C) and modified with selected rare earth elements, namely, Ce, La, and Gd. Structural properties of samples were determined by X-ray powder diffraction (XRD), and the phase ratio was calculated using the Rietveld method. Optical properties were analyzed by ultraviolet and visible light (UV-Vis) spectroscopy. Field emission scanning electron microscope (FE-SEM) was used to determine the morphological properties of samples and to estimate the size of primary crystals. X-ray photoelectron spectroscopy (XPS) was used to determine the chemical bonding properties of samples. Photocatalytic activity of the prepared photocatalysts as well as the titania available on the market (P25) was measured in three different setups, assessing volatile organic compound (VOC) degradation, NOx abatement, and water purification. It was found out that modification with rare earth elements slows down the transformation of anatase and brookite to rutile. Whereas the unmodified sample was composed of only rutile, La- and Gd-modified samples contained anatase and rutile, and Ce-modified samples consisted of anatase, brookite, and rutile. Modification with rare earth metals has turned out to be detrimental to photocatalytic activity. In all cases, pure TiO2 outperformed the modified samples. Cerium-modified TiO2 was the least active sample, despite having a light absorption tail up to 585 nm wavelength. La- and Gd-modified samples did not show a significant shift in light absorption when compared to the pure TiO2 sample. The reason for the lower activity of modified samples was attributed to a greater Ti3+/Ti4+ ratio and a large amount of hydroxyl oxygen found in pure TiO2. All the modified samples had a smaller Ti3+/Ti4+ ratio and less hydroxyl oxygen.


Author(s):  
Leonard V. Smith

Revolution in various forms had been endemic to the Great War. The Paris Peace Conference sought not so much to oppose revolution as to master it in the formation of a new international system. It created the International Labour Organization to institutionalize a transnational approach to labor relations, and thus head off worker unrest as a source of revolution. The Mandate Principle put all mandates at least theoretically on the path to independence, however indefinite the period of tutelage. The Mandate Principle, at least discursively, provided a means of pre-empting anti-colonialism as a source of international instability. The conference also sought to master revolution in successor states. Recognizing Czechoslovakia as a model liberal democracy provided a template ill-suited to recognizing the other successor states. The war between Romania and Hungary in 1919–20 left the Supreme Council with recognition as its only means to control the behavior of successor states.


1999 ◽  
Vol 52 (6) ◽  
pp. 497 ◽  
Author(s):  
David L. Kepert ◽  
Peter C. Junk ◽  
Brian W. Skelton ◽  
Allan H. White

Room-temperature single-crystal X-ray structure determinations are known for a number of ‘maximally hydrated" nitrates of, in particular, the lighter lanthanoid elements; in all cases, all nitrates coordinate as O,O′-bidentate ligands so that the series may be represented at the outset as Ln(O2NO)3.x H2O. Two distinct triclinic P 1 hexahydrate phases of similar cell dimensions are recognized, the most distinctive distinguishing feature being that in the La, Ce phase the 11-coordinate Ln is surrounded by three O,O′-bidentate nitrate and five O-unidentate water molecule ligands; the domain of the other, with four coordinated water molecules, extends from Ln = Pr to Ln = Dy (inclusive of Y). At local ambience, we have crystallized heavier members of the series as pentahydrates, isomorphous with the previously characterized Ln = Eu example, also containing a molecule of the form [Ln(O2NO)3(OH2)4] (with a molecule of water of crystallization), but a different stereoisomer to that found in the Ln = Pr(-)Dy array. Structure determinations are recorded for Ln = Dy, Er, Yb, conventional R on |F| 0·042, 0·034, 0·029 for No = 3858, 3980, 3935 independent ‘observed’ (I > 3σ(I)) diffractometer reflections. For Ln = Lu a new tetrahydrate phase is described, monoclinic P21/n, a 7·379(7), b 10·364(5), c 14·26(1) Å, β 96·09(7)°, Z = 4, R 0·048 for No 2324, together with a new triclinic P 1 trihydrate, a 12·591(4), b 12·144(3), c 7·355(2) Å, α 80·22(2), β 77·68(3), γ 62·30(2)°, Z = 4, R 0·051 for No 4552. In both of the latter, Lu is nine-coordinate, with three bidentate nitrate groups and three coordinated water molecules; remarkably, the two independent molecules of the asymmetric unit in the triclinic phase are distinct isomers, one having the water molecules fac, derivative of the 10-coordinate array of the Pr(-)Yb series with quasi-3 symmetry, while the other, like that in the monoclinic phase, is mer.


