Early Responses to the Periodic System
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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). -
Hexagon Fall
Redis co very of the Elements The Rare Earth s–The Beginnings I 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] 1 Rare earths —introduction. The rare earths Figure 1. The “rare earths” are defined by IUPAC as the 15 lanthanides (green) and the upper two elements include the 17 chemically similar elements of the Group III family (yellow). These elements have similar chemical properties and all can exhibit the +3 occupying the f-block of the Periodic Table as oxidation state by the loss of the highest three electrons (two s electrons and either a d or an f electron, well as the Group III chemical family (Figure 1). depending upon the particular element). A few rare earths can exhibit other oxidation states as well; for These elements include the 15 lanthanides example, cerium can lose four electrons —4f15d 16s 2—to attain the Ce +4 oxidation state. (atomic numbers 57 through 71, lanthanum through lutetium), as well as scandium (atomic number 21) and yttrium (atomic number 39). The chemical similarity of the rare earths arises from a common ionic configuration of their valence electrons, as the filling f-orbitals are buried in an inner core and generally do not engage in bonding. The term “rare earths” is a misnome r—these elements are not rare (except for radioactive promethium). They were named as such because they were found in unusual minerals, and because they were difficult to separate from one another by ordinary chemical manipula - tions. -
An Account of the Progress in Chemistry in the Year [1882-1886]
QD 15 .B7 % » 1882 Copy 1 530 j AN ACCOUNT OF THE PROGRESS I TAT / CHEMISTRY IN THE YEAR 18.8 2. • PROF. H. CARRINGTON BOLTON. FROM THE SMITHSONIAN REPORT FOR 1882. * WASHINGTON: GOVERNMENT PRINTING OFFICE. 1883. 53© AN ACCOUNT OF THE PROGRESS IN CHEMISTEY IN THE YEAR 1882 BY PROF. H. CARRINGTON BOLTON. 1t FROM THE SMITHSONIAN REPORT FOR 1882. WASHINGTON: GOVERNMENT PRINTING OFFICE. 1883. ^ \ CHEMISTRY. By H. Carhington Bolton, Ph. D., Professor of Chemistry in Trinity College, Hartford, Conn. The year 1882 is marked by great industry in all departments of •chemistry; no startling announcements have been made, but several extremely interesting syntheses of organic bodies have been accom- plished, viz, tyrosine and uric acid, both of the animal organism. Great activity is noted in the revision of the atomic weights. Progress has been made in unraveling the knotty problem of the rare earths in cerite, samarskite, and gadolinite, but no satisfactory conclusions have been reached as to the existence of the larger number of elementary bodies announced since 1877. In the brief space at our disposal we can barely note the salient fea- tures of the year's work in a series of short abstracts, and these we con- fine chiefly to pure chemistry, paying little attention to analytical and industrial chemistry. Periodical literature, devoted exclusively to chem- istry and its applications, is becoming voluminous ; the fifteen principal journals of America, England, France, and Germany publish annually about 18,000 pages; in this rough estimate journals of physics and transactions of societies are not included, and both classes of serials contain much chemical'material. -
An Excerpt from Sakurai's Lectures on Organic Chemistry and The
Appendix: An Excerpt from Sakurai’s Lectures on Organic Chemistry and the Corresponding Part of Majima’s Notebook of Sakurai’s Lectures Sakurai’s Original Lecture Notes ⎡ CO ⎤ Alizarine ⎢CHH ::CHH (OH) ⎥ C HOO . ⎣ 64CO 62 21⎦ 4 84 Alizarine is a well known red colouring matter extracted from the roots of ‘madder’ plant, botanically known as Rubia tinctoricum. The colouring matter, however, does not exist as such in the plant, but in the form of a glucoside. This glucoside called rubian or ruberythric acid undergoes hydrolysis under the influence of a ferment, called erythrozym [sic] also cont[aine]d in the plant. No action takes place so long as the plant is living, but when it is cut and the roots are left in a moist condition, alizarine separates out. + 26 28OH14 H2OCO 14HO84O 2C61HOH 26O Ruberythric acid alizarinei glucose The above equation represents the change according to Graebe and Liebermann. Alizarine is almost insoluble in water. It dissolves in alkali form- ing a beautiful violet colour, from which carbonic acid precipitates it. The p[reci]p[ita]te on drying and sublimation forms fine orange-red needles. M[elting] P[oint] 290. It dissolves easily in alcohol, ether, benzene, etc. The alkaline sol[utio]n treated with aluminium sulphate gives a red lake. (carmine red) ferric salts give purple. stannic salts give red (orange red) ferrous salts give brown. 176 APPENDIX On account of the production of these comp[oun]ds alizarine has long been employed as one of the most important dyes, and for this purpose “Madder” plant was extensively planted. -
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). -
Holmium Same As Santa’S Signature Hearty Laugh
