Elements - CRC Handbook Definitions Flashcards

Question

Manganese - Rubber Bible Definition

Answer 1

Manganese — (L. magnes, magnet, from magnetic properties of pyrolusite; It. manganese, corrupt form of magnesia), Mn; at. wt. 54.938049(9); at. no. 25; m.p. 1246°C; b.p. 2061°C; sp. gr. 7.21 to 7.44, depending on allotropic form; valence 1, 2, 3, 4, 6, or 7. Recognized by Scheele, Bergman, and others as an element and isolated by Gahn in 1774 by reduction of the dioxide with carbon. Manganese minerals are widely distributed; oxides, silicates, and carbonates are the most common. The discovery of large quantities of manganese nodules on the floor of the oceans holds promise as a source of manganese. These nodules contain about 24% manganese together with many other elements in lesser abundance. Most manganese today is obtained from ores found in the Ukraine, Brazil, Australia, Republic of So. Africa, Gabon, China, and India. Pyrolusite (MnO2) and rhodochrosite (MnCO3) are among the most common manganese minerals. The metal is obtained by reduction of the oxide with sodium, magnesium, aluminum, or by electrolysis. It is gray-white, resembling iron, but is harder and very brittle. The metal is reactive chemically, and decomposes cold water slowly. Manganese is used to form many important alloys. In steel, manganese improves the rolling and forging qualities, strength, toughness, stiffness, wear resistance, hardness, and hardenability. With aluminum and antimony, especially with small amounts of copper, it forms highly ferromagnetic alloys. Manganese metal is ferromagnetic only after special treatment. The pure metal exists in four allotropic forms. The alpha form is stable at ordinary temperature; gamma manganese, which changes to alpha at ordinary temperatures, is said to be flexible, soft, easily cut, and capable of being bent. The dioxide (pyrolusite) is used as a depolarizer in dry cells, and is used to “decolorize” glass that is colored green by impurities of iron. Manganese by itself colors glass an amethyst color, and is responsible for the color of true amethyst. The dioxide is also used in the preparation of oxygen and chlorine, and in drying black paints. The permanganate is a powerful oxidizing agent and is used in quantitative analysis and in medicine. Manganese is widely distributed throughout the animal kingdom. It is an important trace element and may be essential for utilization of vitamin B1. Twenty-seven isotopes and isomers are known. Manganese metal (99.95%) is priced at about $800/kg. Metal of 99.6% purity is priced at about $80/kg.

Answer 2

Iron — (Anglo-Saxon, iron), Fe (L. ferrum); at. wt. 55.845(2); at. no. 26; m.p. 1538°C; b.p. 2861°C; sp. gr. 7.874 (20°C); valence 2, 3, 4, or 6. The use of iron is prehistoric. Genesis mentions that Tubal-Cain, seven generations from Adam, was “an instructor of every artificer in brass and iron.” A remarkable iron pillar, dating to about A.D. 400, remains standing today in Delhi, India. This solid shaft of wrought iron is about 71/4 m high by 40 cm in diameter. Corrosion to the pillar has been minimal although it has been exposed to the weather since its erection. Iron is a relatively abundant element in the universe. It is found in the sun and many types of stars in considerable quantity. Its nuclei are very stable. It has been suggested that the iron we have here on earth may have originated in a supernova. Iron is a very difficult element to produce in ordinary nuclear reactions, such as would take place in the sun. Iron is found native as a principal component of a class of iron-nickel meteorites known as siderites, and is a minor constituent of the other two classes of meteorites. The core of the earth, 2150 miles in radius, is thought to be largely composed of iron with about 10% occluded hydrogen. The metal is the fourth most abundant element, by weight, making up the crust of the earth. The most common ore is hematite (Fe2O3). Magnetite (Fe3O4) is frequently seen as black sands along beaches and banks of streams. Lodestone is another form of magnetite. Taconite is becoming increasingly important as a commercial ore. Iron is a vital constituent of plant and animal life, and appears in hemoglobin. The pure metal is not often encountered in commerce, but is usually alloyed with carbon or other metals. The pure metal is very reactive chemically, and rapidly corrodes, especially in moist air or at elevated temperatures. It has four allotropic forms, or ferrites, known as α, β, γ, and δ, with transition points at 700, 928, and 1530°C. The α form is magnetic, but when transformed into the β form, the magnetism disappears although the lattice remains unchanged. The relations of these forms are peculiar. Pig iron is an alloy containing about 3% carbon with varying amounts of S, Si, Mn, and P. It is hard, brittle, fairly fusible, and is used to produce other alloys, including steel. Wrought iron contains only a few tenths of a percent of carbon, is tough, malleable, less fusible, and has usually a “fibrous” structure. Carbon steel is an alloy of iron with carbon, with small amounts of Mn, S, P, and Si. Alloy steels are carbon steels with other additives such as nickel, chromium, vanadium, etc. Iron is the cheapest and most abundant, useful, and important of all metals. Natural iron contains four isotopes and isomers. Twenty-six other isotopes and isomers, all radioactive, are now recognized.

Answer 3

Cobalt — (Kobald, from the German, goblin or evil spirit, cobalos, Greek, mine), Co; at. wt. 58.93320(1); at. no. 27; m.p. 1495°C; b.p. 2927°C; sp. gr. 8.9 (20°C); valence 2 or 3. Discovered by Brandt about 1735. Cobalt occurs in the mineral cobaltite, smaltite, and erythrite, and is often associated with nickel, silver, lead, copper, and iron ores, from which it is most frequently obtained as a by-product. It is also present in meteorites. Important ore deposits are found in Congo-Kinshasa, Australia, Zambia, Russia, Canada, and elsewhere. The U.S. Geological Survey has announced that the bottom of the north central Pacific Ocean may have cobalt-rich deposits at relatively shallow depths in waters close to the Hawaiian Islands and other U.S. Pacific territories. Cobalt is a brittle, hard metal, closely resembling iron and nickel in appearance. It has a magnetic permeability of about two thirds that of iron. Cobalt tends to exist as a mixture of two allotropes over a wide temperature range; the β-form predominates below 400°C, and the α above that temperature. The transformation is sluggish and accounts in part for the wide variation in reported data on physical properties of cobalt. It is alloyed with iron, nickel and other metals to make Alnico, an alloy of unusual magnetic strength with many important uses. Stellite alloys, containing cobalt, chromium, and tungsten, are used for high-speed, heavy-duty, high temperature cutting tools, and for dies. Cobalt is also used in other magnet steels and stainless steels, and in alloys used in jet turbines and gas turbine generators. The metal is used in electroplating because of its appearance, hardness, and resistance to oxidation. The salts have been used for centuries for the production of brilliant and permanent blue colors in porcelain, glass, pottery, tiles, and enamels. It is the principal ingredient in Sevre’s and Thenard’s blue. A solution of the chloride (CoCl2 · 6H2O) is used as sympathetic ink. The cobalt ammines are of interest; the oxide and the nitrate are important. Cobalt carefully used in the form of the chloride, sulfate, acetate, or nitrate has been found effective in correcting a certain mineral deficiency disease in animals. Soils should contain 0.13 to 0.30 ppm of cobalt for proper animal nutrition.Cobalt is found in Vitamin B-12, which is essential for human nutrition. Cobalt of 99.9+% purity is priced at about$250/kg. Cobalt-60, an artificial isotope, is an important gamma ray source, and is extensively used as a tracer and a radiotherapeutic agent. Single compact sources of Cobalt-60 vary from about $1 to $10/curie, depending on quantity and specific activity. Thirty isotopes and isomers of cobalt are known.

Answer 4

Copper — (L. cuprum, from the island of Cyprus), Cu; at. wt. 63.546(3); at. no. 29; f.p. 1084.62 °C; b.p. 2562°C; sp. gr. 8.96 (20°C); valence 1 or 2. The discovery of copper dates from prehistoric times. It is said to have been mined for more than 5000 years. It is one of man’s most important metals. Copper is reddish colored, takes on a bright metallic luster, and is malleable, ductile, and a good conductor of heat and electricity (second only to silver in electrical conductivity). The electrical industry is one of the greatest users of copper. Copper occasionally occurs native, and is found in many minerals such as cuprite, malachite, azurite, chalcopyrite, and bornite. Large copper ore deposits are found in the U.S., Chile, Zambia, Zaire, Peru, and Canada. The most important copper ores are the sulfides, oxides, and carbonates. From these, copper is obtained by smelting, leaching, and by electrolysis. Its alloys, brass and bronze, long used, are still very important; all American coins are now copper alloys; monel and gun metals also contain copper. The most important compounds are the oxide and the sulfate, blue vitriol; the latter has wide use as an agricultural poison and as an algicide in water purification. Copper compounds such as Fehling’s solution are widely used in analytical chemistry in tests for sugar. High-purity copper (99.999 + %) is readily available commercially. The price of commercial copper has fluctuated widely. The price of copper in December 2001 was about $1.50/kg. Natural copper contains two isotopes. Twenty-six other radioactive isotopes and isomers are known.

Answer 5

Nickel — (Ger. Nickel, Satan or Old Nick’s and from kupfernickel, Old Nick’s copper), Ni; at. wt. 58.6934(2); at. no. 28; m.p. 1455°C; b.p. 2913°C; sp. gr. 8.902 (25°C); valence 0, 1, 2, 3. Discovered by Cronstedt in 1751 in kupfernickel (niccolite). Nickel is found as a constituent in most meteorites and often serves as one of the criteria for distinguishing a meteorite from other minerals. Iron meteorites, or siderites, may contain iron alloyed with from 5 to nearly 20% nickel. Nickel is obtained commercially from pentlandite and pyrrhotite of the Sudbury region of Ontario, a district that produces much of the world’s nickel. It is now thought that the Sudbury deposit is the result of an ancient meteorite impact. Large deposits of nickel, cobalt, and copper have recently been developed at Voisey’s Bay, Laborador. Other deposits of nickel are found in Russia, New Caledonia, Australia, Cuba, Indonesia, and elsewhere. Nickel is silvery white and takes on a high polish. It is hard, malleable, ductile, somewhat ferromagnetic, and a fair conductor of heat and electricity. It belongs to the iron-cobalt group of metals and is chiefly valuable for the alloys it forms. It is extensively used for making stainless steel and other corrosion-resistant alloys such as Invar®, Monel®, Inconel®, and the Hastelloys®. Tubing made of a copper-nickel alloy is extensively used in making desalination plants for converting sea water into fresh water. Nickel is also now used extensively in coinage and in making nickel steel for armor plate and burglar-proof vaults, and is a component in Nichrome®, Permalloy®, and constantan. Nickel added to glass gives a green color. Nickel plating is often used to provide a protective coating for other metals, and finely divided nickel is a catalyst for hydrogenating vegetable oils. It is also used in ceramics, in the manufacture of Alnico magnets, and in the Edison® storage battery. The sulfate and the oxides are TeamLRN THE ELEMENTS (continued) 4-21 important compounds. Natural nickel is a mixture of five stable isotopes; twenty-five other unstable isotopes are known. Nickel sulfide fume and dust is recognized as having carcinogenic potential. Nickel metal (99.9%) is priced at about $2/g or less in larger quantities.

Answer 6

Zinc — (Ger. Zink, of obscure origin), Zn; at. wt. 65.39(2); at. no. 30; m.p. 419.53°C; b.p. 907°C; sp. gr. 7.133 (25°C); valence 2. Centuries before zinc was recognized as a distinct element, zinc ores were used for making brass. Tubal-Cain, seven generations from Adam, is mentioned as being an “instructor in every artificer in brass and iron.” An alloy containing 87% zinc has been found in prehistoric ruins in Transylvania. Metallic zinc was produced in the 13th century A.D. in India by reducing calamine with organic substances such as wool. The metal was rediscovered in Europe by Marggraf in 1746, who showed that it could be obtained by reducing calamine with charcoal. The principal ores of zinc are sphalerite or blende (sulfide), smithsonite (carbonate), calamine (silicate), and franklinite (zinc, manganese, iron oxide). Canada, Japan, Belgium, Germany, and The Netherlands are suppliers of zinc ores. Zinc is also mined in Alaska, Tennessee, Missouri, and elsewhere in the U.S. Zinc can be obtained by roasting its ores to form the oxide and by reduction of the oxide with coal or carbon, with subsequent distillation of the metal. Other methods of extraction are possible. Naturally occurring zinc contains five stable isotopes. Twenty-five other unstable isotopes and isomers are recognized. Zinc is a bluish-white, lustrous metal. It is brittle at ordinary temperatures but malleable at 100 to 150°C. It is a fair conductor of electricity, and burns in air at high red heat with evolution of white clouds of the oxide. The metal is employed to form numerous alloys with other metals. Brass, nickel silver, typewriter metal, commercial bronze, spring brass, German silver, soft solder, and aluminum solder are some of the more important alloys. Large quantities of zinc are THE ELEMENTS (continued) 4-36 used to produce die castings, used extensively by the automotive, electrical, and hardware industries. An alloy called Prestal®, consisting of 78% zinc and 22% aluminum is reported to be almost as strong as steel but as easy to mold as plastic. It is said to be so plastic that it can be molded into form by relatively inexpensive die casts made of ceramics and cement. It exhibits superplasticity. Zinc is also extensively used to galvanize other metals such as iron to prevent corrosion. Neither zinc nor zirconium is ferromagnetic; but ZrZn2 exhibits ferromagnetism at temperatures below 35 K. Zinc oxide is a unique and very useful material to modern civilization. It is widely used in the manufacture of paints, rubber products, cosmetics, pharmaceuticals, floor coverings, plastics, printing inks, soap, storage batteries, textiles, electrical equipment, and other products. It has unusual electrical, thermal, optical, and solid-state properties that have not yet been fully investigated. Lithopone, a mixture of zinc sulfide and barium sulfate, is an important pigment. Zinc sulfide is used in making luminous dials, X-ray and TV screens, and fluorescent lights. The chloride and chromate are also important compounds. Zinc is an essential element in the growth of human beings and animals. Tests show that zinc-deficient animals require 50% more food to gain the same weight as an animal supplied with sufficient zinc. Zinc is not considered to be toxic, but when freshly formed ZnO is inhaled a disorder known as the oxide shakes or zinc chills sometimes occurs. It is recommended that where zinc oxide is encountered good ventilation be provided. The commercial price of zinc in January 2002 was roughly 40¢/lb ($90 kg). Zinc metal with a purity of 99.9999% is priced at about $5/g.

Answer 7

Gallium — (L. Gallia, France; also from Latin, gallus, a translation of Lecoq, a cock), Ga; at. wt. 69.723(1); at. no. 31; m.p. 29.76°C; b.p. 2204°C; sp. gr. 5.904 (29.6°C) solid; sp. gr. 6.095 (29.6°C) liquid; valence 2 or 3. Predicted and described by Mendeleev as ekaaluminum, and discovered spectroscopically by Lecoq de Boisbaudran in 1875, who in the same year obtained the free metal by electrolysis of a solution of the hydroxide in KOH. Gallium is often found as a trace element in diaspore, sphalerite, germanite, bauxite, and coal. Some flue dusts from burning coal have been shown to contain as much as 1.5% gallium. It is the only metal, except for mercury, cesium, and rubidium, which can be liquid near room temperatures; this makes possible its use in high-temperature thermometers. It has one of the longest liquid ranges of any metal and has a low vapor pressure even at high temperatures. There is a strong tendency for gallium to supercool below its freezing point. Therefore, seeding may be necessary to initiate solidification. Ultra-pure gallium has a beautiful, silvery appearance, and the solid metal exhibits a conchoidal fracture similar to glass. The metal expands 3.1% on solidifying; therefore, it should not be stored in glass or metal containers, as they may break as the metal solidifies. Gallium wets glass or porcelain, and forms a brilliant mirror when it is painted on glass. It is widely used in doping semiconductors and producing solid-state devices such as transistors. High-purity gallium is attacked only slowly by mineral acids. Magnesium gallate containing divalent impurities such as Mn+2 is finding use in commercial ultraviolet activated powder phosphors. Gallium nitride has been used to produce blue light-emitting diodes. Blue LED’s used in compact disc applications can be used to store a 2-hr movie, for example, on one 5-in. diameter disc. Extensive use of gallium has found recent application in the Gallex Detector Experiment located in the Gran Sasso Underground Laboratory in Italy. This underground facility has been built by the Italian Istituto Nazionale di Fisica Nucleare in the middle of a highway tunnel through the Abruzzese mountains, about 150 km east of Rome. The experiment is shielded by a 3300-m water-equivalent of rock. In this experiment, 30.3 tons of gallium in the form of 110 tons of GaCl3-HCl solution are being used to detect solar neutrinos. The production of 71Ge from gallium is being measured.Gallium arsenide is capable of converting electricity directly into coherent light. Gallium readily alloys with most metals, and has been used as a component in low-melting alloys. Its toxicity appears to be of a low order, but should be handled with care until more data are forthcoming. Natural gallium contains two stable isotopes. Twenty-six other isotopes, one of which is an isomer, are known. The metal can be supplied in ultrapure form (99.99999+%). The cost is about $5/g (99.999%).

Answer 8

Germanium — (L. Germania, Germany), Ge; at. wt. 72.61(2); at. no. 32; m.p. 938.25°C; b.p. 2833°C; sp. gr. 5.323 (25°C); valence 2 and 4. Predicted by Mendeleev in 1871 as ekasilicon, and discovered by Winkler in 1886. The metal is found in argyrodite, a sulfide of germanium and silver; in germanite, which contains 8% of the element; in zinc ores; in coal; and in other minerals. The element is frequently obtained commercially from flue dusts of smelters processing zinc ores, and has been recovered from the by-products of combustion of certain coals. Its presence in coal insures a large reserve of the element in the years to come. Germanium can be separated from other metals by fractional distillation of its volatile tetrachloride. The tetrachloride may then be hydrolyzed to give GeO2; the dioxide can be reduced with hydrogen to give the metal. Recently developed zone-refining techniques permit the production of germanium of ultra-high purity. The element is a gray-white metalloid, and in its pure state is crystalline and brittle, retaining its luster in air at room temperature. It is a very important semiconductor material. Zone-refining techniques have led to production of crystalline germanium for semiconductor use with an impurity of only one part in 1010. Doped with arsenic, gallium, or other elements, it is used as a transistor element in thousands of electronic applications. Its application in fiber optics and infra-red optical systems now provides the largest use for germanium. Germanium is also finding many other applications including use as an alloying agent, as a phosphor in fluorescent lamps, and as a catalyst. Germanium and germanium oxide are transparent to the infrared and are used in infrared spectroscopes and other optical equipment, including extremely sensitive infrared detectors. Germanium oxide’s high index of refraction and dispersion has made it useful as a component of glasses used in wide-angle camera lenses and microscope objectives. The field of organogermanium chemistry is becoming increasingly important. Certain germanium compounds have a low mammalian toxicity, but a marked activity against certain bacteria, which makes them of interest as chemotherapeutic agents. The cost of germanium is about $10/g (99.999% purity). Thirty isotopes and isomers are known, five of which occur naturally.

