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The Rare Earths II
Redis co very of the Elements The Ra re Earth s–The Con fusing Years I A gallery of rare earth scientists and a timeline of their research I I James L. Marshall, Beta Eta 1971 , and Virginia R. Marshall, Beta Eta 2003 , Department of Chemistry, University of North Texas, Denton, TX 76203-5070, [email protected] The rare earths after Mosander. In the pre - vi ou s HEXAGON “Rediscovery” article, 1p we were introduced to the 17 rare earths, found in the f-block and the Group III chemical family of Figure 1. Important scientists dealing with rare earths through the nineteenth century. Johan Gadolin the Periodic Table. Because of a common (1760 –1852) 1g —discovered yttrium (1794). Jöns Jacob Berzelius (1779 –1848) and Martin Heinrich valence electron configuration, the rare earths Klaproth (1743 –1817) 1d —discovered cerium (1803). Carl Gustaf Mosander (1787 –1858) 1p —discovered have similar chemical properties, and their lanthanum (1839), didymium (1840), terbium, and erbium (1843). Jean-Charles deGalissard Marignac chemical separation from one another can be (1817 –1894) 1o —discovered ytterbium (1878) and gadolinium (1880). Per Teodor Cleve (1840 –1905) 1n — difficult. From preparations of the first two rare discovered holmium and thulium (1879). Lars Fredrik Nilson (1840 –1899) 1n —discovered scandium earth element s—yttrium and ceriu m—the (1879). Paul-Émile Lecoq de Boisbaudran (1838 –1912) —discovered samarium (1879) and dysprosium Swedish chemist Carl Gustaf Mosander (Figure (1886). 1b Carl Auer von Welsbach (1858 –1929) 1c —discovered praseodymium and neodymium (1885); 1, 2) was able to separate four additional ele - co-discovered lutetium (1907). -
The Life and Work of Charles James by Marion James
9/26/2016 UNH Magazine: UNH Magazine The Life and Work of Charles James Easy to print version Return to UNH Magazine Fall '10 web extras The Life and Work of Charles James A professor emeritus of history writes about her father, a UNH professor and prominent chemist. By Marion James '40 One hundred years ago, Charles James arrived at New Hampshire College to teach chemistry and begin a distinguished career. Early Years Charles James was born in England on April 27, 1880. His father died when he was 6, and he was brought up by his mother, Mary Diana ShatfordJames, in Holly House in the small village of Broughton, Northamptonshire. He was educated first by a governess and later at a school in the neighboring town of Wellinborough, where he took the program run by Cambridge University. He said he was introduced to chemistry through reading his father's books on the subject. He also may have taken a chemistry course at school. Becoming fascinated with the field, he set up a laboratory at home at age 15 for his own experiments. A friend of his later remembered seeing him making bombs to blow up decaying tree stumps in the area. ¹ Around the same time, his studies encouraged him to establish connections to the scientific world. He collected the names and addresses of great English chemists, and wrote to Sir William Crookes and Sir William Ramsey, the latter about to win the Noble Prize and who "was considered the greatest chemist of his time." ² Both men replied, and he and Ramsey continued to correspond. -
THE MAJOR RARE-EARTH-ELEMENT DEPOSITS of AUSTRALIA: GEOLOGICAL SETTING, EXPLORATION, and RESOURCES Figure 1.1