Author(s):  
M. Fendorf ◽  
S.W. Keller ◽  
A.M. Stacy ◽  
R. Gronsky

Several new rare earth cuprates having the chemical form RxCuyOz (where R represents the rare earths La, Nd, Sm, Eu, and Gd) have recently been synthesized using a NaOH flux at 400°C. The materials are polycrystalline, and contain varying amounts of R2CuO4 and CuO. During subsequent susceptibility measurements using a SQUID magnetometer, it was found that the Gd material orders antiferromagnetically at approximately 14K, while the other compounds become ferromagnetic between 18K and 28K. Treatment of the powders with 12M HC1 for several minutes dissolves the impurity R2CuO4 and CuO phases, thus facilitating efforts to determine the composition and crystal structure of the new ferromagnetic and antiferromagnetic cuprates. Details of synthesis and magnetic behavior of these materials are to be published elsewhere. In this study, a first attempt is made to characterize the Eu and Gd materials.Energy dispersive x-ray analysis carried out during scanning electron microscopy work indicates that the R:Cu ratio in the Gd material is 1:1.70 (close to 3:5) and that in the Eu material is 1:1.96 (close to 1:2).


Author(s):  
William Brooks ◽  
Christina Bashford ◽  
Gayle Magee

The path to this volume has occupied nearly the full duration of the centennial of the Great War. The three collaborators and coeditors (who are still friends, amazingly) began by organizing a pair of international conferences: Over Here and Over There (University of York, England, February 27–28, 2015); and 1915: Music, Memory, and the Great War (University of Illinois, March 10–11, 2015). The first of these, conducted in tandem with an undergraduate module taught by William Brooks, included numerous performances, presentations, and exhibits by students and scholars, including Gayle Magee, Christina Bashford, and Deniz Ertan, each of whom has contributed to the present volume. The second conference included papers by many of the other authors represented here, with yet others in attendance; it included a performance by a Canadian troupe that re-created an entertainment given by Canada’s legendary “Dumbells” at the western front during the war and a recital by tenor Justin Vickers and pianist Geoffrey Duce, who presented multiple settings by English and American composers of the iconic text “In Flanders Fields.”...


Author(s):  
Frank C. Zagare

This chapter focuses on the outbreak of World War I, which remains one of the most perplexing events of international history. It should be no surprise that rationalist interpretations of the July Crisis are a diverse lot, ranging from the sinister to the benign. This chapter constructs a theoretically rigorous rationalist explanation of World War I, the 1914 European war that involved Austria–Hungary, Germany, Russia, and France. On the one hand, this chapter confirms the view that one does not have to take a particularly dark view of German intentions to explain the onset of war in 1914; on the other hand, it also calls into question the “accidental war” thesis. A number of related questions about the Great War are addressed in the context of a generic game-theoretic escalation model with incomplete information.


2020 ◽  
pp. 301-316
Author(s):  
Rohan McWilliam

This chapter provides a conclusion to the book. It shows that by 1900 the West End functioned as the heart of empire. This was evident in the Mafeking celebrations but also in the way West End shows helped explain the empire to the British. The conservatism of West End culture provided a backdrop for popular imperialism. Whilst the book has emphasized the West End as the source of a conservative consensus, it ends by drawing on the experience of working-class people to show how its opulence could be the source of resentment and conflict. The chapter discusses the Blood Sunday riots which took place in the pleasure district and ends with the Suffragettes window smashing campaign where women attacked an area that was built to attract them. On the eve of the Great War, the West End served as a magnet for protest and pleasure.


Hitherto the widest gap in our knowledge of the isotopic constitution of the elements has been in that part of the periodic Table containing rare earths. A means of obtaining the mass rays of these substances was discovered 10 years ago. By this it was possible to demonstrate the simplicity of lanthanum and praseodymium and to obtain a provisional analysis of the complex elements cerium and neodymium. Beyond these the only positive result was a faint blurr which suggested that erbium was complex and it was decided to postpone further attempts until an instrument of higher resolving power was available. When this was constructed it was naturally first applied to the numerous problems which appeared to be of more fundamental importance so that the complete lack of information on elements 62 to 76 remained.


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