Answer 9

Arsenic — (L. arsenicum, Gr. arsenikon, yellow orpiment, identified with arsenikos, male, from the belief that metals were different sexes; Arabic, Az-zernikh, the orpiment from Persian zerni-zar, gold), As; at. wt. 74.92160(2); at. no. 33; valence –3, 0, +3 or +5. Elemental arsenic occurs in two solid modifications: yellow, and gray or metallic, with specific gravities of 1.97, and 5.73, respectively. Gray arsenic, the ordinary stable form, has a triple point of 817°C and sublimes at 614°C and has a critical temperature of 1400°C. Several other allotropic forms of arsenic are reported in the literature. It is believed that Albertus Magnus obtained the element in 1250 A.D. In 1649 Schroeder published two methods of preparing the element. It is found native, in the sulfides realgar and orpiment, as arsenides and sulfarsenides of heavy metals, as the oxide, and as arsenates. Mispickel, arsenopyrite, (FeSAs) is the most common mineral, from which on heating the arsenic sublimes leaving ferrous sulfide. The element is a steel gray, very brittle, crystalline, semimetallic solid; it tarnishes in air, and when heated is rapidly oxidized to arsenous oxide (As2O3) with the odor of garlic. Arsenic and its compounds are poisonous. Exposure to arsenic and its compounds should not exceed 0.2 mg/m3 as elemental As during an 8-h work day. These values, however, are being studied, and may be lowered. Arsenic is also used in bronzing, pyrotechny, and for hardening and improving the sphericity of shot. The most important compounds are white arsenic (As2O3), the sulfide, Paris green 3Cu(AsO2)2 · Cu(C2H3O2)2, calcium arsenate, and lead arsenate; the last three have been used as agricultural insecticides and poisons. Marsh’s test makes use of the formation and ready decomposition of arsine (AsH3). Arsenic is available in high-purity form. It is finding increasing uses as a doping agent in solid-state devices such as transistors. Gallium arsenide is used as a laser material to convert electricity directly into coherent light. Natural arsenic is made of one isotope 75As. Thirty other radioactive isotopes and isomers are known. Arsenic (99%) costs about $75/50g. Purified arsenic (99.9995%) costs about $50/g.

Answer 10

Bromine — (Gr. bromos, stench), Br; at. wt. 79.904(1); at. no. 35; m.p. –7.2°C; b.p. 58.8°C; tc 315°C; density of gas 7.59 g/l, liquid 3.12 (20°C); valence 1, 3, 5, or 7. Discovered by Balard in 1826, but not prepared in quantity until 1860. A member of the halogen group of elements, it is obtained from natural brines from wells in Michigan and Arkansas. Little bromine is extracted today from seawater, which contains only about 85 ppm. Bromine is the only liquid nonmetallic element. It is a heavy, mobile, reddish-brown liquid, volatilizing readily at room temperature to a red vapor with a strong disagreeable odor, resembling chlorine, and having a very irritating effect on the eyes and throat; it is readily soluble in water or carbon disulfide, forming a red solution, is less active than chlorine but more so than iodine; it unites readily with many elements and has a bleaching action; when spilled on the skin it produces painful sores. It presents a serious health hazard, and maximum safety precautions should be taken when handling it. Much of the bromine output in the U.S. was used in the production of ethylene dibromide, a lead scavenger used in making gasoline antiknock compounds. Lead in gasoline, however, has been drastically reduced, due to environmental considerations. This will greatly affect future production of bromine. Bromine is also used in making fumigants, flameproofing agents, water purification compounds, dyes, medicinals, sanitizers, inorganic bromides for photography, etc. Organic bromides are also important. Natural bromine is made of two isotopes, 79Br and 81Br. Thirty-four isotopes and isomers are known. Bromine (99.8%) costs about $70/kg.

Answer 11

Selenium — (Gr. Selene, moon), Se; at. wt. 78.96(3); at. no. 34; m.p. (gray) 221°C; b.p. (gray) 685°C; sp. gr. (gray) 4.79, (vitreous) 4.28; valence –2, +4, or +6. Discovered by Berzelius in 1817, who found it associated with tellurium, named for the earth. Selenium is found in a few rare minerals, such as crooksite and clausthalite. In years past it has been obtained from flue dusts remaining from processing copper sulfide ores, but the anode muds from electrolytic copper refineries now provide the source of most of the world’s selenium. Selenium is recovered by roasting the muds with soda or sulfuric acid, or by smelting them with soda and niter. Selenium exists in several allotropic forms. Three are generally recognized, but as many as six have been claimed. Selenium can be prepared with either an amorphous or crystalline structure. The color of amorphous selenium is either red, in powder form, or black, in vitreous form. Crystalline monoclinic selenium is a deep red; crystalline hexagonal selenium, the most stable variety, is a metallic gray. Natural selenium contains six stable isotopes. Twenty-nine other isotopes and isomers have been characterized. The element is a member of the sulfur family and resembles sulfur both in its various forms and in its compounds. Selenium exhibits both photovoltaic action, where light is converted directly into electricity, and photoconductive action, where the electrical resistance decreases with increased illumination. These properties make selenium useful in the production of photocells and exposure meters for photographic use, as well as solar cells. Selenium is also able to convert a.c. electricity to d.c., and is extensively used in rectifiers. Below its melting point selenium is a p-type semiconductor and is finding many uses in electronic and solid-state applications. It is used in Xerography for reproducing and copying documents, letters, etc., but recently its use in this application has been decreasing in favor of certain organic compounds. It is used by the glass industry to decolorize glass and to make ruby-colored glasses and enamels. It is also used as a photographic toner, and as an additive to stainless steel. Elemental selenium has been said to be practically nontoxic and is considered to be an essential trace element; however, hydrogen selenide and other selenium compounds are extremely toxic, and resemble arsenic in their physiological reactions. Hydrogen selenide in a concentration of 1.5 ppm is intolerable to man. Selenium occurs in some soils in amounts sufficient to produce serious effects on animals feeding on plants, such as locoweed, grown in such soils. Selenium (99.5%) is priced at about $250/kg. It is also available in high-purity form at a cost of about $350/kg (99.999%).

Answer 12

Krypton — (Gr. kryptos, hidden), Kr; at. wt. 83.80(1); at. no. 36; m.p. –157.36°C; b.p. –153.22 ± 0.10°C; tc -63.74°C; density 3.733 g/l (0°C); valence usually 0. Discovered in 1898 by Ramsay and Travers in the residue left after liquid air had nearly boiled away. Krypton is present in the air to the extent of about 1 ppm. The atmosphere of Mars has been found to contain 0.3 ppm of krypton. It is one of the “noble” gases. It is characterized by its brilliant green and orange spectral lines. Naturally occurring krypton contains six stable isotopes. Thirty other unstable isotopes and isomers are now recognized. The spectral lines of krypton are easily produced and some are very sharp. In 1960 it was internationally agreed that the fundamental unit of length, the meter, should be defined in terms of the orange-red spectral line of 86Kr. This replaced the standard meter of Paris, which was defined in terms of a bar made of a platinum-iridium alloy. In October 1983 the meter, which originally was defined as being one ten millionth of a quadrant of the earth’s polar circumference, was again redefined by the International Bureau of Weights and Measures as being the length of path traveled by light in a vacuum during a time interval of 1/299,792,458 of a second. Solid krypton is a white crystalline substance with a face-centered cubic structure which is common to all the “rare gases”. While krypton is generally thought of as a rare gas that normally does not combine with other elements to form compounds, it now appears that the existence of some krypton compounds is established. Krypton difluoride has been prepared in gram quantities and can be made by several methods. A higher fluoride of krypton and a salt of an oxyacid of krypton also have been reported. Molecule-ions of ArKr+ and KrH+ have been identified and investigated, and evidence is provided for the formation of KrXe or KrXe+. Krypton clathrates have been prepared with hydroquinone and phenol. 85Kr has found recent application in chemical analysis. By imbedding the isotope in various solids, kryptonates are formed. The activity of these kryptonates is sensitive to chemical reactions at the surface. Estimates of the concentration of reactants are therefore made possible. Krypton is used in certain photographic flash lamps for high-speed photography. Uses thus far have been limited because of its high cost. Krypton gas presently costs about $690/100 L.

Answer 13

Rubidium — (L. rubidus, deepest red), Rb; at. wt. 85.4678(3); at. no. 37; m.p. 39.31°C; b.p. 688°C; sp. gr. (solid) 1.532 (20°C), (liquid) 1.475 (39°C); valence 1, 2, 3, 4. Discovered in 1861 by Bunsen and Kirchoff in the mineral lepidolite by use of the spectroscope. The element is much more abundant than was thought several years ago. It is now considered to be the 16th most abundant element in the earth’s crust. Rubidium occurs in pollucite, carnallite, leucite, and zinnwaldite, which contains traces up to 1%, in the form of the oxide. It is found in lepidolite to the extent of about 1.5%, and is recovered commercially from this source. Potassium minerals, such as those found at Searles Lake, California, and potassium chloride recovered from brines in Michigan also contain the element and are commercial sources. It is also found along with cesium in the extensive deposits of pollucite at Bernic Lake, Manitoba. Rubidium can be liquid at room temperature. It is a soft, silvery-white metallic element of the alkali group and is the second most electropositive and alkaline element. It ignites spontaneously in air and reacts violently in water, setting fire to the liberated hydrogen. As with other alkali metals, it forms amalgams with mercury and it alloys with gold, cesium, sodium, and potassium. It colors a flame yellowish violet. Rubidium metal can be prepared by reducing rubidium chloride with calcium, and by a number of other methods. It must be kept under a dry mineral oil or in a vacuum or inert atmosphere. Thirty five isotopes and isomers of rubidium are known. Naturally occurring rubidium is made of two isotopes, 85Rb and 87Rb. Rubidium-87 is present to the extent of 27.83% in natural rubidium and is a beta emitter with a half-life of 4.9 × 1010 years. Ordinary rubidium is sufficiently radioactive to expose a photographic film in about 30 to 60 days. Rubidium forms four oxides: Rb2O, Rb2O2, Rb2O3, Rb2O4. Because rubidium can be easily ionized, it has been considered for use in “ion engines” for space vehicles; however, cesium is somewhat more efficient for this purpose. It is also proposed for use as a working fluid for vapor turbines and for use in a thermoelectric generator using the magnetohydrodynamic principle where rubidium ions are formed by heat at high temperature and passed through a magnetic field. These conduct electricity and act like an armature of a generator thereby generating an electric current. Rubidium is used as a getter in vacuum tubes and as a photocell component. It has been used in making special glasses. RbAg4I5 is important, as it has the highest room conductivity of any known ionic crystal. At 20°C its conductivity is about the same as dilute sulfuric acid. This suggests use in thin film batteries and other applications. The present cost in small quantities is about $50/g (99.8% pure).

Answer 14

Yttrium — (Ytterby, village in Sweden near Vauxholm), Y; at. wt. 88.90585(2); at. no. 39; m.p. 1522°C; b.p. 3345°C; sp. gr. 4.469 (25°C); valence 3. Yttria, which is an earth containing yttrium, was discovered by Gadolin in 1794. Ytterby is the site of a quarry which yielded many unusually minerals containing rare earths and other elements. This small town, near Stockholm, bears the honor of giving names to erbium, terbium, and ytterbium as well as yttrium. In 1843 Mosander showed that yttria could be resolved into the oxides (or earths) of three elements. The name yttria was reserved for the most basic one; the others were named erbia and terbia. Yttrium occurs in nearly all of the rare-earth minerals. Analysis of lunar rock samples obtained during the Apollo missions show a relatively high yttrium content. It is recovered commercially from monazite sand, which contains about 3%, and from bastnasite, which contains about 0.2%. Wohler obtained the impure element in 1828 by reduction of the anhydrous chloride with potassium. The metal is now produced commercially by reduction of the fluoride with calcium metal. It can also be prepared by other techniques. Yttrium has a silvermetallic luster and is relatively stable in air. Turnings of the metal, however, ignite in air if their temperature exceeds 400°C, and finely divided yttrium is very unstable in air. Yttrium oxide is one of the most important compounds of yttrium and accounts for the largest use. It is widely used in making YVO4 europium, and Y2O3 europium phosphors to give the red color in color television tubes. Many hundreds of thousands of pounds are now used in this application. Yttrium oxide also is used to produce yttrium-iron-garnets, which are very effective microwave filters. Yttrium iron, aluminum, and gadolinium garnets, with formulas such as Y3Fe5O12 and Y3Al5O12, have interesting magnetic properties. Yttrium iron garnet is also exceptionally efficient as both a transmitter and transducer of acoustic energy. Yttrium aluminum garnet, with a hardness of 8.5, is also finding use as a gemstone (simulated diamond). Small amounts of yttrium (0.1 to 0.2%) can be used to reduce the grain size in chromium, molybdenum, zirconium, and titanium, and to increase strength of aluminum and magnesium alloys. Alloys with other useful properties can be obtained by using yttrium as an additive. The metal can be used as a deoxidizer for vanadium and other nonferrous metals. The metal has a low cross section for nuclear capture. 90Y, one of the isotopes of yttrium, exists in equilibrium with its parent 90Sr, a product of atomic explosions. Yttrium has been considered for use as a nodulizer for producing nodular cast iron, in which the graphite forms compact nodules instead of the usual flakes. Such iron has increased ductility. Yttrium is also finding application in laser systems and as a catalyst for ethylene polymerization.It has also potential use in ceramic and glass formulas, as the oxide has a high melting point and imparts shock resistance and low expansion characteristics to glass. Natural yttrium contains but one isotope, 89Y. Fortythree other unstable isotopes and isomers have been characterized. Yttrium metal of 99.9% purity is commercially available at a cost of about $5/g.

Answer 15

Strontium — (Strontian, town in Scotland), Sr; at. wt. 87.62(1); at. no. 38; m.p. 777°C; b.p. 1382°C; sp. gr. 2.54; valence 2. Isolated by Davey by electrolysis in 1808; however, Adair Crawford in 1790 recognized a new mineral (strontianite) as differing from other barium minerals (baryta). THE ELEMENTS (continued) 4-30 Strontium is found chiefly as celestite (SrSO4) and strontianite (SrCO3). Celestite is found in Mexico, Turkey, Iran, Spain, Algeria, and in the U.K. The U.S. has no active celestite mines. The metal can be prepared by electrolysis of the fused chloride mixed with potassium chloride, or is made by reducing strontium oxide with aluminum in a vacuum at a temperature at which strontium distills off. Three allotropic forms of the metal exist, with transition points at 235 and 540°C. Strontium is softer than calcium and decomposes water more vigorously. It does not absorb nitrogen below 380°C. It should be kept under mineral oil to prevent oxidation. Freshly cut strontium has a silvery appearance, but rapidly turns a yellowish color with the formation of the oxide. The finely divided metal ignites spontaneously in air. Volatile strontium salts impart a beautiful crimson color to flames, and these salts are used in pyrotechnics and in the production of flares. Natural strontium is a mixture of four stable isotopes. Thirty-two other unstable isotopes and isomers are known to exist. Of greatest importance is 90Sr with a half-life of 29 years. It is a product of nuclear fallout and presents a health problem. This isotope is one of the best long-lived high-energy beta emitters known, and is used in SNAP (Systems for Nuclear Auxiliary Power) devices. These devices hold promise for use in space vehicles, remote weather stations, navigational buoys, etc., where a lightweight, long-lived, nuclear-electric power source is needed. The major use for strontium at present is in producing glass for color television picture tubes. All color TV and cathode ray tubes sold in the U.S. are required by law to contain strontium in the face plate glass to block X-ray emission. Strontium also improves the brilliance of the glass and the quality of the picture. It has also found use in producing ferrite magnets and in refining zinc. Strontium titanate is an interesting optical material as it has an extremely high refractive index and an optical dispersion greater than that of diamond. It has been used as a gemstone, but it is very soft. It does not occur naturally. Strontium metal (99% pure) costs about $220/kg.

Answer 16

Zirconium — (Syriac, zargun, color of gold), Zr; at. wt. 91.224(2); at. no. 40; m.p. 1855°C; b.p. 4409°C; sp. gr. 6.506 (20°C); valence +2, +3, and +4. The name zircon may have originated from the Syriac word zargono, which describes the color of certain gemstones now known as zircon, jargon, hyacinth, jacinth, or ligure.This mineral, or its variations, is mentioned in biblical writings. These minerals were not known to contain this element until Klaproth, in 1789, analyzed a jargon from Sri Lanka and found a new earth, which Werner named zircon (silex circonius), and Klaproth called Zirkonerde (zirconia). The impure metal was first isolated by Berzelius in 1824 by heating a mixture of potassium and potassium zirconium fluoride in a small iron tube. Pure zirconium was first prepared in 1914. Very pure zirconium was first produced in 1925 by van Arkel and de Boer by an iodide decomposition process they developed. Zirconium is found in abundance in S-type stars, and has been identified in the sun and meteorites. Analyses of lunar rock samples obtained during the various Apollo missions to the moon show a surprisingly high zirconium oxide content, compared with terrestial rocks. Naturally occurring zirconium contains five isotopes. Thirty-one other radioactive isotopes and isomers are known to exist. Zircon, ZrSiO4, the principal ore, is found in deposits in Florida, South Carolina, Australia, South Africa, and elsewhere. Baddeleyite, found in Brazil, is an important zirconium mineral. It is principally pure ZrO2in crystalline form having a hafnium content of about 1%. Zirconium also occurs in some 30 other recognized mineral species. Zirconium is produced commercially by reduction of the chloride with magnesium (the Kroll Process), and by other methods. It is a grayish-white lustrous metal. When finely divided, the metal may ignite spontaneously in air, especially at elevated temperatures. The solid metal is much more difficult to ignite. The inherent toxicity of zirconium compounds is low. Hafnium is invariably found in zirconium ores, and the separation is difficult. Commercial-grade zirconium contains from 1 to 3% hafnium. Zirconium has a low absorption cross section for neutrons, and is therefore used for nuclear energy applications, such as for cladding fuel elements. Commercial nuclear power generation now takes more than 90% of zirconium metal production. Reactors of the size now being made may use as much as a half-million lineal feet of zirconium alloy tubing. Reactor-grade zirconium is essentially free of hafnium. Zircaloy® is an important alloy developed specifically for nuclear applications. Zirconium is exceptionally resistant to corrosion by many common acids and alkalis, by sea water, and by other agents. It is used extensively by the chemical industry where corrosive agents are employed. Zirconium is used as a getter in vacuum tubes, as an alloying agent in steel, in surgical appliances, photoflash bulbs, explosive primers, rayon spinnerets, lamp filaments, etc. It is used in poison ivy lotions in the form of the carbonate as it combines with urushiol. With niobium, zirconium is superconductive at low temperatures and is used to make superconductive magnets, which offer hope of direct large-scale generation of electric power. Alloyed with zinc, zirconium becomes magnetic at temperatures below 35 K. Zirconium oxide (zircon) has a high index of refraction and is used as a gem material. The impure oxide, zirconia, is used for laboratory crucibles that will withstand heat shock, for linings of metallurgical furnaces, and by the glass and ceramic industries as a refractory material. Its use as a refractory material accounts for a large share of all zirconium consumed. Zirconium tungstate is an unusual material that shrinks, rather than expands, when heated. While this compound has been known for more than 30 years, it is only now that it is being studied to determine the nature of this unusual behavior. A few other compounds are known to possess this property, but they tend to shrink in one direction, while they stretch out in others in order to maintain an overall volume. Zirconium tungstate shrinks in all directions over a wide temperature range of from near absolute zero to +777°C. This material is being considered for use in very small computer chips, which are subject to severe temperature changes. It is also being considered for use in composite materials where thermal expansion may be a problem. Zirconium of about 99.5% purity is available at a cost of about $2000/kg or about $4/g.