CHAPTER ONE WHAT ARE RARE- EARTH ELEMENTS? 1.1. INTRODUCTION latter two elements are classified as REE because of their similar physical and chemical properties to the The rare-earth elements (REE) are a group of seventeen lanthanides, and they are commonly associated with speciality metals that form the largest chemically these elements in many ore deposits. Chemically, coherent group in the Periodic Table of the Elements1 yttrium resembles the lanthanide metals more closely (Haxel et al., 2005). The lanthanide series of inner- than its neighbor in the periodic table, scandium, and transition metals with atomic numbers ranging from if its physical properties were plotted against atomic 57 to 71 is located on the second bottom row of the number then it would have an apparent number periodic table (Fig. 1.1). The lanthanide series of of 64.5 to 67.5, placing it between the lanthanides elements are often displayed in an expanded field at gadolinium and erbium. Some investigators who want the base of the table directly above the actinide series to emphasise the lanthanide connection of the REE of elements. In order of increasing atomic number the group, use the prefix ‘lanthanide’ (e.g., lanthanide REE: REE are: lanthanum (La), cerium (Ce), praseodymium see Chapter 2). In some classifications, the second element of the actinide series, thorium (Th: Mernagh (Pr), neodymium (Nd), promethium (Pm), samarium 1 (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), and Miezitis, 2008), is also included in the REE dysprosium (Dy), holmium (Ho), erbium (Er), thulium group, while promethium (Pm), which is a radioactive (Tm), ytterbium (Yb), and lutetium (Lu). -
The Coordination Chemistry of Solvated Metal Ions in DMPU
The Coordination Chemistry of Solvated Metal Ions in DMPU A Study of a Space-Demanding Solvent Daniel Lundberg Faculty of Natural Resources and Agricultural Sciences Department of Chemistry Uppsala Doctoral thesis Swedish University of Agricultural Sciences Uppsala 2006 Acta Universitatis Agriculturae Sueciae 2006: 23 ISSN 1652-6880 ISBN 91-576-7072-2 © 2006 Daniel Lundberg, Uppsala Tryck: SLU Service/Repro, Uppsala 2006 Abstract Lundberg, D., 2006, The Coordination Chemistry of Solvated Metal Ions in DMPU – A Study of a Space-Demanding Solvent. Doctor’s dissertation. ISSN 1652-6880, ISBN 91-576-7072-2 This thesis summarizes and discusses the results of several individual studies on the solvation of metal ions in the solvent N,N’-dimethylpropyleneurea, DMPU, including the iron(II), iron(III), zinc(II), cadmium(II), and lanthanoid(III) ions. These studies have shown that the solvation process in DMPU is sometimes very different to those in corresponding aqueous systems. This is due to the the space-demanding properties the DMPU molecule has when coordinating to metal ions, with its two methyl groups close to the coordinating oxygen atom. The methyl groups effectively hinder/hamper the metal ion from reaching the coordination numbers present in hydrate and solvate complexes with solvent molecules with much lower spatial demands. The investigations were performed with different X-ray techniques, including extended X-ray absorption fine structure (EXAFS), large angle X-ray scattering (LAXS), and single crystal X-ray diffraction (XRD) and included both studies in solution (EXAFS and LAXS) and solid state (EXAFS and XRD). A coordination number reduction, compared to the corresponding hydrates, was found in all of the studied systems, except cadmium(II). -
Element 72- Hafnium
Rediscovery of the Elements Element 72- Hafnium - A mine the atomic numbers of 38 elements After the hiatus of World War I, Urbain ranging from aluminum (13) to gold (79).2b resumed his research on rare earths. He per- Urbain wished to study some of his rare earth suaded Alexandre Dauvillier (1892-1979), samples which he had been investigating for assistant to Louis-Victor-Pierre-Raymond de two decades." The preparations he brought Broglie (1892-1987; Nobel Laureate in physics, from his laboratory in Paris had been separat- 1929), to reinvestigate his rare earth mixtures.4 ed from ytterbium, originally discovered in In 1919 Dauvillier set up an x-ray laboratory in 1878 by Jean-Charles Galissard de Marignac de Broglie's Parisian mansion, and three years (1817-1894) in Geneva, Switzerland. Urbain later he and Urbain published papers' identi- had previously