Ho Ho Ho, Merry Christmas! It’s that time of the year, it’s Christmas time! Council of the 118 Elements I’m thrilled to introduce you to the element who has a chemical symbol the Santa Claus ~ Ho…Ho…Holmium same as Santa’s signature hearty laugh. Let’s give a warm welcome to Holmium in this chilly month of Christmas. Name Holmium He is a member of the Lanthanide series. The Lanthanides are put in a Atomic No. Atomic Weight disembodied block below the main body of the Periodic Table. It comprises 67 164.9303 15 elements with atomic numbers 57 to 71, from Lanthanum to Lutetium. Origin of the Name Home town of Cleve Holmia ‘Stockholm’ (the discoverer) Holmium has the highest magnetic strength of any element, and therefore is used to create the strongest artificially generated magnetic Melting Point 1461 °C Electronic fields. Another special trait is that he readily absorbs excess neutrons Arrangement Boiling Point 2720 °C 2,8,18,29,8,2 and so controls the chain reaction that fuels the nuclear reactor. Density 8.54 g/cm3 Humans also owe a huge thanks to Holmium for his Abundance 1.3 mg/kg significant contributions in the medical and dental fields. Category Metal Holmium lasers can produce a wavelength of light close to that of a microwave oven. Such electromagnetic radiation Discovery of the is efficiently absorbed by water molecules because it Santa Element Discoverer : Swede perfectly excites the hydrogen-oxygen bonds in water. Per Teodor Cleve Soft tissue in our bodies is largely made up of water and Year of Discovery: 1878 Cleve removed all of the known these lasers are energetic enough to cut through flesh. -
The Rare Earths I
The Mountain Pass rare earth ore body in Southern California, 86 km (54 mi) south-southwest of LasLas Vegas,Vegas, Nevada,Nevada, isis oneone ofof thethe largest,largest, richest,richest, andand mostmost readilyreadily mineablemineable rarerare earthearth depositsdeposits inin thethe worldworld (N35°(N35° 28.7428.74 W115°W115° 31.98).31.98). ItsIts provenproven andand probableprobable reservesreserves exceedexceed 1.31.3 millionmillion metricmetric tonstons ofof rarerare earthearth oxideoxide (REO)(REO) equivalentequivalent containedcontained inin 18.418.4 millionmillion metricmetric tonstons ofof oreore withwith ~8%~8% ore grade and a 5% cut-off grade. ItIt containscontains allall ofof thethe naturallynaturally occurringoccurring rarerare earthearth elements.elements. Photo,Photo, courtesycourtesy ofof Molycorp,Molycorp, Inc.Inc. Rediscovery ...pg 40 2016 Solicitation...pg 52 2015 Awards . ..pg 54 Collegiate News ...pg 57 FALL 2015 THE Rediscovering The Rare Earths A new series starts on page 40. Redis co very of the Elements The Rare Earth s–The Beginnings I 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] 1 Rare earths —introduction. The rare earths Figure 1. The “rare earths” are defined by IUPAC as the 15 lanthanides (green) and the upper two elements include the 17 chemically similar elements of the Group III family (yellow). These elements have similar chemical properties and all can exhibit the +3 occupying the f-block of the Periodic Table as oxidation state by the loss of the highest three electrons (two s electrons and either a d or an f electron, well as the Group III chemical family (Figure 1). -
By EDWARD DIVERS, M.D
View Article Online / Journal Homepage / Table of Contents for this issue DIVERS : NON-SATURATED OXYGENOUS SALTS. 205 XXX.-The Constitution, of some Non-satuyated Oxygenous Salts. and the Reaction of Phosphorus OxycAloride with Sulpkites and Nitrites. By EDWARDDIVERS, M.D. THE object of the present paper is to show that non-saturated oxygenous salts differ from those which are saturated, not in the Published on 01 January 1885. Downloaded by Rensselaer Polytechnic Institute 23/10/2014 03:50:39. manner in which they are universally represented as doing-namely, in having their chlorous elements of a lower than their maximum valency-but in being less oxylic than the saturated salts of the same element, or, in the case of metallic salts of monobasic acids, not oxylic at all. Sulph,ites--no Evidence that they are Diosylic. Two views have been held concerning the constitution of sulphitea as salts. According to the one, they are half halo'id salts, half oxylic, as represented by the formula *g >SO,. This view was proposed Ago by Odling very many years ago, but ha8 long since been given up by him for the other.* According to this view, the constitution of * It was also held by Strecker and others, and in England the late Henry Watts VOL. XLVII. Q View Article Online 206 DIVERS: THE CONSTITUTION OF SOME sulphites is the same as that of sulphonates, and may therefore be for brevity called the sulphonic constitution. On the other view, sulphites are dioxylic, as represented by the formula (AgO),SO. This view is now generally accepted, in spite of several well-known reactions not in harmony with it. -
Towards the Recovery of Rare Earth Elements from End-Of-Life Products: Hydrometallurgical Routes and Mathematical Modelling of Extraction Systems