Answer 17

Niobium — (Niobe, daughter of Tantalus), Nb; or Columbium (Columbia, name for America); at. wt. 92.90638(2); at. no. 41; m.p. 2477°C; b.p. 4744°C, sp. gr. 8.57 (20°C); valence 2, 3, 4?, 5. Discovered in 1801 by Hatchett in an ore sent to England more that a century before by John Winthrop the Younger, first governor of Connecticut. The metal was first prepared in 1864 by Blomstrand, who reduced the chloride by heating it in a hydrogen atmosphere. The name niobium was adopted by the International Union of Pure and Applied Chemistry in 1950 after 100 years of controversy. Many leading chemical societies and government organizations refer to it by this name. Most metallurgists, leading metal societies, and all but one of the leading U.S. commercial producers, however, still refer to the metal as “columbium”. The element is found in niobite(or columbite), niobite-tantalite, pyrochlore, and euxenite. Large deposits of niobium have been found associated with carbonatites (carbon-silicate rocks), as a constituent of pyrochlore. Extensive ore reserves are found in Canada, Brazil, Congo-Kinshasa, Rwanda, and Australia. The metal can be isolated from tantalum, and prepared in several ways. It is a shiny, white, soft, and ductile metal, and takes on a bluish cast when exposed to air at room temperatures for a long time. The metal starts to oxidize in air at 200°C, and when processed at even moderate temperatures must be placed in a protective atmosphere. It is used in arc-welding rods for stabilized grades of stainless steel. Thousands of pounds of niobium have been used in advance air frame systems such as were used in the Gemini space program. It has also found use in super-alloys for applications such as jet engine components, rocket subassemblies, and heat-resisting equipment. The element has superconductive properties; superconductive magnets have been made with Nb-Zr wire, which retains its superconductivity in strong magnetic fields. This type of application offers hope of direct large-scale generation of electric power. Natural niobium is composed of only one isotope, 93Nb. Forty-seven other isotopes and isomers of niobium are now recognized. Niobium metal (99.9% pure) is priced at about 50¢/g.

Answer 18

Molybdenum — (Gr. molybdos, lead), Mo; at. wt. 95.94(1); at. no. 42; m.p. 2623°C; b.p. 4639°C; sp. gr. 10.22 (20°C); valence 2, 3, 4?, 5?, or 6. Before Scheele recognized molybdenite as a distinct ore of a new element in 1778, it was confused with graphite and lead ore. The metal was prepared in an impure form in 1782 by Hjelm. Molybdenum does not occur native, but is obtained principally from molybdenite (MoS2). Wulfenite (PbMoO4) and powellite (Ca(MoW)O4) are also minor commercial ores. Molybdenum is also recovered as a by-product of copper and tungsten mining operations. The U.S., Canada, Chile, and China produce most of the world’s molybdenum ores. The metal is prepared from the powder made by the hydrogen reduction of purified molybdic trioxide or ammonium molybdate. The metal is silvery white, very hard, but is softer and more ductile than tungsten. It has a high elastic modulus, and only tungsten and tantalum, of the more readily available metals, have higher melting points. It is a valuable alloying agent, as it contributes to the hardenability and toughness of quenched and tempered steels. It also improves the strength of steel at high temperatures. It is used in certain nickel-based alloys, such as the “Hastelloys®” which are heat-resistant and corrosion-resistant to chemical solutions. Molybdenum THE ELEMENTS (continued) 4-20 oxidizes at elevated temperatures. The metal has found recent application as electrodes for electrically heated glass furnaces and forehearths. The metal is also used in nuclear energy applications and for missile and aircraft parts. Molybdenum is valuable as a catalyst in the refining of petroleum. It has found application as a filament material in electronic and electrical applications. Molybdenum is an essential trace element in plant nutrition. Some lands are barren for lack of this element in the soil. Molybdenum sulfide is useful as a lubricant, especially at high temperatures where oils would decompose. Almost all ultra-high strength steels with minimum yield points up to 300,000 psi(lb/in.2) contain molybdenum in amounts from 0.25 to 8%. Natural molybdenum contains seven isotopes. Thirty other isotopes and isomers are known, all of which are radioactive. Molybdenum metal costs about $1/g (99.999% purity). Molybdenum metal (99.9%) costs about $160/kg.

Answer 19

Technetium — (Gr. technetos, artificial), Tc; at. wt. (98); at. no. 43; m.p. 2157°C; b.p. 4265°C; sp. gr. 11.50 (calc.); valence 0, +2, +4, +5, +6, and +7. Element 43 was predicted on the basis of the periodic table, and was erroneously reported as having been discovered in 1925, at which time it was named masurium. The element was actually discovered by Perrier and Segre in Italy in 1937. It was found in a sample of molybdenum, which was bombarded by deuterons in the Berkeley cyclotron, and which E. Lawrence sent to these investigators. Technetium was the first element to be produced artificially. Since its discovery, searches for the element in terrestrial materials have been made without success. If it does exist, the concentration must be very small. Technetium has been found in the spectrum of S-, M-, and N-type stars, and its presence in stellar matter is leading TeamLRN THE ELEMENTS (continued) 4-31 to new theories of the production of heavy elements in the stars. Forty-three isotopes and isomers of technetium, with atomic masses ranging from 86 to 113, are known. 97Tc has a half-life of 2.6 × 106 years. 98Tc has a half-life of 4.2 × 106 years. The isomeric isotope 95mTc, with a half-life of 61 days, is useful for tracer work, as it produces energetic gamma rays. Technetium metal has been produced in kilogram quantities. The metal was first prepared by passing hydrogen gas at 1100°C over Tc2S7. It is now conveniently prepared by the reduction of ammonium pertechnetate with hydrogen. Technetium is a silvery-gray metal that tarnishes slowly in moist air. Until 1960, technetium was available only in small amounts and the price was as high as $2800/g. 99Tc is now commercially available to holders of O.R.N.L. permits at a price of $83/g plus packing charges. 99Tc is available at a cost of $1.56/μCi. The chemistry of technetium is said to be similar to that of rhenium. Technetium dissolves in nitric acid, aqua regia, and conc. sulfuric acid, but is not soluble in hydrochloric acid of any strength. The element is a remarkable corrosion inhibitor for steel. It is reported that mild carbon steels may be effectively protected by as little as 55 ppm of KTcO4 in aerated distilled water at temperatures up to 250°C. This corrosion protection is limited to closed systems, since technetium is radioactive and must be confined. 99Tc has a specific activity of 6.2 × 108 Bq/g. Activity of this level must not be allowed to spread. 99Tc is a contamination hazard and should be handled in a glove box. The metal is an excellent superconductor at 11°K and below.

Answer 20

Ruthenium — (L. Ruthenia, Russia), Ru; at. wt. 101.07(2); at. no. 44, m.p. 2334°C; b.p. 4150°C; sp. gr. 12.41 (20°C); valence 0, 1, 2, 3, 4, 5, 6, 7, 8. Berzelius and Osann in 1827 examined the residues left after dissolving crude platinum from the Ural mountains in aqua regia. While Berzelius found no unusual metals, Osann thought he found three new metals, one of which he named ruthenium. In 1844 Klaus, generally recognized as the discoverer, showed that Osann’s ruthenium oxide was very impure and that it contained a new metal. Klaus obtained 6 g of ruthenium from the portion of crude platinum that is insoluble in aqua regia. A member of the platinum group, ruthenium occurs native with other members of the group in ores found in the Ural mountains and in North and South America. It is also found along with other platinum metals in small but commercial quantities in pentlandite of the Sudbury, Ontario, nickel-mining region, and in pyroxinite deposits of South Africa. Natural ruthenium contains seven isotopes. Twenty-eight other isotopes and isomers are known, all of which are radioactive. The metal is isolated commercially by a complex chemical process, the final stage of which is the hydrogen reduction of ammonium ruthenium chloride, which yields a powder. The powder is consolidated by powder metallurgy techniques or by argon-arc welding. Ruthenium is a hard, white metal and has four crystal modifications. It does not tarnish at room temperatures, but oxidizes in air at about 800°C. The metal is not attacked by hot or cold acids or aqua regia, but when potassium chlorate is added to the solution, it oxidizes explosively. It is attacked by halogens, hydroxides, etc. Ruthenium can be plated by electrodeposition or by thermal TeamLRN THE ELEMENTS (continued) 4-27 decomposition methods. The metal is one of the most effective hardeners for platinum and palladium, and is alloyed with these metals to make electrical contacts for severe wear resistance. A ruthenium-molybdenum alloy is said to be superconductive at 10.6 K. The corrosion resistance of titanium is improved a hundredfold by addition of 0.1% ruthenium. It is a versatile catalyst. Hydrogen sulfide can be split catalytically by light using an aqueous suspension of CdS particles loaded with ruthenium dioxide. It is thought this may have application to removal of H2S from oil refining and other industrial processes. Compounds in at least eight oxidation states have been found, but of these, the +2. +3. and +4 states are the most common. Ruthenium tetroxide, like osmium tetroxide, is highly toxic. In addition, it may explode. Ruthenium compounds show a marked resemblance to those of osmium. The metal is priced at about $25/g (99.95% pure).

Answer 21

Rhodium — (Gr. rhodon, rose), Rh; at. wt. 102.90550(3); at. no. 45; m.p. 1964°C; b.p. 3695°C; sp. gr. 12.41 (20°C); valence 2, 3, 4, 5, and 6. Wollaston discovered rhodium in 1803-4 in crude platinum ore he presumably obtained from South America. Rhodium occurs native with other platinum metals in river sands of the Urals and in North and South America. It is also found with other platinum metals in the copper-nickel sulfide ores of the Sudbury, Ontario region. Although the quantity occurring here is very small, the large tonnages of nickel processed make the recovery commercially feasible. The annual world production of rhodium in 1999 was only about 9000 kg. The metal is silvery white and at red heat slowly changes in air to the sesquioxide. At higher temperatures it converts back to the element. Rhodium has a higher melting point and lower density than platinum. Its major use is as an alloying agent to harden platinum and palladium. Such alloys are used for furnace windings, thermocouple elements, bushings for glass fiber production, electrodes for aircraft spark plugs, and laboratory crucibles. It is useful as an electrical contact material as it has a low electrical resistance, a low and stable contact resistance, and is highly resistant to corrosion. Plated rhodium, produced by electroplating or evaporation, is exceptionally hard and is used for optical instruments. It has a high reflectance and is hard and durable. Rhodium is also used for jewelry, for decoration, and as a catalyst. Fifty-two isotopes and isomers are now known. Rhodium metal (powder) costs about $180/g (99.9%).

Answer 22

Palladium — (named after the asteroid Pallas, discovered about the same time; Gr. Pallas, goddess of wisdom), Pd. at. wt. 106.42(1) at. no. 46; m.p. 1554.9°C; b.p. 2963°C; sp. gr. 12.02 (20°C); valence 2, 3, or 4. Discovered in 1803 by Wollaston. Palladium is found along with platinum and other metals of the platinum group in deposits of Russia, South Africa, Canada (Ontario), and elsewhere. Natural palladium contains six stable isotopes. Twenty-nine other isotopes are recognized, all of which are radioactive. It is frequently found associated with the nickel-copper deposits such as those found in Ontario. Its separation from the platinum metals depends upon the type of ore in which it is found. It is a steel-white metal, does not tarnish in air, and is the least dense and lowest melting of the platinum group of metals. When annealed, it is soft and ductile; cold working greatly increases its strength and hardness. Palladium is attacked by nitric and sulfuric acid. At room temperatures the metal has the unusual property of absorbing up to 900 times its own volume of hydrogen, possibly forming Pd2H. It is not yet clear if this a true compound. Hydrogen readily diffuses through heated palladium and this provides a means of purifying the gas. Finely divided palladium is a good catalyst and is used for hydrogenation and dehydrogenation reactions. It is alloyed and used in jewelry trades. White gold is an alloy of gold decolorized by the addition of palladium. Like gold, palladium can be beaten into leaf as thin as 1/250,000 in. The metal is used in dentistry, watchmaking, and in making surgical instruments and electrical contacts. Palladium recently has been substituted for higher priced platinum in catalytic converters by some automobile companies. This has caused a large increase in the cost of palladium. The price of the two metals are now, in 2002, about the same. Palladium, however, is less resistant to poisoning by sulfur and lead, than platinum, but it may prove useful in controlling emissions from diesel vehicles. The metal sells for about $350/tr. oz. ($11/g).

Answer 23

Silver — (Anglo-Saxon, Seolfor siolfur), Ag (L. argentum), at. wt. 107.8682(2); at. no. 47; m.p. 961.78°C; b.p. 2162°C; sp. gr. 10.50 (20°C); valence 1, 2. Silver has been known since ancient times. It is mentioned in Genesis. Slag dumps in Asia Minor and on islands in the Aegean Sea indicate that man learned to separate silver from lead as early as 3000 B.C. Silver occurs native and in ores such as argentite (Ag2S) and horn silver (AgCl); lead, lead-zinc, copper, gold, and copper-nickel ores are principal sources. Mexico, Canada, Peru, and the U.S. are the principal silver producers in the western hemisphere. Silver is also recovered during electrolytic refining of copper. Commercial fine silver contains at least 99.9% silver. Purities of 99.999+% are available commercially. Pure silver has a brilliant white metallic luster. It is a little harder than gold and is very ductile and malleable, being exceeded only by gold and perhaps palladium. Pure silver has the highest electrical and thermal conductivity of all metals, and possesses the lowest contact resistance. It is stable in pure air and water, but tarnishes when exposed to ozone, hydrogen sulfide, or air containing sulfur. The alloys of silver are important. Sterling silver is used for jewelry, silverware, etc. where appearance is paramount. This alloy contains 92.5% silver, the remainder being copper or some other metal. Silver is of utmost importance in photography, about 30% of the U.S. industrial consumption going into this application. It is used for dental alloys. Silver is used in making solder and brazing alloys, electrical contacts, and high capacity silver-zinc and silver-cadmium batteries. Silver paints are used for making printed circuits. It is used in mirror production and may be deposited on glass or metals by chemical deposition, electrodeposition, or by evaporation. When freshly deposited, it is the best reflector of visible light known, but is rapidly tarnishes and loses much of its reflectance. It is a poor reflector of ultraviolet. Silver fulminate (Ag2C2N2O2), a powerful explosive, is sometimes formed during the silvering process. Silver iodide is used in seeding clouds to produce rain. Silver chloride has interesting optical properties as it can be made transparent; it also is a cement for glass. Silver nitrate, or lunar caustic, the most important silver compound, is used extensively in photography. While silver itself is not considered to be toxic, most of its salts are poisonous. Natural silver contains two stable isotopes. Fifty-six other radioactive isotopes and isomers are known. Silver compounds can be absorbed in the circulatory system and reduced silver deposited in the various tissues of the body. A condition, known as argyria, results with a greyish pigmentation of the skin and mucous membranes. Silver has germicidal effects and kills many lower organisms effectively without harm to higher animals. Silver for centuries has been used traditionally for coinage by many countries of the world. In recent times, however, consumption of silver has at times greatly exceeded the output. In 1939, the price of silver was fixed by the U.S. Treasury at 71¢/troy oz., and at 90.5¢/troy oz. in 1946. In November 1961 the U.S. Treasury suspended sales of nonmonetized silver, and the price stabilized for a time at about $1.29, the melt-down value of silver U.S. coins. The Coinage Act of 1965 authorized a change in the metallic composition of the three U.S. subsidiary denominations to clad or composite type coins. This was the first change in U.S. coinage since the monetary system was established in 1792. Clad dimes and quarters are made of an outer layer of 75% Cu and 25% Ni bonded to a central core of pure Cu. The composition of the one- and five-cent pieces remains unchanged. One-cent coins are 95% Cu and 5% Zn. Five-cent coins are 75% Cu and 25% Ni. Old silver dollars are 90% Ag and 10% Cu. Earlier subsidiary coins of 90% Ag and 10% Cu officially were to circulate alongside the clad coins; however, in practice they have largely disappeared (Gresham’s Law), as the value of the silver is now greater than their exchange value. Silver coins of other countries have largely been replaced with coins made of other metals. On June 24, 1968, the U.S. Government ceased to redeem U.S. Silver Certificates with silver. Since that time, the price of silver has fluctuated widely. As of January 2002, the price of silver was about $4.10/troy oz. (13¢/g); however the price has fluctuated considerably due to market instability. The price of silver in 2001 was only about four times the cost of the metal about 150 years ago. This has largely been caused by Central Banks disposing of some of their silver reserves and the development of more productive mines with better refining methods. Also, silver has been displaced by other metals or processes, such as digital photography.