announced the discovery of fying two faint lines as element 72 which lutetium' in these ytterbium mixtures, but he "demonstrated the existence of a trace of also wanted to confirm "celtium," a new ele- celtium." Urbain explained the earlier negative ment which he had proposed on the basis of results in 1914: Moseley's crude instrumenta- James L. Marshall, beta Eta 1 971, and its different optical spectrum and magnetic tion "had not been sensitive enough."' Even Virginia R. Marshall, Beta Eta 2003, properties." though Urbain was never able to gather any Department of Chemistry, University of In the matter of a few hours, Moseley was further evidence beyond these "two faint lines," North Texas, Denton,TX 76203-5070, able to establish that indeed ytterbium and for years he maintained his claim to the discov- lutetium were present in the mixtures; their ery of element 72. -
Charles James, B. Smith Hopkins, and the Tangled Web of Element 61
Bull. Hist. Chem., VOLUME 31, Number 1 (2006) 9 CHARLES JAMES, B. SMITH HOPKINS, AND THE TANGLED WEB OF ELEMENT 61 Clarence J. Murphy, East Stroudsburg University of Pennsylvania Introduction claimed they found an element that almost certainly does not exist in nature. The history of the search for and discovery of Element 61 is one of the most complex and confused of any of James and Hopkins the elements in the periodic table. Certainly no element has been “discovered” and named more times than 61. Two American chemists, Charles James (1) of the Uni- At least seven claims for discovery were made and 61 versity of New Hampshire and B. Smith Hopkins (2) of has been named at various times illinium, florentium, the University of Illinois were involved in the contro- cyclonium, and promethium. The story of element 61 is versies that surrounded claims of discovery for element also intimately connected with the development of the 61 in the 1920s. understanding of atomic structure and of the Periodic The conventional wisdom on Professor Jamesʼs Table, and of advances in science and technology in the contributions is probably best summarized by a quote late 19th and early 20th centuries. The story involves from an article on Element 61 by Gould, which appeared Roentgenʼs discovery of X-rays and Moseleyʼs use of in Chemical and Engineering News in 1949 (3): X-ray spectra to determine atomic numbers. It involves the more than one hundred-year effort to separate the rare When Hopkins made his announcement in March earths and to find a place for them in the Periodic Table. -
The Development of a Lutetium Recovery Plant
University of Tennessee, Knoxville TRACE: Tennessee Research and Creative Exchange Doctoral Dissertations Graduate School 8-2000 The Development of a Lutetium Recovery Plant Peter Michael Smith University of Tennessee, Knoxville Follow this and additional works at: https://trace.tennessee.edu/utk_graddiss Part of the Chemistry Commons Recommended Citation Smith, Peter Michael, "The Development of a Lutetium Recovery Plant. " PhD diss., University of Tennessee, 2000. https://trace.tennessee.edu/utk_graddiss/4599 This Dissertation is brought to you for free and open access by the Graduate School at TRACE: Tennessee Research and Creative Exchange. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of TRACE: Tennessee Research and Creative Exchange. For more information, please contact [email protected]. To the Graduate Council: I am submitting herewith a dissertation written by Peter Michael Smith entitled "The Development of a Lutetium Recovery Plant." I have examined the final electronic copy of this dissertation for form and content and recommend that it be accepted in partial fulfillment of the requirements for the degree of Doctor of Philosophy, with a major in Chemistry. George K. Schweitzer, Major Professor We have read this dissertation and recommend its acceptance: Laurence Miller, Clifton Woods Accepted for the Council: Carolyn R. Hodges Vice Provost and Dean of the Graduate School (Original signatures are on file with official studentecor r ds.) To the Graduate Council: I am submitting herewith a dissertation written by Peter Michael Smith entitled "The Development of a Lutetium Recovery Plant." I have examined the final copy of this dissertation forform and content and recommend that it be accepted in partial fulfillment of the requirements forthe degree of Doctor of losophy, w· a major in Chemistry. -