Chemical Engineering Department PhD Program: Chemical Processes Engineering TOWARDS THE RECOVERY OF RARE EARTH ELEMENTS FROM END-OF-LIFE PRODUCTS: HYDROMETALLURGICAL ROUTES AND MATHEMATICAL MODELLING OF EXTRACTION SYSTEMS Author: Eleonora Obón Estrada Director: Dr. Ana Maria Sastre Requena Codiretor: Dr. Agustín Fortuny Sanromà Escola Tècnica Superior d’Enginyeria Industrial de Barcelona (ETSEIB) Universitat Politècnica de Catalunya, Barcelona, July 2019 Thesis presented to obtain the qualification of Doctor awarded by the Universitat Politècnica de Catalunya II Abstract The rare earth elements (REEs) are essential ingredients for the development of modern industry and the transition to a more sustainable economy model. The unique physicochemical features of these elements, such as their magnetism and optical properties, are greatly expanding their application. They have become key elements for the manufacture of many ordinary consumer goods like hybrid cars, fluorescent lamps or electronic devices like mobile phones or tablets. The growing popularity of the rare earth elements derivatives is leading to an increase in the global demand and the price of these elements. Unfortunately, the current availability of these resources is limited due to three main factors: their heterogeneous geological location, their low concentration in the ores, and the environmental issues related with their mining. All these disadvantages concerning the supply of the rare earth elements have led to the study of new techniques to obtain them, such as the recycling of end- of-life products. Recycling of REEs arises as a new secondary source of supply of REEs, especially in Europe where large amounts of technological waste are generated every year. Currently, the recycling of rare earth elements represents less than 1% of the global supply. -
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). -
Historical Group
Historical Group NEWSLETTER and SUMMARY OF PAPERS No. 65 Winter 2014 Registered Charity No. 207890 COMMITTEE Chairman: Dr J A Hudson ! Dr C Ceci (RSC) Graythwaite, Loweswater, Cockermouth, ! Dr N G Coley (Open University) Cumbria, CA13 0SU ! Dr C J Cooksey (Watford, Hertfordshire) [e-mail [email protected]] ! Prof A T Dronsfield (Swanwick, Secretary: Prof. J. W. Nicholson ! Derbyshire) School of Sport, Health and Applied Science, ! Prof E Homburg (University of St Mary's University College, Waldegrave Road, ! Maastricht) Twickenham, Middlesex, TW1 4SX ! Prof F James (Royal Institution) [e-mail: [email protected]] ! Dr D Leaback (Biolink Technology) Membership Prof W P Griffith ! Mr P N Reed (Steensbridge, Secretary: Department of Chemistry, Imperial College, ! Herefordshire) London, SW7 2AZ [e-mail [email protected]] ! Dr V Quirke (Oxford Brookes University) Treasurer: Dr P J T Morris ! Prof. H. Rzepa (Imperial College) Science Museum, Exhibition Road, South ! Dr. A Sella (University College) Kensington, London, SW7 2DD [e-mail: [email protected]] Newsletter Dr A Simmons Editor Epsom Lodge, La Grande Route de St Jean, St John, Jersey, JE3 4FL [e-mail [email protected]] Newsletter Dr G P Moss Production: School of Biological and Chemical Sciences, Queen Mary University of London, Mile End Road, London E1 4NS [e-mail [email protected]] http://www.chem.qmul.ac.uk/rschg/ http://www.rsc.org/membership/networking/interestgroups/historical/index.asp RSC Historical Group Newsletter No. 65 Winter 2014 Contents -
The Dual-Fuel Strategy: an Energy Transition Plan the Transition from Fossil to Renewable and Nuclear Energy Sources Is Enabled by Developing Liquid Renewable Fuels
CONTRIBUTED PAPER The Dual-Fuel Strategy: An Energy Transition Plan The transition from fossil to renewable and nuclear energy sources is enabled by developing liquid renewable fuels. Electric power and electrochemical energy conversion have central roles. By William L. Ahlgren ABSTRACT | Depletion of easily accessible petroleum reserves renewable fuels and relies on the force of free enterprise to has created unstable oil supply and price, opening the create a postpetroleum civilization powered by a zero-net- opportunity to replace oil as an energy source with other fossil carbon energy system. The strategy enables global carbon sources and ultimately with renewable and perhaps nuclear emissions to be reduced significantly early in the transition, sources. The dual-fuel strategy is a plan to facilitate the transi- perhapsbyasmuchasanorderofmagnitudeby2030,with tion from fossil to renewable sources by first replacing fossil zero-emissions perhaps as early as 2050. with renewable fuels. It stipulates that all energy sources (fossil, renewable, and nuclear) will be most efficiently mone- KEYWORDS | Alternative fuel; ammonia; ammonia fuel; carbo- tized by conversion to three primary energy vectors: electric fuel; carbon emissions; coal-to-liquid; electric power; electro- power and two liquid renewable fuels, all compatible with chemical energy conversion; energy chain; energy policy; existing infrastructure. One member of a dual-fuel pair is energy strategy; energy vector; fuel; gas-to-liquid; greenhouse nitrogen-based, for example, ammonia, and the other is gases; hydrogen; hydrogen economy; methanol; methanol fuel; carbon-based, for example, methanol. The two are comple- nitrofuel; postpetroleum; renewable fuel; sustainable energy; mentary: ammonia is carbon-free, but has high relative toxicity, synthetic fuel while methanol has low relative toxicity, but contains carbon.