Answer 24

Cadmium — (L. cadmia; Gr. kadmeia — ancient name for calamine, zinc carbonate), Cd; at. wt. 112.411(8); at. no. 48; m.p. 321.07°C; b.p. 767°C; sp. gr. 8.65 (20°C); valence 2. Discovered by Stromeyer in 1817 from an impurity in zinc carbonate. Cadmium most often occurs in small quantities associated with zinc ores, such as sphalerite (ZnS). Greenockite (CdS) is the only mineral of any consequence bearing cadmium. Almost all cadmium is obtained as a by-product in the treatment of zinc, copper, and lead ores. It is a soft, bluish-white metal which is easily cut with a knife. It is similar in many respects to zinc. It is a component of some of the lowest melting alloys; it is used in bearing alloys with low coefficients of friction and great resistance to fatigue; it is used extensively in electroplating, which accounts for about 60% of its use. It is also used in many types of solder, for standard E.M.F. cells, for Ni-Cd batteries, and as a barrier to control atomic fission. The market for Ni-Cd batteries is expected to grow significantly in the next few years. Cadmium compounds are used in black and white television phosphors and in blue and green phosphors for color TV tubes. It forms a number of salts, of which the sulfate is most common; the sulfide is used as a yellow pigment. Cadmium and solutions of its compounds are toxic. Failure to appreciate the toxic properties of cadmium may cause workers to be unwittingly exposed to dangerous fumes. Some silver solders, for example, contain cadmium and should be handled with care. Serious toxicity problems have been found from long-term exposure and work with cadmium plating baths. Cadmium is present in certain phosphate rocks. This has raised concerns that the long-term use of certain phosphate fertilizers might pose a health hazard from levels of cadmium that might enter the food chain. In 1927 the International Conference on Weights and Measures redefined the meter in terms of the wavelength of the red cadmium spectral line (i.e. 1 m = 1,553,164.13 wavelengths). This definition has been changed (see under TeamLRN THE ELEMENTS (continued) 4-7 Krypton). The current price of cadmium is about 50¢/g (99.5%). It is available in high purity form for about $550/kg. Natural cadmium is made of eight isotopes. Thirty four other isotopes and isomers are now known and recognized.

Answer 25

Indium — (from the brilliant indigo line in its spectrum),In; at. wt. 114.818(3); at. no. 49; m.p. 156.60°C; b.p. 2072°C; sp. gr. 7.31 (20°C); valence 1, 2, or 3. Discovered by Reich and Richter, who later isolated the metal. Indium is most frequently associated with zinc materials, and it is from these that most commercial indium is now obtained; however, it is also found in iron, lead, and copper ores. Until 1924, a gram or so constituted the world’s supply of this element in isolated form. It is probably about as abundant as silver. About 4 million troy ounces of indium are now produced annually in the Free World. Canada is presently producing more than 1,000,000 troy ounces annually. The present cost of indium is about $2 to $10/g, depending on quantity and purity. It is available in ultrapure form. Indium is a very soft, silvery-white metal with a brilliant luster. The pure metal gives a highpitched “cry” when bent. It wets glass, as does gallium. It has found application in making low-melting alloys; an alloy of 24% indium-76% gallium is liquid at room temperature. Indium is used in making bearing alloys, germanium transistors, rectifiers, thermistors, liquid crystal displays, high definition television, batteries, and photoconductors. It can be plated onto metal and evaporated onto glass, forming a mirror as good as that made with silver but with more resistance to atmospheric corrosion. There is evidence that indium has a low order of toxicity; however, care should be taken until further information is available. Seventy isotopes and isomers are now recognized (more than any other element). Natural indium contains two isotopes. One is stable. The other, 115In, comprising 95.71% of natural indium is slightly radioactive with a very long half-life.

Answer 26

Tin — (anglo-Saxon, tin), Sn (L. stannum); at. wt. 118.710(7); at. no. 50; m.p. 231.93°C; b.p. 2602°C; sp. gr. (gray) 5.75, (white) 7.31; valence 2, 4. Known to the ancients. Tin is found chiefly in cassiterite (SnO2). Most of the world’s supply comes from China, Indonesia, Peru, Brazil, and Bolivia. The U.S. produces almost none, although occurrences have been found in Alaska and Colorado. Tin is obtained by reducing the ore with coal in a reverberatory furnace. Ordinary tin is composed of ten stable isotopes; thirty-six unstable isotopes and isomers are also known. Ordinary tin is a silver-white metal, is malleable, somewhat ductile, and has a highly crystalline structure. Due to the breaking of these crystals, a “tin cry” is heard when a bar is bent. The element has two allotropic forms at normal pressure. On warming, gray, or α tin, with a cubic structure, changes at 13.2°C into white, or β tin, the ordinary form of the metal. White tin has a tetragonal structure. When tin is cooled below 13.2°C, it changes slowly from white to gray. This change is affected by impurities such as aluminum and zinc, and can be prevented by small additions of antimony or bismuth. This change from the α to β form is called the tin pest. Tin-lead alloys are used to make organ pipes. There are few if any uses for gray tin. Tin takes a high polish and is used to coat other metals to prevent corrosion or other chemical action. Such tin plate over steel is used in the so-called tin can for preserving food. Alloys of tin are very important. Soft solder, type metal, fusible metal, pewter, bronze, bell metal, Babbitt metal, White metal, die casting alloy, and phosphor bronze are some of the important alloys using tin. Tin resists distilled sea and soft tap water, but is attacked by strong acids, alkalis, and acid salts. Oxygen in solution accelerates the attack. When heated in air, tin forms SnO2, which is feebly acid, forming stannate salts with basic oxides. The most important salt is the chloride (SnCl2 · H2O), which is used as a reducing agent and as a mordant in calico printing. Tin salts sprayed onto glass are used to produce electrically conductive coatings. These have been used for panel lighting and for frost-free windshields. Most window glass is now made by floating molten glass on molten tin (float glass) to produce a flat surface (Pilkington process). Of recent interest is a crystalline tinniobium alloy that is superconductive at very low temperatures. This promises to be important in the construction of superconductive magnets that generate enormous field strengths but use practically no power. Such magnets, made of tin-niobium wire, weigh but a few pounds and produce magnetic fields that, when started with a small battery, are comparable to that of a 100 ton electromagnet operated continuously with a large power supply. The small amount of tin found in canned foods is quite harmless. The agreed limit of tin content in U.S. foods is 300 mg/kg. The trialkyl and triaryl tin compounds are used as biocides and must be handled carefully. Over the past 25 years the price of commercial tin has varied from 50¢/lb ($1.10/kg) to its present price of about $6/kg in January 2002. Tin (99.99% pure) costs about $260/kg.

Answer 27

Tellurium — (L. tellus, earth), Te; at. wt. 127.60(3); at. no. 52; m.p. 449.51°C; b.p. 988°C; sp. gr. 6.24 (20°C); valence 2, 4, or 6. Discovered by Muller von Reichenstein in 1782; named by Klaproth, who isolated it in 1798. Tellurium is occasionally found native, but is more often found as the telluride of gold (calaverite), and combined with other metals. It is recovered commercially from the anode muds produced during the electrolytic refining of blister copper. The U.S., Canada, Peru, and Japan are the largest Free World producers of the element. Crystalline tellurium has a silverywhite appearance, and when pure exhibits a metallic luster. It is brittle and easily pulverized. Amorphous tellurium is formed by precipitating tellurium from a solution of telluric or tellurous acid. Whether this form is truly amorphous, or made of minute crystals, is open to question. Tellurium is a ptype semiconductor, and shows greater conductivity in certain directions, depending on alignment of the atoms. Its conductivity increases slightly with exposure to light. It can be doped with silver, copper, gold, tin, or other elements. In air, tellurium burns with a greenish-blue flame, forming the dioxide. Molten tellurium corrodes iron, copper, and stainless steel. Tellurium and its compounds are probably toxic and should be handled with care. Workmen exposed to as little as 0.01 mg/m3 of air, or less, develop “tellurium breath,” which has a garlic-like odor. Forty two isotopes and isomers of tellurium are known, with atomic masses ranging from 106 to 138. Natural tellurium consists of eight isotopes, two of which are radioactive with very long halflives. Tellurium improves the machinability of copper and stainless steel, and its addition to lead decreases the corrosive action of sulfuric acid on lead and improves its strength and hardness. Tellurium catalysts are used in the oxidation of organic compounds and are used in hydrogenation and halogenation reactions. Tellurium is also used in electronic and semi-conductor devices. It is also used as a basic ingredient in blasting caps, and is added to cast iron for chill control. Tellurium is used in ceramics. Bismuth telluride has been used in thermoelectric devices. Tellurium costs about 50¢/g, with a purity of about 99.5%. The metal with a purity of 99.9999% costs about $5/g.

Answer 28

Antimony — (Gr. anti plus monos — a metal not found alone), Sb; at. wt. 121.760(1); at. no. 51; m.p. 630.63°C; b.p. 1587°C; sp. gr. 6.691 (20°C); valence 0, –3, +3, or +5. Antimony was recognized in compounds by the ancients and was known as a metal at the beginning of the 17th century and possibly much earlier. It is not abundant, but is found in over 100 mineral species. It is sometimes found native, but more frequently as the sulfide, stibnite (Sb2S3); it is also found as antimonides of the heavy metals, and as oxides. It is extracted from the sulfide by roasting to the oxide, which is reduced by salt and scrap iron; from its oxides it is also prepared by reduction with carbon. Two allotropic forms of antimony exist: the normal stable, metallic form, and the amorphous gray form. The so-called explosive antimony is an ill-defined material always containing an appreciable amount of halogen; therefore, it no longer warrants consideration as a separate allotrope. The yellow form, obtained by oxidation of stibine, SbH3, is probably impure, and is not a distinct form. Natural antimony is made of two stable isotopes, 121Sb and 123Sb. Forty five other radioactive isotopes and isomers are now recognized. Metallic antimony is an extremely brittle metal of a flaky, crystalline texture. It is bluish white and has a metallic luster. It is not acted on by air at room temperature, but burns brilliantly when heated with the formation of white fumes of Sb2O3. It is a poor conductor of heat and electricity, and has a hardness of 3 to 3.5. Antimony, available commercially with a purity of 99.999 + %, is finding use in semiconductor technology for making infrared detectors, diodes, and Hall-effect devices. Commercial-grade antimony is widely used in alloys with percentages ranging from 1 to 20. It greatly increases the hardness and mechanical strength of lead. Batteries, antifriction alloys, type metal, small arms and tracer bullets, cable sheathing, and minor products use about half the metal produced. Compounds taking up the other half are oxides, sulfides, sodium antimonate, and antimony trichloride. These are used in manufacturing flame-proofing compounds, paints, ceramic enamels, glass, and pottery. Tartar emetic (hydrated potassium antimonyl tartate) has been used in medicine. Antimony and many of its compounds are toxic. Antimony costs about $1.30/kg or about $12/g (99.999%).

Answer 29

Iodine — (Gr. iodes, violet), I; at. wt. 126.90447(3); at. no. 53; m.p. 113.7°C; b.p. 184.4°C; tc 546°C; density of the gas 11.27 g/l; sp. gr. solid 4.93 (20°C); valence 1, 3, 5, or 7. Discovered by Courtois in 1811. Iodine, a halogen, occurs sparingly in the form of iodides in sea water from which it is assimilated by seaweeds, in Chilean saltpeter and nitrate-bearing earth, known as caliche in brines from old sea deposits, and in brackish waters from oil and salt wells. Ultrapure iodine can be obtained from the reaction of potassium iodide with copper sulfate. Several other methods of isolating the element are known. Iodine is a bluish-black, lustrous solid, volatilizing at ordinary temperatures into a blue-violet gas with an irritating odor; it forms compounds with many elements, but is less active than the other halogens, which displace it from iodides. Iodine exhibits some metallic-like properties. It dissolves readily in chloroform, carbon tetrachloride, or carbon disulfide to form beautiful purple solutions. It is only slightly soluble in water. Iodine compounds are important in organic chemistry and very useful in medicine. Forty two isotopes and isomers are recognized. Only one stable isotope, 127I is found in nature. The artificial radioisotope 131I, with a half-life of 8 days, has been used in treating the thyroid gland. The most common compounds are the iodides of sodium and potassium (KI) and the iodates (KIO3). Lack of iodine is the cause of goiter. Iodides, and thyroxin which contains iodine, are used internally in medicine, and a solution of KI and iodine in alcohol is used for external wounds. Potassium iodide finds use in photography. The deep blue color with starch solution is characteristic of the free element. Care should be taken in handling and using iodine, as contact with the skin can cause lesions; iodine vapor is intensely irritating to the eyes and mucous membranes. Elemental iodine costs about 25 to 75¢/g depending on purity and quantity.

Answer 30

Cesium — (L. caesius, sky blue), Cs; at. wt. 132.90545(2); at. no. 55; m.p. 28.44°C; b.p. 671°C; sp. gr. 1.873 (20°C); valence 1. Cesium was discovered spectroscopically by Bunsen and Kirchhoff in 1860 in mineral water from Durkheim. Cesium, an alkali metal, occurs in lepidolite, pollucite (a hydrated silicate of aluminum and cesium), and in other sources. One of the world’s richest sources of cesium is located at Bernic Lake, Manitoba. The deposits are estimated to contain 300,000 tons of pollucite, averaging 20% cesium. It can be isolated by electrolysis of the fused cyanide and by a number of other methods. Very pure, gas-free cesium can be prepared by thermal decomposition of cesium azide. The metal is characterized by a spectrum containing two bright lines in the blue along with several others in the red, yellow, and green. It is silvery white, soft, and ductile. It is the most electropositive and most alkaline element. Cesium, gallium, and mercury are the only three metals that are liquid at room temperature. Cesium reacts explosively with cold water, and reacts with ice at temperatures above –116°C. Cesium hydroxide, the strongest base known, attacks glass. Because of its great affinity for oxygen the metal is used as a “getter” in electron tubes. It is also used in photoelectric cells, as well as a catalyst in the hydrogenation of certain organic compounds. The metal has recently found application in ion propulsion systems. Cesium is used in atomic clocks, which are accurate to 5 s in 300 years. A second of time is now defined as being the duration of 9,192,631,770 periods of the radiation corresponding to the transition between the two hyper-fine levels of the ground state of the cesium-133 atom. Its chief compounds are the chloride and the nitrate. Cesium has 52 isotopes and isomers with masses ranging from 112 to 148. The present price of cesium is about $50/g (99.98%) sealed in a glass ampoule.

Answer 31

Xenon — (Gr. xenon, stranger), Xe; at. wt. 131.29(2); at. no. 54; m.p. –111.79°C; b.p. –108.12°C; tc 16.62°C; density (gas) 5.887 ± 0.009 g/l, sp. gr (liquid) 3.52 (–109°C); valence usually 0. Discovered by Ramsay and Travers in 1898 in the residue left after evaporating liquid air components. Xenon is a member of the so-called noble or “inert” gases. It is present in the atmosphere to the extent of about one part in twenty million. Xenon is present in the Martian atmosphere to the extent of 0.08 ppm. The element is found in the gases evolved from certain mineral springs, and is commercially obtained by extraction from liquid air. Natural xenon is composed of nine stable isotopes. In addition to these, thirty five unstable isotopes and isomers have been characterized. Before 1962, it had generally been assumed that xenon and other noble gases were unable to form compounds. Evidence has 232 Th(n, γ )→233Thβ→233 Paβ→233U 238U(n, γ )→239Uβ→239Npβ→239 Pu TeamLRN THE ELEMENTS (continued) 4-35 been mounting in the past few years that xenon, as well as other members of the zero valence elements, do form compounds. Among the “compounds” of xenon now reported are xenon hydrate, sodium perxenate, xenon deuterate, difluoride, tetrafluoride, hexafluoride, and XePtF6 and XeRhF6. Xenon trioxide, which is highly explosive, has been prepared. More than 80 xenon compounds have been made with xenon chemically bonded to fluorine and oxygen. Some xenon compounds are colored. Metallic xenon has been produced, using several hundred kilobars of pressure. Xenon in a vacuum tube produces a beautiful blue glow when excited by an electrical discharge. The gas is used in making electron tubes, stroboscopic lamps, bactericidal lamps, and lamps used to excite ruby lasers for generating coherent light. Xenon is used in the atomic energy field in bubble chambers, probes, and other applications where its high molecular weight is of value. The perxenates are used in analytical chemistry as oxidizing agents. 133Xe and 135Xe are produced by neutron irradiation in air cooled nuclear reactors. 133Xe has useful applications as a radioisotope. The element is available in sealed glass containers for about $20/l of gas at standard pressure. Xenon is not toxic, but its compounds are highly toxic because of their strong oxidizing characteristics.

Answer 32

Barium — (Gr. barys, heavy), Ba; at. wt. 137.327(7), at. no. 56; m.p. 727°C; b.p. 1897°C; sp. gr. 3.5 (20°C); valence 2. Baryta was distinguished from lime by Scheele in 1774; the element was discovered by Sir Humphrey Davy in 1808. It is found only in combination with other elements, chiefly in barite or heavy spar (sulfate) and witherite (carbonate) and is prepared by electrolysis of the chloride. Large deposits of barite are found in China, Germany, India, Morocco, and in the U.S. Barium is a metallic element, soft, and when pure is silvery white like lead; it belongs to the alkaline earth group, resembling calcium chemically. The metal oxidizes very easily and should be kept under petroleum or other suitable oxygen-free liquids to exclude air. It is decomposed by water or alcohol. The metal is used as a “getter” in vacuum tubes. The most important compounds are the peroxide (BaO2), chloride, sulfate, carbonate, nitrate, and chlorate. Lithopone, a pigment containing barium sulfate and zinc sulfide, has good covering power, and does not darken in the presence of sulfides. The sulfate, as permanent white or blanc fixe, is also used in paint, in X-ray diagnostic work, and in glassmaking. Barite is extensively used as a weighting agent in oilwell drilling fluids, and also in making rubber. The carbonate has been used as a rat poison, while the nitrate and chlorate give green colors in pyrotechny. The impure sulfide phosphoresces after exposure to the light. The compounds and the metal are not expensive. Barium metal (99.2 + % pure) costs about $3/g. All barium compounds that are water or acid soluble are poisonous. Naturally occurring barium is a mixture of seven stable isotopes. Thirty six other radioactive isotopes and isomers are known to exist.