Materials for Nuclear Industry: Some Historical Perspectives
J. Chem. Sci. (2019) 131:97 Ó Indian Academy of Sciences https://doi.org/10.1007/s12039-019-1669-7 Sadhana(0123456789().,-volV)FT3](0123456789().,-volV) REGULAR ARTICLE Special Issue on Materials Chemistry Materials for nuclear industry: some historical perspectives P R VASUDEVA RAO Homi Bhabha National Institute, Mumbai 400 094, Maharashtra, India E-mail: [email protected] MS received 29 March 2019; revised 17 May 2019; accepted 22 May 2019; published online 14 October 2019 Abstract. Materials play a key role in the safe and economical operation of nuclear reactors. Materials used in reactors also have to meet stringent chemical specifications for efficient performance. Commercial scale realization of nuclear materials has been a challenge to the nuclear industry. The history of development of nuclear materials has fascinating and unique examples of theoretical prowess as well as innovative experi- mentation and success in nuclear material development is characterized by synergy between the domains of laboratory research and industry. This paper describes the development of some of the important nuclear materials (uranium, plutonium, zirconium, boron, sodium and graphite), providing a historical perspective. Keywords. Nuclear materials; uranium; plutonium; zirconium; boron; graphite; sodium; lanthanides; history; scale-up. 1. Introduction roles other than as fuels or control rod materials should also have very low neutron absorption so that Among the 118 elements known today, some elements they do not affect neutron economy. Fuel materials and their compounds play important roles in nuclear should also have very low concentrations of impu- energy, such as fuel, neutron absorber, moderator, rities that can cause parasitic neutron absorption structural material, coolant, etc. -
Controversial Elements: Priority Disputes and the Discovery of Citation: H
Firenze University Press www.fupress.com/substantia Controversial Elements: Priority Disputes and the Discovery of Citation: H. Kragh (2019) Controver- sial Elements: Priority Disputes and Chemical Elements the Discovery of Chemical Elements. Substantia 3(2) Suppl. 5: 79-90. doi: 10.13128/Substantia-740 Helge Kragh Copyright: © 2019 H. Kragh. This is an open access, peer-reviewed article Niels Bohr Institute, University of Copenhagen, Blegdamsvej 17, Copenhagen, Denmark. published by Firenze University Press E-mail: [email protected] (http://www.fupress.com/substantia) and distributed under the terms of the Creative Commons Attribution License, Abstract. There are only a limited number of chemical elements and to be credited which permits unrestricted use, distri- with the discovery of a new one is therefore considered of great importance. Adding bution, and reproduction in any medi- to the honour and fame is that traditionally the discoverer has the right to name the um, provided the original author and element in question. For these and other reasons, element discoveries are often fol- source are credited. lowed by controversies regarding priority. While some of these are contemporary with Data Availability Statement: All rel- the discovery process, others occur much later and are attempts to rewrite history. evant data are within the paper and its But what is a scientific discovery, more precisely, and why does it sometimes become Supporting Information files. controversial? From a scientific point of view, does it really matter who is recognised for the discovery of a new element? These are some of the questions considered in the Competing Interests: The Author(s) paper, together with a few concrete cases from the history of chemistry. -