Answer 33

Lanthanum — (Gr. lanthanein, to lie hidden), La; at. wt. 138.9055(2); at. no. 57; m.p. 918°C; b.p. 3464°C; sp. gr. 6.145 (25°C); valence 3. Mosander in 1839 extracted a new earth lanthana, from impure cerium nitrate, and recognized the new element. Lanthanum is found in rare-earth minerals such as cerite, monazite, allanite, and bastnasite. Monazite and bastnasite are principal ores in which lanthanum occurs in percentages up to 25 and 38%, respectively. Misch metal, used in making lighter flints, contains about 25% lanthanum. Lanthanum was isolated in relatively pure form in 1923. Ion-exchange and solvent extraction techniques have led to much easier isolation of the so-called “rare-earth” elements. The availability of lanthanum and other rare earths has improved greatly in recent years. The metal can be produced by reducing the anhydrous fluoride with calcium. Lanthanum is silvery white, malleable, ductile, and soft enough to be cut with a knife. It is one of the most reactive of the rare-earth metals. It oxidizes rapidly when exposed to air. Cold water attacks lanthanum slowly, and hot water attacks it much more rapidly. The metal reacts directly with elemental carbon, nitrogen, boron, selenium, silicon, phosphorus, sulfur, and with halogens. At 310°C, lanthanum changes from a hexagonal to a face-centered cubic structure, and at 865°C it again transforms into a body-centered cubic structure. Natural lanthanum is mixture of two isotopes, one of which is stable and one of which is radioactive with a very long half-life. Thirty other radioactive isotopes are recognized. Rare-earth compounds containing lanthanum are extensively used in carbon lighting applications, especially by the motion picture industry for studio lighting and projection. This application consumes about 25% of the rare-earth compounds produced. La2O3 improves the alkali resistance of glass, and is used in making special optical glasses. Small amounts of lanthanum, as an additive, can be used to produce nodular cast iron. There is current interest in hydrogen sponge alloys containing lanthanum. These alloys take up to 400 times their own volume of hydrogen gas, and the process is reversible. Heat energy is released every time they do so; therefore these alloys have possibilities in energy conservation systems. Lanthanum and its compounds have a low to moderate acute toxicity rating; therefore, care should be taken in handling them. The metal costs about $2/g (99.9%).

Answer 34

Cerium — (named for the asteroid Ceres, which was discovered in 1801 only 2 years before the element), Ce; at. wt. 140.115(4); at. no. 58; m.p. 798°C; b.p. 3424°C; sp. gr. 6.770 (25°C); valence 3 or 4. Discovered in 1803 by Klaproth and by Berzelius and Hisinger; metal prepared by Hillebrand and Norton in 1875. Cerium is the most abundant of the metals of the so-called rare earths. It is found in a number of minerals including allanite (also known as orthite), monazite, bastnasite, cerite, and samarskite. Monazite and bastnasite are presently the two most important sources of cerium. Large deposits of monazite found on the beaches of Travancore, India, in river sands in Brazil, and deposits of allanite in the western United States, and bastnasite in Southern California will supply cerium, thorium, and the other rare-earth metals for many years to come. Metallic cerium is prepared by metallothermic reduction techniques, such as by reducing cerous fluoride with calcium, or by electrolysis of molten cerous chloride or other cerous halides. The metallothermic technique is used to produce high-purity cerium. Cerium is especially interesting because of its variable electronic structure. The energy of the inner 4f level is nearly the same as that of the outer or valence electrons, and only small amounts of energy are required to change the relative occupancy of these electronic levels. This gives rise to dual valency states. For example, a volume change of about 10% occurs when cerium is subjected to high pressures or low temperatures. It appears that the valence changes from about 3 to 4 when it is cooled or compressed. The low temperature behavior of cerium is complex. Four allotropic modifications are thought to exist: cerium at room temperature and at atmospheric pressure is known as γ cerium. Upon cooling to –16°C, γ cerium changes to β cerium. The remaining γ cerium starts to change to α cerium when cooled to –172°C, and the transformation is complete at –269°C. α Cerium has a density of 8.16; δ cerium exists above 726°C. At atmospheric pressure, liquid cerium is more dense than its solid form at the melting point. Cerium is an iron-gray lustrous metal. It is malleable, and oxidizes very readily at room temperature, especially in moist air. Except for europium, cerium is the most reactive of the “rare-earth” metals. It slowly decomposes in cold water, and rapidly in hot water. Alkali solutions and dilute and concentrated acids attack the metal rapidly. The pure metal is likely to ignite if scratched with a knife. Ceric salts are orange red or yellowish; cerous salts are usually white. Cerium is a component of misch metal, which is extensively used in the manufacture of pyrophoric alloys for cigarette lighters, etc. Natural cerium is stable and contains four isotopes. Thirty-two other radioactive isotopes and isomers are known. While cerium is not radioactive, the impure commercial grade may contain traces of thorium, which is radioactive. The oxide is an important constituent of incandescent gas mantles and it is emerging as a hydrocarbon catalyst in “self-cleaning” ovens. In this application it can be incorporated into oven walls to prevent the collection of cooking residues. As ceric sulfate it finds extensive use as a volumetric oxidizing agent in quantitative analysis. Cerium compounds are used in the manufacture of glass, both as a component and as a decolorizer. The oxide is finding increased use as a glass polishing agent instead of rouge, for it is much faster than rouge in polishing glass surfaces. Cerium compounds are finding use in automobile exhaust catalysts. Cerium is also finding use in making permanent magnets. Cerium, with other rare earths, is used in carbon-arc lighting, especially in the motion picture industry. It is also finding use as an important catalyst in petroleum refining and in metallurgical and nuclear applications. In small lots, cerium costs about $5/g (99.9%).

Answer 35

Praseodymium — (Gr. prasios, green, and didymos, twin), Pr; at. wt. 140.90765(2); at. no. 59; m.p. 931°C; b.p. 3520°C; sp. gr. 6.773; valence 3. In 1841 Mosander extracted the rare earth didymia from lanthana; in 1879, Lecoq de Boisbaudran isolated a new earth, samaria, from didymia obtained from the mineral samarskite. Six years later, in 1885, von Welsbach separated didymia into two others, praseodymia and neodymia, which gave salts of different colors. As with other rare earths, compounds of these elements in solution have distinctive sharp spectral absorption bands or lines, some of which are only a few Angstroms wide. The element occurs along with other rare-earth elements in a variety of minerals. Monazite and bastnasite are the two principal commercial sources of the rare-earth metals. Ion-exchange and solvent extraction techniques have led to much easier isolation of the rare earths and the cost has dropped greatly in the past few years. Thirty-seven isotopes and isomers are now recognized. Praseodymium can be prepared by several methods, such as by calcium reduction of the anhydrous chloride of fluoride. Misch metal, used in making cigarette lighters, contains about 5% praseodymium metal. Praseodymium is soft, silvery, malleable, and ductile. It was prepared in relatively pure form in 1931. It is somewhat more resistant to corrosion in air than europium, lanthanum, cerium, or neodymium, but it does develop a green oxide coating that spalls off when exposed to air. As with other rare-earth metals it should be kept under a light mineral oil or sealed in plastic. The rare-earth oxides, including Pr2O3, are among the most refractory substances known. Along with other rare earths, it is widely used as a core material for carbon arcs used by the motion picture industry for studio lighting and projection. Salts of praseodymium are used to color glasses and enamels; when mixed with certain other materials, praseodymium produces an intense and unusually clean yellow color in glass. Didymium glass, of which praseodymium is a component, is a colorant for welder’s goggles. The metal (99.9% pure) is priced at about $4/g.

Answer 36

Neodymium — (Gr. neos, new, and didymos, twin), Nd; at. wt. 144.24(3); at. no. 60; m.p. 1021°C; b.p. 3074°C; sp. gr. 7.008 (25°C); valence 3. In 1841, Mosander, extracted from cerite a new rose-colored oxide, which he believed contained a new element. He named the element didymium, as it was an inseparable twin brother of lanthanum. In 1885 von Welsbach separated didymium into two new elemental components, neodymia and praseodymia, by repeated fractionation of ammonium didymium nitrate. While the free metal is in misch metal, long known and used as a pyrophoric alloy for light flints, the element was not isolated in relatively pure form until 1925. Neodymium is present in misch metal to the extent of about 18%. It is present in the minerals monazite and bastnasite, which are principal sources of rare-earth metals. The element may be obtained by separating neodymium salts from other rare earths by ion-exchange or solvent extraction techniques, and by reducing anhydrous halides such as NdF3 with calcium metal. Other separation techniques are possible. The metal has a bright silvery metallic luster. Neodymium is one of the more reactive rare-earth metals and quickly tarnishes in air, forming an oxide that spalls off and exposes metal to oxidation. The metal, therefore, should be kept under light mineral oil or sealed in a plastic material. Neodymium exists in two allotropic forms, with a transformation from a double hexagonal to a body-centered cubic structure taking place at 863°C. Natural neodymium is a mixture of seven isotopes, one of which has a very long half-life. Twenty seven other radioactive isotopes and isomers are recognized. Didymium, of which neodymium is a component, is used for coloring glass to make welder’s goggles. By itself, neodymium colors glass delicate shades ranging from pure violet through wine-red and warm gray. Light transmitted through such glass shows unusually sharp absorption bands. The glass has been used in astronomical work to produce sharp bands by which spectral lines may be calibrated. Glass containing neodymium can be used as a laser material to produce coherent light. Neodymium salts are also used as a colorant for enamels. The element is also being used with iron and boron to produce extremely strong magnets having energy densities as high as 27 to 35 million gauss oersteds. These are the most compact magnets commercially available. The price of the metal is about $4/g. Neodymium has a low-to-moderate acute toxic rating. As with other rare earths, neodymium should be handled with care.

Answer 37

Promethium — (Prometheus, who, according to mythology, stole fire from heaven), Pm; at. no. 61; at. wt. (145); m.p. 1042°C; b.p. 3000°C (est.); sp. gr. 7.264 (25°C); valence 3. In 1902 Branner predicted the existence of an element between neodymium and samarium, and this was confirmed by Moseley in 1914. Unsuccessful searches were made for this predicted element over two decades, and various investigators proposed the names “illinium”, “florentium”, and “cyclonium” for this element. In 1941, workers at Ohio State University irradiated neodymium and praseodymium with neutrons, deuterons, and alpha particles, resp., and produced several new radioactivities, which most likely were those of element 61. Wu and Segre, and Bethe, in 1942, confirmed the formation; however, chemical proof of the production of element 61 was lacking because of the difficulty in separating the rare earths from each other at that time. In 1945, Marinsky, Glendenin, and Coryell made the first chemical identification by use of ionexchange chromatography. Their work was done by fission of uranium and by neutron bombardment of neodymium. These investigators named the newly discovered element. Searches for the element on earth have been fruitless, and it now appears that promethium is completely missing from the earth’s crust. Promethium, however, has been reported to be in the spectrum of the star HR465 in Andromeda. This element is being formed recently near the star’s surface, for no known isotope of promethium has a half-life longer than 17.7 years. Thirty five isotopes and isomers of promethium, with atomic masses from 130 to 158 are now known. Promethium-145,with a half-life of 17.7 years, is the most useful. Promethium-145 has a specific TeamLRN THE ELEMENTS (continued) 4-25 activity of 940 Ci/g. It is a soft beta emitter; although no gamma rays are emitted, X-radiation can be generated when beta particles impinge on elements of a high atomic number, and great care must be taken in handling it. Promethium salts luminesce in the dark with a pale blue or greenish glow, due to their high radioactivity. Ion-exchange methods led to the preparation of about 10 g of promethium from atomic reactor fuel processing wastes in early 1963. Little is yet generally known about the properties of metallic promethium. Two allotropic modifications exist. The element has applications as a beta source for thickness gages, and it can be absorbed by a phosphor to produce light. Light produced in this manner can be used for signs or signals that require dependable operation; it can be used as a nuclear-powered battery by capturing light in photocells which convert it into electric current. Such a battery, using 147Pm, would have a useful life of about 5 years. It is being used for fluorescent lighting starters and coatings for self-luminous watch dials. Promethium shows promise as a portable X-ray source, and it may become useful as a heat source to provide auxiliary power for space probes and satellites. More than 30 promethium compounds have been prepared. Most are colored. Promethium-147 is available upon special order from the Idaho National Engineering Laboratory, Idaho Falls, ID, or from the Westinghouse Hanford Co., Richland, WA.

Answer 38

Samarium — (Samarskite a mineral), Sm; at. wt. 150.36(3); at. no. 62; m.p. 1074°C; b.p. 1794°C; sp. gr (α) 7.520 (25°C); valence 2 or 3. Discovered spectroscopically by its sharp absorption lines in 1879 by Lecoq de Boisbaudran in the mineral samarskite, named in honor of a Russian mine official, Col. Samarski. Samarium is found along with other members of the rare-earth elements in many minerals, including monazite and bastnasite, which are commercial sources. The largest producer of rare earth minerals is now China, followed by the U.S., India, and Russia. It occurs in monazite to the extent of 2.8%. While misch metal containing about 1% of samarium metal, has long been used, samarium has not been isolated in relatively pure form until recent years. Ion-exchange and solvent extraction techniques have recently simplified separation of the rare earths from one another; more recently, electrochemical deposition, using an electrolytic solution of lithium citrate and a mercury electrode, is said to be a simple, fast, and highly specific way to separate the rare earths. Samarium metal can be produced by reducing the oxide with barium or lanthanum. Samarium has a bright silver luster and is reasonably stable in air. Three crystal modifications of the metal exist, with transformations at 734 and 922°C. The metal ignites in air at about 150°C. Thirty-three isotopes and isomers of samarium are now recognized. Natural samarium is a mixture of seven isotopes, three of which are unstable but have long half-lives. Samarium, along with other rare earths, is used for carbon-arc lighting for the motion picture industry. The sulfide has excellent high-temperature stability and good thermoelectric efficiencies up to 1100°C. SmCo5 has been used in making a new permanent magnet material with the highest resistance to demagnetization of any known material. It is said to have an intrinsic coercive force as high as 2200 kA/m. Samarium oxide has been used in optical glass to absorb the infrared. Samarium is used to dope calcium fluoride crystals for use in optical masers or lasers. Compounds of the metal act as sensitizers for phosphors excited in the infrared; the oxide exhibits catalytic properties in the dehydration and dehydrogenation of ethyl alcohol. It is used in infrared absorbing glass and as a neutron absorber in nuclear reactors. The metal is priced at about $3.50/g (99.9%). Little is known of the toxicity of samarium; therefore, it should be handled carefully.

Answer 39

Europium — (Europe), Eu; at. wt. 151.964(1); at. no. 63; m.p. 822°C; b.p. 1596°C; sp. gr. 5.244 (25°C); valence 2 or 3. In 1890 Boisbaudran obtained basic fractions from samarium-gadolinium concentrates which had spark spectral lines not accounted for by samarium or gadolinium. These lines subsequently have been shown to belong to europium. The discovery of europium is generally credited to Demarcay, who separated the rare earth in reasonably pure form in 1901. The pure metal was not isolated until recent years. Europium is now prepared by mixing Eu2O3 with a 10%-excess of lanthanum metal and heating the mixture in a tantalum crucible under high vacuum. The element is collected as a silvery-white metallic deposit on the walls of the crucible. As with other rare-earth metals, except for lanthanum, europium ignites in air at about 150 to 180°C. Europium is about as hard as lead and is quite ductile. It is the most reactive of the rare-earth metals, quickly oxidizing in air. It resembles calcium in its reaction with water. Bastnasite and monazite are the principal ores containing europium. Europium has been identified spectroscopically in the sun and certain stars. Europium isotopes are good neutron absorbers and are being studied for use in nuclear control applications. Europium oxide is now widely used as a phosphor activator and europium-activated yttrium vanadate is in commercial use as the red phosphor in color TV tubes. Europium-doped plastic has been used as a laser material. With the development of ion-exchange techniques and special processes, the cost of the metal has been greatly reduced in recent years. Natural europium contains two stable isotopes. Thirty five other radioactive isotopes and isomers are known. Europium is one of the rarest and most costly of the rare-earth metals. It is priced at about $60/g (99.9% pure).

Answer 40

Gadolinium — (gadolinite, a mineral named for Gadolin, a Finnish chemist), Gd; at. wt. 157.25(3); at. no. 64; m.p. 1313°C; b.p. 3273°C; sp. gr. 7.901 (25°C); valence 3. Gadolinia, the oxide of gadolinium, was separated by Marignac in 1880 and Lecoq de Boisbaudran independently isolated the element from Mosander’s “yttria” in 1886. The element was named for the mineral gadolinite from which this rare earth was originally obtained. Gadolinium is found in several other minerals, including monazite and bastnasite, which are of commercial importance. The element has been isolated only in recent years. With the development of ion-exchange and solvent extraction techniques, the availability and price of gadolinium and the other rare-earth metals have greatly improved. Thirty-one isotopes and isomers of gadolinium are now recognized; seven are stable and occur naturally. The metal can be prepared by the reduction of the anhydrous fluoride with metallic calcium. As with other related rare-earth metals, it is silvery white, has a metallic luster, and is malleable and ductile. At room temperature, gadolinium crystallizes in the hexagonal, close-packed α form. Upon heating to 1235°C, α gadolinium transforms into the β form, which has a body-centered cubic structure. The metal is relatively stable in dry air, but in moist air it tarnishes with the formation of a loosely adhering oxide film which spalls off and exposes more surface to oxidation. The metal reacts slowly with water and is soluble in dilute acid. Gadolinium has the highest thermal neutron capture cross-section of any known element (49,000 barns). Natural gadolinium is a mixture of seven isotopes. Two of these, 155Gd and 157Gd, have excellent capture characteristics, but they are present naturally in low concentrations. As a result, gadolinium has a very fast burnout rate and has limited use as a nuclear control rod material. It has been used in making gadolinium yttrium garnets, which have microwave applications. Compounds of gadolinium are used in making phosphors for color TV tubes. The metal has unusual superconductive properties. As little as 1% gadolinium has been found to improve the workability and resistance of iron, chromium, and related alloys to high temperatures and oxidation. Gadolinium ethyl sulfate has extremely low noise characteristics and may find use in duplicating the performance of amplifiers, such as the maser. The metal is ferromagnetic. Gadolinium is unique for its high magnetic moment and for its special Curie temperature (above which ferromagnetism vanishes) lying just at room temperature. This suggests uses as a magnetic component that senses hot and cold. The price of the metal is about $5/g (99.9% purity).