Textbooks: Other References
Textbooks: •S. Cotton, Lanthanide and Actinide Chemistry, Wiley 2006. •H.C. Aspinall, Chemistry of the f-Block Elements, Gordon and Breach 2001. •N. Kaltsoyannis, P. Scott, The f elements, Oxford Science 1999. •Holleman-Wiberg, Inorganic Chemistry, Academic Press 2001. Other references: •Handbook on the Physics and Chemistry of Rare Earths, North Holland. •Modern Aspects of Rare Earths and their Complexes, Elsevier. •Organoderivatives of Rare Earth Elements, Kluwer. •Optical Spectroscopy of Lanthanides, CRC. THE LANTHANIDES Ana de Bettencourt-Dias University of Nevada, Reno CHEMISTRY IN 19TH CENTURY • “Lanthanons: These elements perplex us in our researches, baffle us in our speculations, and haunt us in our very dreams. They stretch like an unknown sea before us; mocking, mystifying and murmuring strange revelations and possibilities.“ • Sir William Crookes, Royal Society of Chemistry, 1887. • Rare Earths discovered 1838 – 1947, in 1887 all but Eu, Lu and Pm • Emission spectroscopy – Bunsen and Kirchhoff (1859) • Periodic table – Mendeleyev (1869) William Crookes The fontana history of chemistry, • Atomic model/orbitals Mendeleyev at his desk W.H. Brock, Fontana Mendeleyev’s Dream, The Quest for Press. – Bohr (1913) the Elements, P. Strathern, St. 2 Martin’s Press. HISTORY OF LANTHANIDES I • 1787 – Carl Axel Arrhenius (1757-1824, Swedish artillery officer and amateur geologist ) discovers new mineral, Ytterbyte (Ytterby, Sweden) Gadolin • 1794 – Johan Gadolin (1760-1852) analyzes Ytterbyte and finds it contains Wikipedia new earths (oxides) -
“Ytterbite”, Ytterby, Sweden (Carl Axel Arrhenius, 1757-1824) Late 1780S
“Ytterbite”, Ytterby, Sweden Unknown heavy mineral, Bastnäs, Sweden (Carl Axel Arrhenius, 1757‐1824) (Axel Fredrik Cronstedt, 1722‐1765) late 1780s 1751 Renamed cerite and analyzed to contain a new “earth”, named ceria Analyzed to contain a new “earth” (Wilhelm Hisinger, 1766‐1852 & (Johan Gadolin, 1760‐1852) Renamed gadolinite Jöns Jacob Berzelius , 1779‐1848; 1789‐1794 (Martin Heinrich Klaproth, 1743‐1817) Martin Heinrich Klaproth, 1743‐1817) 1800 1803 Confirmed and named yttria (Anders Gustaf Ekeberg, 1767‐1813) 1797 Metallic yttrium (Yt, then Y) isolated Lanthanum (La) and didymium (Di) identified (Friedrich Wöhler, 1800‐1882) “Uranotantal”, Blyumovskaya pit, as components of ceria (Carl Gustaf Mosander, 1797‐1858) 1828 Ilmeny Mts., Russia 1839‐1841 (Gustav Rose, 1798‐1873) 1840 Yttria = yttria + erbia + terbia (Carl Gustaf Mosander, 1797‐1858) 1843 Renamed samarskite (Heinrich Rose, 1795‐1864) Metallic cerium (Ce) isolated Renamed terbia Renamed erbia 1847 (William F. Hillebrand, 1853‐1925 late 1870s 1860s & Thomas H. Norton, 1851‐1941) 1875 Erbia = erbia + ytterbia (Jean C.G. de Marignac, 1817‐1894) Gadolinia idenitified in Didymium = neodymium (Nd) + praseodymium (Pr) (Carl Auer von Welsbach, 1872‐1938) Dysprosium (Dy) identified in “holmia” Erbia = erbia + holmia + thulia 1878 didymium and yttria samples (Jean C.G. de Marignac, 1817‐1894; 1885 (Paul É.L. de Boisbaudran, 1838‐1912) (Per Teodor Cleve, 1840‐1905) Ytterbia = neoytterbia + lutecia Europium is isolated from samaria Paul É.L. de Boisbaudran, 1838‐1912) 1878 1878‐1879 (Georges Urbain, 1872‐1938) (Eugène‐Anatole Demarçay, 1852‐1904) 1880‐1886 1907 1901 Metallic neodymium isolated Metallic thulium (Tm) isolated Ytterbia = aldebaranium + cassiopeum 1925 (Charles James, 1880‐1928) (Carl Auer von Welsbach, 1872‐1938) Metallic praseodymium isolated 1911 1908 1931 Metallic erbium (Er) isolated Promethium Fission products of uranium fuel irradiated ina (W.