Answer 41

Terbium — (Ytterby, village in Sweden), Tb; at. wt. 158.92534(2); at. no. 65; m.p. 1356°C; b.p. 3230°C; sp. gr. 8.230; valence 3, 4. Discovered by Mosander in 1843. Terbium is a member of the lanthanide or “rare earth” group of elements. It is found in cerite, gadolinite, and other minerals along with other rare earths. It is recovered commercially from monazite in which it is present to the extent of 0.03%, from xenotime, and from euxenite, a complex oxide containing 1% of more of terbia. Terbium has been isolated only in recent years with the development of ion-exchange techniques for separating the rare-earth elements. As with other rare earths, it can be produced by reducing the anhydrous chloride or fluoride with calcium metal in a tantalum crucible. Calcium and tantalum impurities can be removed by vacuum remelting. Other methods of isolation are possible. Terbium is reasonably stable in air. It is a silver-gray metal, and is malleable, ductile, and soft enough to be cut with a knife. Two crystal modifications exist, with a transformation temperature of 1289°C. Forty-two isotopes and isomers are recognized. The oxide is a chocolate or dark maroon color. Sodium terbium borate is used as a laser material and emits coherent light at 0.546 μm. Terbium is used to dope calcium fluoride, calcium tungstate, and strontium molybdate, used in solid-state devices. The oxide has potential application as an activator for green phosphors used in color TV tubes. It can be used with ZrO2 as a crystal stabilizer of fuel cells which operate at elevated temperature. Few other uses have been found. The element is priced at about $40/g (99.9%). Little is known of the toxicity of terbium. It should be handled with care as with other lanthanide elements.

Answer 42

Dysprosium — (Gr. dysprositos, hard to get at), Dy; at. wt. 162.50(3); at. no. 66; m.p. 1412°C; b.p. 2567°C; sp. gr. 8.551 (25°C); valence 3. Dysprosium was discovered in 1886 by Lecoq de Boisbaudran, but not isolated. Neither the oxide nor the metal was available in relatively pure form until the development of ion-exchange separation and metallographic reduction techniques by Spedding and associates about 1950. Dysprosium occurs along with other so-called rare-earth or lanthanide elements in a variety of minerals such as xenotime, fergusonite, gadolinite, euxenite, polycrase, and blomstrandine. The most important sources, however, are from monazite and bastnasite. Dysprosium can be prepared by reduction of the trifluoride with calcium. The element has a metallic, bright silver luster. It is relatively stable in air at room temperature, and is readily attacked and dissolved, with the evolution of hydrogen, by dilute and concentrated mineral acids. The metal is soft enough to be cut with a knife and can be machined without sparking if overheating is avoided. Small amounts of impurities can greatly affect its physical properties. While dysprosium has not yet found many applications, its thermal neutron absorption cross-section and high melting point suggest metallurgical uses in nuclear control applications and for alloying with special stainless steels. A dysprosium oxide-nickel cermet has found use in cooling nuclear reactor rods. This cermet absorbs neutrons readily without swelling or contracting under prolonged neutron bombardment. In combination with vanadium and other rare earths, dysprosium has been used in making laser materials. Dysprosium-cadmium chalcogenides, as sources of infrared radiation, have been used for studying chemical reactions. The cost of dysprosium metal has dropped in recent years since the development of ion-exchange and solvent extraction techniques, and the discovery of large ore bodies. Thirty two isotopes and isomers are now known. The metal costs about $6/g (99.9% purity).

Answer 43

Holmium — (L. Holmia , for Stockholm), Ho; at. wt. 164.93032(2); at. no 67; m.p. 1474°C; b.p. 2700°C; sp. gr. 8.795 (25°C); valence + 3. The spectral absorption bands of holmium were noticed in 1878 by the Swiss chemists Delafontaine and Soret, who announced the existence of an “Element X”. Cleve, of Sweden, later independently discovered the element while working on erbia earth. The element is named after Cleve’s native city. Pure holmia, the yellow oxide, was prepared by Homberg in 1911. Holmium occurs in gadolinite, monazite, and in other rare-earth minerals. It is commercially obtained from monazite, occurring in that mineral to the extent of about 0.05%. It has been isolated by the reduction of its anhydrous chloride or fluoride with calcium metal. Pure holmium has a metallic to bright silver luster. It is relatively soft and malleable, and is stable in dry air at room temperature, but rapidly oxidizes in moist air and at elevated temperatures. The metal has unusual magnetic properties. Few uses have yet been found for the element. The element, as with other rare earths, seems to have a low acute toxic rating. Natural holmium consists of one isotope 165Ho, which is not radioactive. Holmium has 49 other isotopes known, all of which are radioactive. The price of 99.9% holmium metal is about $20/g.

Answer 44

Erbium — (Ytterby, a town in Sweden), Er; at. wt. 167.26(3); at. no. 68; m.p. 1529°C; b.p. 2868°C; sp. gr. 9.066 (25°C); valence 3, Erbium, one of the so-called rare-earth elements of the lanthanide series, is found in the minerals mentioned under dysprosium above. In 1842 Mosander separated “yttria,” found in the mineral gadolinite, into three fractions which he called yttria, erbia, and terbia. The names erbia and terbia became confused in this early period. After 1860, Mosander’s terbia was known as erbia, and after 1877, the earlier known erbia became terbia. The erbia of this period was later shown to consist of five oxides, now known as erbia, scandia, holmia, thulia and ytterbia. By 1905 Urbain and James independently succeeded in isolating fairly pure Er2O3. Klemm and Bommer first produced reasonably pure erbium metal in 1934 by reducing the anhydrous chloride with potassium vapor. The pure metal is soft and malleable and has a bright, silvery, metallic luster. As with other rare-earth metals, its properties depend to a certain extent on the impurities present. The metal is fairly stable in air and does not oxidize as rapidly as some of the other rare-earth metals. Naturally occurring erbium is a mixture of six isotopes, all of which are stable. Twenty-seven radioactive isotopes of erbium are also recognized. Recent production techniques, using ion-exchange reactions, have resulted in much lower prices of the rare-earth metals and their compounds in recent years. THE ELEMENTS (continued) 4-12 The cost of 99.9% erbium metal is about $21/g. Erbium is finding nuclear and metallurgical uses. Added to vanadium, for example, erbium lowers the hardness and improves workability. Most of the rare-earth oxides have sharp absorption bands in the visible, ultraviolet, and near infrared. This property, associated with the electronic structure, gives beautiful pastel colors to many of the rare-earth salts. Erbium oxide gives a pink color and has been used as a colorant in glasses and porcelain enamel glazes.

Answer 45

Thulium — (Thule, the earliest name for Scandinavia), Tm; at. wt. 168.93421(3); at. no. 69; m.p. 1545°C; b.p. 1950°C; sp. gr. 9.321 (25°C); valence 3. Discovered in 1879 by Cleve. Thulium occurs in small quantities along with other rare earths in a number of minerals. It is obtained commercially from monazite, which contains about 0.007% of the element. Thulium is the least abundant of the rare earth elements, but with new sources recently discovered, it is now considered to be about as rare as silver, gold, or cadmium. Ion-exchange and solvent extraction techniques have recently permitted much easier separation of the rare earths, with much lower costs. Only a few years ago, thulium metal was not obtainable at any cost; in 1996 the oxide cost $20/g. Thulium metal powder now costs $70/g (99.9%). Thulium can be isolated by reduction of the oxide with lanthanum metal or by calcium reduction of the anhydrous fluoride. The pure metal has a bright, silvery luster. It is reasonably stable in air, but the metal should be protected from moisture in a closed container. The element is silver-gray, soft, malleable, and ductile, and can be cut with a knife. Forty-one isotopes and isomers are known, with atomic masses ranging from 146 to 176. Natural thulium, which is 100% 169Tm, is stable. Because of the relatively high price of the metal, thulium has not yet found many practical applications. 169Tm bombarded in a nuclear reactor can be used as a radiation source in portable Xray equipment. 171Tm is potentially useful as an energy source. Natural thulium also has possible use in ferrites (ceramic magnetic materials) used in microwave equipment. As with other lanthanides, thulium has a low-to-moderate acute toxic rating. It should be handled with care.

Answer 46

Ytterbium — (Ytterby, village in Sweden), Yb; at. wt. 173.04(3); at. no. 70; m.p. 819°C; b.p. 1196°C; sp. gr (α) 6.903 (β) 6.966; valence 2, 3. Marignac in 1878 discovered a new component, which he called ytterbia, in the earth then known as erbia. In 1907, Urbain separated ytterbia into two components, which he called neoytterbia and lutecia. The elements in these earths are now known as ytterbium and lutetium, respectively. These elements are identical with aldebaranium and cassiopeium, discovered independently and at about the same time by von Welsbach. Ytterbium occurs along with other rare earths in a number of rare minerals. It is commercially recovered principally from monazite sand, which contains about 0.03%. Ion-exchange and solvent extraction techniques developed in recent years have greatly simplified the separation of the rare earths from one another. The element was first prepared by Klemm and Bonner in 1937 by reducing ytterbium trichloride with potassium. Their metal was mixed, however, with KCl. Daane, Dennison, and Spedding prepared a much purer form in 1953 from which the chemical and physical properties of the element could be determined. Ytterbium has a bright silvery luster, is soft, malleable, and quite ductile. While the element is fairly stable, it should be kept in closed containers to protect it from air and moisture. Ytterbium is readily attacked and dissolved by dilute and concentrated mineral acids and reacts slowly with water. Ytterbium has three allotropic forms with transformation points at –13° and 795°C. The beta form is a room-temperature, face-centered, cubic modification, while the high-temperature gamma form is a body-centered cubic form. Another body-centered cubic phase has recently been found to be stable at high pressures at room temperatures. The beta form ordinarily has metallic-type conductivity, but becomes a semiconductor when the pressure is increased above 16,000 atm. The electrical resistance increases tenfold as the pressure is increased to 39,000 atm and drops to about 80% of its standard temperature-pressure resistivity at a pressure of 40,000 atm. Natural ytterbium is a mixture of seven stable isotopes. Twenty six other unstable isotopes and isomers are known. Ytterbium metal has possible use in improving the grain refinement, strength, and other mechanical properties of stainless steel. One isotope is reported to have been used as a radiation source as a substitute for a portable X-ray machine where electricity is unavailable. Few other uses have been found. Ytterbium metal is available with a purity of about 99.9% for about $10/g. Ytterbium has a low acute toxic rating, but may present a carcinogenic hazard.

Answer 47

Lutetium — (Lutetia, ancient name for Paris, sometimes called cassiopeium by the Germans), Lu; at. wt. 174.967(1); at. no. 71; m.p. 1663°C; b.p. 3402°C; sp. gr. 9.841 (25°C); valence 3. In 1907, Urbain described a process by which Marignac’s ytterbium (1879) could be separated into the two elements, ytterbium (neoytterbium)and lutetium. These elements were identical with “aldebaranium” and “cassiopeium,” independently discovered by von Welsbach about the same time. Charles James of the University of New Hampshire also independently prepared the very pure oxide, lutecia, at this time. The spelling of the element was changed from lutecium to lutetium in 1949. Lutetium occurs in very small amounts in nearly all minerals containing yttrium, and is present in monazite to the extent of about 0.003%, which is a commercial source. The pure metal has been isolated only in recent years and is one of the most difficult to prepare. It can be prepared by the reduction of anhydrous LuCl3 or LuF3 by an alkali or alkaline earth metal. The metal is silvery white and relatively stable in air. While new techniques, including ion-exchange reactions, have been developed to separate the various rare-earth elements, lutetium is still the most costly of all rare earths. It is priced at about $100/g (99.9%). 176Lu occurs naturally (97.41%) with 175Lu (2.59%), which is radioactive with a very long half-life. It is radioactive with a half-life of about 4 × 1010 years. Lutetium has 50 isotopes and isomers that are now recognized. Stable lutetium nuclides, which emit pure beta radiation after thermal neutron activation, can be used as catalysts in cracking, alkylation, hydrogenation, and polymerization. Virtually no other commercial uses have been found yet for lutetium. While lutetium, like other rare-earth metals, is thought to have a low toxicity rating, it should be handled with care until more information is available.

Answer 48

Hafnium — (Hafnia, Latin name for Copenhagen), Hf; at. wt. 178.49(2); at. no. 72; m.p. 2233°C; b.p. 4603°C; sp. gr. 13.31 (20°C); valence 4. Hafnium was thought to be present in various minerals and concentrations many years prior to its discovery, in 1923, credited to D. Coster and G. von Hevesey. On the basis of the Bohr theory, the new element was expected to be associated with zirconium. It was finally identified in zircon from Norway, by means of X-ray spectroscopic analysis. It was named in honor of the city in which the discovery was made. Most zirconium minerals contain 1 to 5% hafnium. It was originally separated from zirconium by repeated recrystallization of the double ammonium or potassium fluorides by von Hevesey and Jantzen. Metallic hafnium was first prepared by van Arkel and deBoer by passing the vapor of the tetraiodide over a heated tungsten filament. Almost all hafnium metal now produced is made by reducing the tetrachloride with magnesium or with sodium (Kroll Process). Hafnium is a ductile metal with a brilliant silver luster. Its properties are considerably influenced by the impurities of zirconium present. Of all the elements, zirconium and hafnium are two of the most difficult to separate. Their chemistry is almost identical, however, the density of zirconium is about half that of hafnium. Very pure hafnium has been produced, with zirconium being the major impurity. Natural hafnium contains six isotopes, one of which is slightly radioactive. Hafnium has a total of 41 recognized isotopes and isomers. Because hafnium has a good absorption cross section for thermal neutrons (almost 600 times that of zirconium), has excellent mechanical properties, and is extremely corrosion resistant, it is used for reactor control rods. Such rods are used in nuclear submarines. Hafnium has been successfully alloyed with iron, titanium, niobium, tantalum, and other metals. Hafnium carbide is the most refractory binary composition known, and the nitride is the most refractory of all known metal nitrides (m.p. 3310°C). Hafnium is used in gas-filled and incandescent lamps, and is an efficient “getter” for scavenging oxygen and nitrogen. Finely divided hafnium is pyrophoric and can ignite spontaneously in air. Care should be taken when machining the metal or when handling hot sponge hafnium. At 700°C hafnium rapidly absorbs hydrogen to form the composition HfH1.86. Hafnium is resistant to concentrated alkalis, but at elevated temperatures reacts with oxygen, nitrogen, carbon, boron, sulfur, and silicon. Halogens react directly to form tetrahalides. The price of the metal is about $2/g. The yearly demand for hafnium in the U.S. is now in excess of 50,000 kg.

Answer 49

Tantalum — (Gr. Tantalos, mythological character, father of Niobe), Ta; at. wt. 180.9479(1); at. no. 73; m.p. 3017°C; b.p. 5458°C; sp. gr. 16.654; valence 2?, 3, 4?, or 5. Discovered in 1802 by Ekeberg, but many chemists thought niobium and tantalum were identical elements until Rose, in 1844, and Marignac, in1866, showed that niobic and tantalic acids were two different acids. The early investigators only isolated the impure metal. The first relatively pure ductile tantalum was produced by von Bolton in 1903. Tantalum occurs principally in the mineral columbite-tantalite (Fe, Mn)(Nb, Ta)2O6. Tantalum ores are found in Australia, Brazil, Rwanda, Zimbabwe, Congo-Kinshasa, Nigeria, and Canada. Separation of tantalum from niobium requires several complicated steps. Several methods are used to commercially produce the element, including electrolysis of molten potassium fluorotantalate, reduction of potassium fluorotantalate with sodium, or reacting tantalum carbide with tantalum oxide. Thirty four isotopes and isomers of tantalum are known to exist. Natural tantalum contains two isotopes, one of which is radioactive with a very long half-life. Tantalum is a gray, heavy, and very hard metal. When pure, it is ductile and can be drawn into fine wire, which is used as a filament for evaporating metals such as aluminum. Tantalum is almost completely immune to chemical attack at temperatures below 150°C, and is attacked only by hydrofluoric acid, acidic solutions containing the fluoride ion, and free sulfur trioxide. Alkalis attack it only slowly. At high temperatures, tantalum becomes much more reactive. The element has a melting point exceeded only by tungsten and rhenium. Tantalum is used to make a variety of alloys with desirable properties such as high melting point, high strength, good ductility, etc. Scientists at Los Alamos have produced a tantalum carbide graphite composite material, which is said to be one of the hardest materials ever made. The compound has a melting point of 3738°C. Tantalum has good “gettering” ability at high temperatures, and tantalum oxide films are stable and have good rectifying and dielectric properties. Tantalum is used to make electrolytic capacitors and vacuum furnace parts, which account for about 60% of its use. The metal is also widely used to fabricate chemical process equipment, nuclear reactors, and aircraft and missile parts. Tantalum is completely immune to body liquids and is a nonirritating metal. It has, therefore, found wide use in making surgical appliances. Tantalum oxide is used to make special glass with high index of refraction for camera lenses. The metal has many other uses. The price of (99.9%) tantalum is about $2/g.

Answer 50

Tungsten — (Swedish, tung sten, heavy stone); also known as wolfram (from wolframite, said to be named from wolf rahm or spumi lupi, because the ore interfered with the smelting of tin and was supposed to devour the tin), W; at. wt. 183.84(1); at. no. 74; m.p. 3422°C; b.p. 5555°C; sp. gr. 19.3 (20°C); valence 2, 3, 4, 5, or 6. In 1779 Peter Woulfe examined the mineral now known as wolframite and concluded it must contain a new substance. Scheele, in 1781, found that a new acid could be made from tung sten (a name first applied about 1758 to a mineral now known as scheelite). Scheele and Berman suggested the possibility of obtaining a new metal by reducing this acid. The de Elhuyar brothers found an acid in wolframite in 1783 that was identical to the acid of tungsten(tungstic acid) of Scheele, and in that year they succeeded in obtaining the element by reduction of this acid with charcoal. Tungsten occurs in wolframite, (Fe, Mn)WO4; scheelite, CaWO4; huebnerite, MnWO4; and ferberite, FeWO4. Important deposits of tungsten occur in California, Colorado, Bolivia, Russia, and Portugal. China is reported to have about 75% of the world’s tungsten resources. Natural tungsten contains five stable isotopes. Thirty two other unstable isotopes and isomers are recognized. The metal is obtained commercially by reducing tungsten oxide with hydrogen or carbon. Pure tungsten is a steel-gray to tin-white metal. Very pure tungsten can be cut with a hacksaw, and can be forged, spun, drawn, and extruded. The impure metal is brittle and can be worked only with difficulty. Tungsten has the highest melting point of all metals, and at temperatures over 1650°C has the highest tensile strength. The metal oxidizes in air and must be protected at elevated temperatures. It has excellent corrosion resistance and is attacked only slightly by most mineral acids. The thermal expansion is about the same as borosilicate glass, which makes the metal useful for glass-to-metal seals. Tungsten and its alloys are used extensively for filaments for electric lamps, electron and television tubes, and for metal evaporation work; for electrical contact points for automobile distributors; X-ray targets; windings and heating elements for electrical furnaces; and for numerous spacecraft and high-temperature applications. High-speed tool steels, Hastelloy®, Stellite®, and many other alloys contain tungsten. Tungsten carbide is of great importance to the metal-working, mining, and petroleum industries.Calcium and magnesium tungstates are widely used in fluorescent lighting; other salts of tungsten are used in the chemical and tanning industries. Tungsten disulfide is a dry, high-temperature lubricant, stable to 500°C. Tungsten bronzes and other tungsten compounds are used in paints. Zirconium tungstate has found recent applications (see under Zirconium). Tungsten powder (99.999%) costs about $2900/kg.

Answer 51

Osmium — (Gr. osme, a smell), Os; at. wt. 190.23(3); at. no. 76; m.p. 3033°C; b.p. 5012°C; sp. gr. 22.57; valence 0 to +8, more usually +3, +4, +6, and +8. Discovered in 1803 by Tennant in the residue left when crude platinum is dissolved by aqua regia. Osmium occurs in iridosmine and in platinum-bearing river sands of the Urals, North America, and South America. It is also found in the nickel-bearing ores of Sudbury, Ontario, region along with other platinum metals. While the quantity of platinum metals in these ores is very small, the large tonnages of nickel ores processed make commercial recovery possible. The metal is lustrous, bluish white, extremely hard, and brittle even at high temperatures. It has the highest melting point and the lowest vapor pressure of the platinum group. The metal is very difficult to fabricate, but the powder can be sintered in a hydrogen atmosphere at a temperature of 2000°C. The solid metal is not affected by air at room temperature, but the powdered or spongy metal slowly gives off osmium tetroxide, which is a powerful oxidizing agent and has a strong smell. The tetroxide is highly toxic, and boils at 130°C (760 mm). Concentrations in air as low as 10–7 g/m3 can cause lung congestion, skin damage, or eye damage. The tetroxide has been used to detect fingerprints and to stain fatty tissue for microscope slides. The metal is almost entirely used to produce very hard alloys, with other metals of the platinum group, THE ELEMENTS (continued) 4-22 for fountain pen tips, instrument pivots, phonograph needles, and electrical contacts. The price of 99.9% pure osmium powder — the form usually supplied commercially — is about $100/g, depending on quantity and supplier. Natural osmium contains seven isotopes, one of which, 186Os, is radioactive with a very long half-life. Thirty four other isotopes and isomers are known, all of which are radioactive.The measured densities of iridium and osmium seem to indicate that osmium is slightly more dense than iridium, so osmium has generally been credited with being the heaviest known element. Calculations of the density from the space lattice, which may be more reliable for these elements than actual measurements, however, give a density of 22.65 for iridium compared to 22.61 for osmium. At present, therefore, we know either iridium or osmium is the heaviest element, but the data do not allow selection between the two.

Answer 52

Rhenium — (L. Rhenus, Rhine), Re; at. wt. 186.207(1); at. no. 75; m.p. 3186°C; b.p. 5596°C; sp. gr. 21.02 (20°C); valence –1, +1, 2, 3, 4, 5, 6, 7. Discovery of rhenium is generally attributed to Noddack, Tacke, and Berg, who announced in 1925 they had detected the element in platinum ores and columbite. They also found the element in gadolinite and molybdenite. By working up 660 kg of molybdenite they were able in 1928 to extract 1 g of rhenium. The price in 1928 was $10,000/g. Rhenium does not occur free in nature or as a compound in a distinct mineral species. It is, however, widely spread throughout the earth’s crust to the extent of about 0.001 ppm. Commercial rhenium in the U.S. today is obtained from molybdenite roaster-flue dusts obtained from copper-sulfide ores mined in the vicinity of Miami, Arizona, and elsewhere in Arizona and Utah. Some molybdenites contain from 0.002 to 0.2% rhenium. It is estimated that in 1999 about 16,000 kg of rhenium was being produced. The total estimated world reserves of rhenium is 11,000,000 kg. The total estimated Free World reserve of rhenium metal is 3500 tons. Natural rhenium is a mixture of two isotopes, one of which has a very long half-life. Thirty nine other unstable isotopes are recognized. Rhenium metal is prepared by reducing ammonium perrhenate with hydrogen at elevated temperatures. The element is silvery white with a metallic luster; its density is exceeded only by that of platinum, iridium, and osmium, and its melting point is exceeded only by that of tungsten and carbon. It has other useful properties. The usual commercial form of the element is a powder, but it can be consolidated by pressing and resistance-sintering in a vacuum or hydrogen atmosphere. This produces a compact shape in excess of 90% of the density of the metal. Annealed rhenium is very ductile, and can be bent, coiled, or rolled. Rhenium is used as an additive to tungsten and molybdenum-based alloys to impart useful properties. It is widely used for filaments for mass spectrographs and ion gages. Rheniummolybdenum alloys are superconductive at 10 K. Rhenium is also used as an electrical contact material as it has good wear resistance and withstands arc corrosion. Thermocouples made of Re-W are used for measuring temperatures up to 2200°C, and rhenium wire has been used in photoflash lamps for photography. Rhenium catalysts are exceptionally resistant to poisoning from nitrogen, sulfur, and phosphorus, and are used for hydrogenation of fine chemicals, hydrocracking, reforming, and disproportionation of olefins. Rhenium has recently become especially important as a catalyst for petroleum refining and in making super-alloys for jet engines. Rhenium costs about $16/g (99.99% pure). Little is known of its toxicity; therefore, it should be handled with care until more data are available.

Answer 53

Iridium — (L. iris, rainbow), Ir; at. wt. 192.217(3); at. no. 77; m.p. 2446°C; b.p. 4428°C; sp. gr. 22.42 (17°C); valence 3 or 4. Discovered in 1803 by Tennant in the residue left when crude platinum is dissolved by aqua regia. The name iridium is appropriate, for its salts are highly colored. Iridium, a metal of the platinum family, is white, similar to platinum, but with a slight yellowish cast. It is very hard and brittle, making it very hard to machine, form, or work. It is the most corrosion-resistant metal known, and was used in making the standard meter bar of Paris, which is a 90% platinum-10% iridium alloy. This meter bar was replaced in 1960 as a fundamental unit of length (see under Krypton). Iridium is not attacked by any of the acids nor by aqua regia, but is attacked by molten salts, such as NaCl and NaCN. Iridium occurs uncombined in nature with platinum and other metals of this family in alluvial deposits. It is recovered as a by-product from the nickel mining industry. The largest reserves and production of the platinum group of metals, which includes iridium, is in South Africa, followed by Russia and Canada. The U.S. has only one active mine, located at Nye, MT. The presence of iridium has recently been used in examining the Cretaceous-Tertiary (K-T) boundary. Meteorites contain small amounts of iridium. Because iridium is found widely distributed at the K-T boundary, it has been suggested that a large meteorite or asteroid collided with the earth, killing the dinosaurs, and creating a large dust cloud and crater. Searches for such a crater point to one in the Yucatan, known as Chicxulub. Iridium has found use in making crucibles and apparatus for use at high temperatures. It is also used for electrical contacts. Its principal use is as a hardening agent for platinum. With osmium, it forms an alloy which is used for tipping pens and compass bearings. The specific gravity of iridium is only very slightly lower than that of osmium, which has been generally credited as being the heaviest known element. Calculations of the densities of iridium and osmium from the space lattices gives values of 22.65 and 22.61 g/cm3, respectively. These values may be more reliable than actual physical measurements. TeamLRN THE ELEMENTS (continued) 4-17 At present, therefore, we know that either iridium or osmium is the densest known element, but the data do not yet allow selection between the two. Natural iridium contains two stable isotopes. Forty-five other isotopes, all radioactive, are now recognized. Iridium (99.9%) costs about $100/g.

Answer 54

Platinum — (It. platina, silver), Pt; at. wt. 195.078(2); at. no. 78; m.p. 1768.4°C; b.p. 3825°C; sp. gr. 21.45 (20°C); valence 1?, 2, 3, or 4. Discovered in South America by Ulloa in 1735 and by Wood in 1741. The metal was used by pre-Columbian Indians. Platinum occurs native, accompanied by small quantities of iridium, osmium, palladium, ruthenium, and rhodium, all belonging to the same group of metals. These are found in the alluvial deposits of the Ural mountains and in Columbia. Sperrylite (PtAs2), occurring with the nickel-bearing deposits of Sudbury, Ontario, is a source of a considerable amount of metal. The large production of nickel offsets there being only one part of the platinum metals in two million parts of ore. The largest supplier of the platinum group of metals is now South Africa, followed by Russia and Canada. Platinum is a beautiful silvery-white metal, when pure, and is malleable and ductile. It has a coefficient of expansion almost equal to that of soda-lime-silica glass, and is therefore used to make sealed electrodes in glass systems. The metal does not oxidize in air at any temperature, but is corroded by halogens, cyanides, sulfur, and caustic alkalis. It is insoluble in hydrochloric and nitric acid, but dissolves when they are mixed as aqua regia, forming chloroplatinic acid (H2PtCl6), an important compound. Natural platinum contains six isotopes, one of which, 190Pt, is radioactive with a long half-life. Thirty-seven other radioactive isotopes and isomers are recognized. The metal is extensively used in jewelry, wire, and vessels for laboratory use, and in many valuable instruments including thermocouple elements. It is also used for electrical contacts, corrosion-resistant apparatus, and in dentistry. Platinum-cobalt alloys have magnetic properties. One such alloy made of 76.7% Pt and 23.3% Co, by weight, is an extremely powerful magnet that offers a B-H (max) almost twice that of Alnico V. Platinum resistance wires are used for constructing high-temperature electric furnaces. The metal is used for coating missile nose cones, jet engine fuel nozzles, etc., which must perform reliably for long periods of time at high temperatures. The metal, like palladium, absorbs large volumes, of hydrogen, retaining it at ordinary temperatures but giving it up at red heat. In the finely divided state platinum is an excellent catalyst, having long been used in the contact process for producing sulfuric acid. It is also used as a catalyst in cracking petroleum products. There is also much current interest in the use of platinum as a catalyst in fuel cells and in its use as antipollution devices for automobiles. Platinum anodes are extensively used in cathodic protection systems for large ships and ocean-going vessels, pipelines, steel piers, etc. Pure platinum wire will glow red hot when placed in the vapor of methyl alcohol. It acts here as a catalyst, converting the alcohol to formaldehyde. This phenomenon has been used commercially to produce cigarette lighters and hand warmers. Hydrogen and oxygen explode in the presence of platinum. The price of platinum has varied widely; more than a century ago it was used to adulterate gold. It was nearly eight times as valuable as gold in 1920. The price in January 2002 was about $430/troy oz. ($15/g), higher than the price of gold.

Answer 55

Gold — (Sanskrit Jval; Anglo-Saxon gold), Au (L. aurum, gold); at. wt. 196.96654(3); at. no. 79; m.p. 1064.18°C; b.p. 2856°C; sp. gr. ~19.3 (20°C); valence 1 or 3. Known and highly valued from earliest times, gold is found in nature as the free metal and in tellurides; it is very widely distributed and is almost always associated with quartz or pyrite. It occurs in veins and alluvial deposits, and is often separated from rocks and other minerals by sluicing and panning operations. About 25% of the world’s gold output comes from South Africa, and about two thirds of the total U.S. production now comes from South Dakota and Nevada. The metal is recovered from its ores by cyaniding, amalgamating, and smelting processes. THE ELEMENTS (continued) 4-14 Refining is also frequently done by electrolysis. Gold occurs in sea water to the extent of 0.1 to 2 mg/ton, depending on the location where the sample is taken. As yet, no method has been found for recovering gold from sea water profitably. It is estimated that all the gold in the world, so far refined, could be placed in a single cube 60 ft on a side. Of all the elements, gold in its pure state is undoubtedly the most beautiful. It is metallic, having a yellow color when in a mass, but when finely divided it may be black, ruby, or purple. The Purple of Cassius is a delicate test for auric gold. It is the most malleable and ductile metal; 1 oz. of gold can be beaten out to 300 ft2. It is a soft metal and is usually alloyed to give it more strength. It is a good conductor of heat and electricity, and is unaffected by air and most reagents. It is used in coinage and is a standard for monetary systems in many countries. It is also extensively used for jewelry, decoration, dental work, and for plating. It is used for coating certain space satellites, as it is a good reflector of infrared and is inert. Gold, like other precious metals, is measured in troy weight; when alloyed with other metals, the term carat is used to express the amount of gold present, 24 carats being pure gold. For many years the value of gold was set by the U.S. at $20.67/troy ounce; in 1934 this value was fixed by law at $35.00/troy ounce, 9/10th fine. On March 17, 1968, because of a gold crisis, a two-tiered pricing system was established whereby gold was still used to settle international accounts at the old $35.00/troy ounce price while the price of gold on the private market would be allowed to fluctuate. Since this time, the price of gold on the free market has fluctuated widely. The price of gold on the free market reached a price of $620/ troy oz. in January 1980. More recently, the U.K. and other nations, including the I.M.F. have sold or threatened to sell a sizeable portion of their gold reserves. This has caused wide fluctuations in the price of gold. Because this has damaged the economy of some countries, a moratorium for a few years has been declared. This has tended to stabilize temporarily the price of gold. The most common gold compounds are auric chloride (AuCl3) and chlorauric acid (HAuCl4), the latter being used in photography for toning the silver image. Gold has forty-eight recognized isotopes and isomers; 198Au, with a half-life of 2.7 days, is used for treating cancer and other diseases. Disodium aurothiomalate is administered intramuscularly as a treatment for arthritis. A mixture of one part nitric acid with three of hydrochloric acid is called aqua regia (because it dissolved gold, the King of Metals). Gold is available commercially with a purity of 99.999+%. For many years the temperature assigned to the freezing point of gold has been 1063.0°C; this has served as a calibration point for the International Temperature Scales (ITS-27 and ITS-48) and the International Practical Temperature Scale (IPTS- 48). In 1968, a new International Practical Temperature Scale (IPTS-68) was adopted, which demanded that the freezing point of gold be changed to 1064.43°C. In 1990 a new International Temperature Scale (ITS-90) was adopted bringing the t.p. (triple point) of H2O (t90 (°C)) to 0.01°C and the freezing point of gold to 1064.18°C.The specific gravity of gold has been found to vary considerably depending on temperature, how the metal is precipitated, and cold-worked. As of December 2001, gold was priced at about $275/troy oz. ($8.50/g).

Answer 56

Mercury — (Planet Mercury), Hg (hydrargyrum, liquid silver); at. wt. 200.59(2); at. no. 80; t.p. –38.83°C; b.p. 356.73°C; tc 1447°C; sp. gr. 13.546 (20°C); valence 1 or 2. Known to ancient Chinese and Hindus; found in Egyptian tombs of 1500 B.C. Mercury is the only common metal liquid at ordinary temperatures. It only rarely occurs free in nature. The chief ore is cinnabar (HgS). Spain and China produce about 75% of the world’s supply of the metal. The commercial unit for handling mercury is the “flask,” which weighs 76 lb (34.46 kg). The metal is obtained by heating cinnabar in a current of air and by condensing the vapor. It is a heavy, silvery-white metal; a rather poor conductor of heat, as compared with other metals, and a fair conductor of electricity. It easily forms alloys with many metals, such as gold, silver, and tin, which are called amalgams. Its ease in amalgamating with gold is made use of in the recovery of gold from its ores. The metal is widely used in laboratory work for making thermometers, barometers, diffusion pumps, and many other instruments. It is used in making mercury-vapor lamps and advertising signs, etc. and is used in mercury switches and other electrical apparatus. Other uses are in making pesticides, mercury cells for caustic soda and chlorine production, dental preparations, antifouling paint, batteries, and catalysts. The most important salts are mercuric chloride HgCl2 (corrosive sublimate — a violent poison), mercurous chloride Hg2Cl2(calomel, occasionally still used in medicine), mercury fulminate (Hg(ONC)2), a detonator widely used in explosives, and mercuric sulfide (HgS, vermillion, a high-grade paint pigment). Organic mercury compounds are important. It has been found that an electrical discharge causes mercury vapor to combine with neon, argon, krypton, and xenon. These products, held together with van der Waals’ forces, correspond to HgNe, HgAr, HgKr, and HgXe. Mercury is a virulent poison and is readily absorbed through the respiratory tract, the gastrointestinal tract, or through unbroken skin. It acts as a cumulative poison and dangerous levels are readily attained in air. Air saturated with mercury vapor at 20°C contains a concentration that exceeds the toxic limit many times. The danger increases at higher temperatures. It is therefore important that mercury be handled with care. Containers of mercury should be securely covered and spillage should be avoided. If it is necessary to heat mercury or mercury compounds, it should be done in a well-ventilated hood. Methyl mercury is a dangerous pollutant and is now widely found in water and streams. The triple point of mercury, –38.8344°C, is a fixed point on the International Temperature Scale (ITS-90). Mercury (99.98%) is priced at about $110/kg. Native mercury contains seven isotopes. Thirty-six other isotopes and isomers are known.

Answer 57

Thallium — (Gr. thallos, a green shoot or twig), Tl; at. wt. 204.3833(2); at. no. 81; m.p. 304°C; b.p. 1473°C; sp. gr. 11.85 (20°C); valence 1, or 3. Thallium was discovered spectroscopically in 1861 by Crookes. The element was named after the beautiful green spectral line, which identified the element. The metal was isolated both by Crookes and Lamy in 1862 about the same time. Thallium occurs in crooksite, lorandite, and hutchinsonite. It is also present in pyrites and is recovered from the roasting of this ore in connection with the production of sulfuric acid. It is also obtained from the smelting of lead and zinc ores. Extraction is somewhat complex and depends on the source of the thallium. Manganese nodules, found on the ocean floor, contain thallium. When freshly exposed to air, thallium exhibits a metallic luster, but soon develops a bluish-gray tinge, resembling lead in appearance. A heavy oxide builds up on thallium if left in air, and in the presence of water the hydroxide is formed. The metal is very soft and malleable. It can be cut with a knife. Forty-seven isotopes of thallium, with atomic masses ranging from 179 to 210 are recognized. Natural thallium is a mixture of two isotopes. The element and its compounds are toxic and should be handled carefully. Contact of the metal with skin is dangerous, and when melting the metal adequate ventilation should be provided. Thallium is suspected of carcinogenic potential for man. Thallium sulfate has been widely employed as a rodenticide and ant killer. It is odorless and tasteless, giving no warning of its presence. Its use, however, has been prohibited in the U.S. since 1975 as a household insecticide and rodenticide. The electrical conductivity of thallium sulfide changes with exposure to infrared light, and this compound is used in photocells. Thallium bromide-iodide crystals have been used as infrared optical materials. Thallium has been used, with sulfur or selenium and arsenic, to produce low melting glasses which become fluid between 125 and 150°C. These glasses have properties at room temperatures similar to ordinary glasses and are said to be durable and insoluble in water. Thallium oxide has been used to produce glasses with a high index of refraction. Thallium has been used in treating ringworm and other skin infections; however, its use has been limited because of the narrow margin between toxicity and therapeutic benefits. A mercury-thallium alloy, which forms a eutectic at 8.5% thallium, is reported to freeze at –60°C, some 20° below the freezing point of mercury. Thallium metal (99.999%) costs about $2/g.

Answer 58

Lead — (Anglo-Saxon lead), Pb (L. plumbum); at. wt. 207.2(1); at. no. 82; m.p. 327.46°C; b.p. 1749°C; sp. gr. 11.35 (20°C); valence 2 or 4. Long known, mentioned in Exodus. The alchemists believed lead to be the oldest metal and associated it with the planet Saturn. Native lead occurs in nature, but it is rare. Lead is obtained chiefly from galena (PbS) by a roasting process. Anglesite (PbSO4), cerussite (PbCO3), and minim (Pb3O4) are other common lead minerals. Lead is a bluish-white metal of bright luster, is very soft, highly malleable, ductile, and a poor conductor of electricity. It is very resistant to corrosion; lead pipes bearing the insignia of Roman emperors, used as drains from the baths, are still in service. It is used in containers for corrosive liquids (such as sulfuric acid) and may be toughened by the addition of a small percentage of antimony or other metals. Natural lead is a mixture of four stable isotopes: 204Pb (1.4%), 206Pb (24.1%), 207Pb (22.1%), and 208Pb (52.4%). Lead isotopes are the end products of each of the three series of naturally occurring radioactive elements: 206Pb for the uranium series, 207Pb for the actinium series, and 208Pb for the thorium series. Forty-three other isotopes of lead, all of which are radioactive, are recognized. Its alloys include solder, type metal, and various antifriction metals. Great quantities of lead, both as the metal and as the dioxide, are used in storage batteries. Lead is also used for cable covering, plumbing, and ammunition. The metal is very effective as a sound absorber, is used as a radiation shield around X-ray equipment and nuclear reactors, and is used to absorb vibration. Lead, alloyed with tin, is used in making organ pipes. White lead, the basic carbonate, sublimed white lead (PbSO4), chrome yellow (PbCrO4), red lead (Pb3O4), and other lead compounds are used extensively in paints, although in recent years the use of lead in paints has been drastically curtailed to eliminate or reduce health hazards. Lead oxide is used in producing fine “crystal glass” and “flint glass” of a high index of refraction for achromatic lenses. The nitrate and the acetate are soluble salts. Lead salts such as lead arsenate have been used as insecticides, but their use in recent years has been practically eliminated in favor of less harmful organic compounds. Care must be used in handling lead as it is a cumulative poison. Environmental concern with lead poisoning has resulted in a national program to eliminate the lead tetraethyl in gasoline. The U.S. Occupational Safety and Health Administration (OSHA) has recommended that industries limit airborne lead to 50 μgms/cu. meter. Lead is priced at about 90¢/kg (99.9%).

Answer 59

Bismuth — (Ger. Weisse Masse, white mass; later Wisuth and Bisemutum), Bi; at. wt. 208.98038(2); at. no. 83; m.p. 271.4°C; b.p. 1564°C; sp. gr. 9.747 (20°C); valence 3 or 5. In early times bismuth was confused with tin and lead. Claude Geoffroy the Younger showed it to be distinct from lead in 1753. It is a white crystalline, brittle metal with a pinkish tinge. It occurs native. The most important ores are bismuthinite or bismuth glance (Bi2S3) and bismite (Bi2O3). Peru, Japan, Mexico, Bolivia, and Canada are major bismuth producers. Much of the bismuth produced in the U.S. is obtained as a by-product in refining lead, copper, tin, silver, and gold ores. Bismuth is the most diamagnetic of all metals, and the thermal conductivity is lower than any metal, except mercury. It has a high electrical resistance, and has the highest Hall effect of any metal (i.e., greatest increase in electrical resistance when placed in a magnetic field). “Bismanol” is a permanent magnet of high coercive force, made of MnBi, by the U.S. Naval Surface Weapons Center. Bismuth expands 3.32% on solidification. This property makes bismuth alloys particularly suited to the making of sharp castings of objects subject to damage by high temperatures. With other metals such as tin, cadmium, etc., bismuth forms low-melting alloys which are extensively used for safety devices in fire detection and extinguishing systems. Bismuth is used in producing malleable irons and is finding use as a catalyst for making acrylic fibers. When bismuth is heated in air it burns with a blue flame, forming yellow fumes of the oxide. The metal is also used as a thermocouple material, and has found application as a carrier for U235 or U233 fuel in atomic reactors. Its soluble salts are characterized by forming THE ELEMENTS (continued) 4-6 insoluble basic salts on the addition of water, a property sometimes used in detection work. Bismuth oxychloride is used extensively in cosmetics. Bismuth subnitrate and subcarbonate are used in medicine. Natural bismuth contains only one isotope 209Bi. Forty-four isotopes and isomers of bismuth are known. Bismuth metal (99.5%) costs about $250/kg.

Answer 60

Polonium — (Poland, native country of Mme. Curie [1867–1934]), Po; at. wt. (209); at. no. 84; m.p. 254°C; b.p. 962°C; sp. gr. (alpha modification) 9.32; valence –2, 0, +2, +3(?), +4, and +6. Polonium was the first element discovered by Mme. Curie in 1898, while seeking the cause of radioactivity of pitchblende from Joachimsthal, Bohemia. The electroscope showed it separating with bismuth. Polonium is also called Radium F. Polonium is a very rare natural element. Uranium ores contain only about 100 μg of the element per ton. Its abundance is only about 0.2% of that of radium. In 1934, it was found that when natural bismuth (209Bi) was bombarded by neutrons, 210Bi, the parent of polonium, was obtained. Milligram amounts of THE ELEMENTS (continued) 4-24 polonium may now be prepared this way, by using the high neutron fluxes of nuclear reactors. Polonium-210 is a low-melting, fairly volatile metal, 50% of which is vaporized in air in 45 hours at 55°C. It is an alpha emitter with a half-life of 138.39 days. A milligram emits as many alpha particles as 5 g of radium. The energy released by its decay is so large (140 W/g) that a capsule containing about half a gram reaches a temperature above 500°C. The capsule also presents a contact gamma-ray dose rate of 0.012 Gy/h. A few curies (1 curie = 3.7 × 1010 Bq) of polonium exhibit a blue glow, caused by excitation of the surrounding gas. Because almost all alpha radiation is stopped within the solid source and its container, giving up its energy, polonium has attracted attention for uses as a lightweight heat source for thermoelectric power in space satellites. Thirty-eight isotopes and isomers of polonium are known, with atomic masses ranging from 192 to 218. All are radioactive. Polonium-210 is the most readily available. Isotopes of mass 209 (half-life 102 years) and mass 208 (half-life 2.9 years) can be prepared by alpha, proton, or deuteron bombardment of lead or bismuth in a cyclotron, but these are expensive to produce. Metallic polonium has been prepared from polonium hydroxide and some other polonium compounds in the presence of concentrated aqueous or anhydrous liquid ammonia. Two allotropic modifications are known to exist. Polonium is readily dissolved in dilute acids, but is only slightly soluble in alkalis. Polonium salts of organic acids char rapidly; halide amines are reduced to the metal. Polonium can be mixed or alloyed with beryllium to provide a source of neutrons. It has been used in devices for eliminating static charges in textile mills, etc.; however, beta sources are more commonly used and are less dangerous. It is also used on brushes for removing dust from photographic films. The polonium for these is carefully sealed and controlled, minimizing hazards to the user. Polonium-210 is very dangerous to handle in even milligram or microgram amounts, and special equipment and strict control is necessary. Damage arises from the complete absorption of the energy of the alpha particle into tissue. The maximum permissible body burden for ingested polonium is only 0.03 μCi, which represents a particle weighing only 6.8 × 10–12 g. Weight for weight it is about 2.5 × 1011 times as toxic as hydrocyanic acid. The maximum allowable concentration for soluble polonium compounds in air is about 2 × 1011 μCi/cm3. Polonium-209 is available on special order from the Oak Ridge National Laboratory at a cost of $3600/μCi plus packing costs.

Answer 61

Astatine — (Gr. astatos, unstable), At; at. wt. (210); at. no. 85; m.p. 300°C (est.); valence probably 1, 3, 5, or 7. Synthesized in 1940 by D. R. Corson, K. R. MacKenzie, and E. Segre at the University of California by bombarding bismuth with alpha particles. The longest-lived isotope, 210At, has a half-life of only 8.1 hours. Thirty-six other isotopes and isomers are now known. Minute quantities of 215At, 218At, and 219At exist in equilibrium in nature with naturally occurring uranium and thorium isotopes, and traces of 217At are equilibrium with 233U and 239Np resulting from interaction of thorium and uranium with naturally produced neutrons. The total amount of astatine present in the earth’s crust, however, is probably less than 1 oz. Astatine can be produced by bombarding bismuth with energetic alpha particles to obtain the relatively long-lived 209–211At, which can be distilled TeamLRN THE ELEMENTS (continued) 4-5 from the target by heating it in air. Only about 0.05 μg of astatine has been prepared to date. The “time of flight” mass spectrometer has been used to confirm that this highly radioactive halogen behaves chemically very much like other halogens, particularly iodine. The interhalogen compounds AtI, AtBr, and AtCl are known to form, but it is not yet known if astatine forms diatomic astatine molecules. HAt and CH3At (methyl astatide) have been detected. Astatine is said to be more metallic that iodine, and, like iodine, it probably accumulates in the thyroid gland. Workers at the Brookhaven National Laboratory have recently used reactive scattering in crossed molecular beams to identify and measure elementary reactions involving astatine.

Answer 62

Radon — (from radium; called niton at first, L. nitens, shining), Rn; at. wt. (222); at. no. 86; m.p. –71°C; b.p. –61.7°C; tc 104°C; density of gas 9.73 g/l; sp. gr. liquid 4.4 at –62°C, solid 4; valence usually 0. The element was discovered in 1900 by Dorn, who called it radium emanation. In 1908 Ramsay and Gray, who named it niton, isolated the element and determined its density, finding it to be the heaviest known gas. It is essentially inert and occupies the last place in the zero group of gases in the Periodic Table. Since 1923, it has been called radon. Thirty-seven isotopes and isomers are known. Radon-222, coming from radium, has a half-life of 3.823 days and is an alpha emitter; Radon-220, emanating naturally from thorium and called thoron, has a half-life of 55.6 s and is also an alpha emitter. Radon-219 emanates from actinium and is called actinon. It has a half-life of 3.9 s and is also an alpha emitter. It is estimated that every square mile of soil to a depth of 6 inches contains about 1 g of radium, which releases radon in tiny amounts to the atmosphere. Radon is present in some spring waters, such as those at Hot Springs, Arkansas. On the average, one part of radon is present to 1 × 1021 part of air. At ordinary temperatures radon is a colorless gas; when cooled below the freezing point, radon exhibits a brilliant phosphorescence which becomes yellow as the temperature is lowered and orange-red at the temperature of liquid air. It has been reported that fluorine reacts with radon, forming radon fluoride. Radon clathrates have also been reported. Radon is still produced for therapeutic use by a few hospitals by pumping it from a radium source and sealing it in minute tubes, called seeds or needles, for application to patients. This practice has now been largely discontinued as hospitals can order the seeds directly from suppliers, who make up the seeds with the desired activity for the day of use. Care must be taken in handling radon, as with other radioactive materials. The main hazard is from inhalation of the element and its solid daughters, which are collected on dust in the air. Good ventilation should be provided where radium, thorium, or actinium is stored to prevent build-up of this element. Radon build-up is a health consideration in uranium mines. Recently radon build-up in homes has been a concern. Many deaths from lung cancer are caused by radon exposure. In the U.S. it is recommended that remedial action be taken if the air from radon in homes exceeds 4 pCi/l.

Answer 63

Francium — (France), Fr; at. no. 87; at. wt. [223]; m.p. 27°C; valence 1. Discovered in 1939 by Mlle. Marguerite Perey of the Curie Institute, Paris. Francium, the heaviest known member of the alkali metal series, occurs as a result of an alpha disintegration of actinium. It can also be made artificially by bombarding thorium with protons. While it occurs naturally in uranium minerals, there is probably less than an ounce of francium at any time in the total crust of the earth. It has the highest equivalent weight of any element, and is the most unstable of the first 101 elements of the periodic system. Thirty-six isotopes and isomers of francium are recognized. The longest lived 223Fr(Ac, K), a daughter of 227Ac, has a half-life of 21.8 min. This is the only isotope of francium occurring in nature. Because all known isotopes of francium are highly unstable, knowledge of the chemical properties of this element comes from radiochemical techniques. No weighable quantity of the element has been prepared or isolated. The chemical properties of francium most closely resemble cesium. In 1996, researchers Orozco, Sprouse, and co-workers at the State University of New York, Stony Brook, reported that they had produced francium atoms by bombarding 18O atoms at a gold target heated almost to its melting point. Collisions between gold and oxygen nuclei created atoms of francium-210 which had 87 protons and123 neutrons. This team reported they had generated about 1 million francium-210 ions per second and held 1000 or more atoms at a time for about 20 secs. in a magnetic trap they had devised before the atoms decayed or escaped. Enough francium was trapped so that a video camera could capture the light given off by the atoms as they fluoresced. A cluster of about TeamLRN THE ELEMENTS (continued) 4-13 10,000 francium atoms appeared as a glowing sphere about 1 mm in diameter. It is thought that the francium atoms could serve as miniature laboratoires for probing interactions between electrons and quarks.

Answer 64

Radium — (L. radius, ray), Ra; at. wt. (226); at. no. 88; m.p. 700°C; sp. gr. 5; valence 2. Radium was discovered in 1898 by M. and Mme. Curie in the pitchblende or uraninite of North Bohemia (Czech Republic), where it occurs. There is about 1 g of radium in 7 tons of pitchblende. The element was isolated in 1911 by Mme. Curie and Debierne by the electrolysis of a solution of pure radium chloride, employing a mercury cathode; on distillation in an atmosphere of hydrogen this amalgam yielded the pure metal. Originally, radium was obtained from the rich pitchblende ore found at Joachimsthal, Bohemia. The carnotite sands of Colorado furnish some radium, but richer ores are found in the Republic of Congo-Kinshasa and the Great Bear Lake region of Canada. Radium is present in all uranium minerals, and could be extracted, if desired, from the extensive wastes of uranium processing. Large uranium deposits are located in Ontario, New Mexico, Utah, Australia, and elsewhere. Radium is obtained commercially as the bromide or chloride; it is doubtful if any appreciable stock of the isolated element now exists. The pure metal is brilliant white when freshly prepared, but blackens on exposure to air, probably due to formation of the nitride. It exhibits luminescence, as do its salts; it decomposes in water and is somewhat more volatile than barium. It is a member of the alkaline-earth group of metals. Radium imparts a carmine red color to a flame. Radium emits alpha, beta, and gamma rays and when mixed with beryllium produce neutrons. One gram of 226Ra undergoes 3.7 × 1010 disintegrations per s. The curie (Ci) is defined as that amount of radioactivity which has the same disintegration rate as 1 g of 226Ra. Thirty-six isotopes are now known; radium 226, the common isotope, has a half-life of 1599 years. One gram of radium produces about 0.0001 ml (stp) of emanation, or radon gas, per day. This is pumped from the radium and sealed in minute tubes, which are used in the treatment of cancer and other diseases. One gram of radium yields about 4186 kJ per year. Radium is used in producing self-luminous paints, neutron sources, and in medicine for the treatment of disease. Some of the more recently discovered radioisotopes, such as 60Co, are now being used in place of radium. Some of these sources are much more powerful, and others are safer to use. Radium loses about 1% of its activity in 25 years, being transformed into elements of lower atomic weight. Lead is a final product of disintegration. Stored radium should be ventilated to prevent build-up of radon. Inhalation, injection, or body exposure to radium can cause cancer and other body disorders. The maximum permissible burden in the total body for 226Ra is 7400 becquerel.

Answer 65

Actinium — (Gr. aktis, aktinos, beam or ray), Ac; at. wt. (227); at. no. 89; m.p. 1051°C, b.p. 3200 ± 300°C (est.); sp. gr. 10.07 (calc.). Discovered by Andre Debierne in 1899 and independently by F. Giesel in 1902. Occurs naturally in association with uranium minerals. Thirty four isotopes and isomers are now recognized. All are radioactive. Actinium-227, a decay product of uranium-235, is an alpha and beta emitter with a 21.77-year halflife. Its principal decay products are thorium-227 (18.72-day half-life), radium-223 (11.4-day half-life), and a number of short-lived products including radon, bismuth, polonium, and lead isotopes. In equilibrium with its decay products, it is a powerful source of alpha rays. Actinium metal has been prepared by the reduction of actinium fluoride with lithium vapor at about 1100 to 1300°C. The chemical behavior of actinium is similar to that of the rare earths, particularly lanthanum. Purified actinium comes into equilibrium with its decay products at the end of 185 days, and then decays according to its 21.77-year half-life. It is about 150 times as active as radium, making it of value in the production of neutrons. Actinium-225, with a purity of 99%, is available from the Oak Ridge National Laboratory to holders of a permit for about $500/millicurie, plus packing charges.

Answer 66

Thorium — (Thor, Scandinavian god of war), Th; at. wt. 232.0381(1); at. no. 90; m.p. 1750°C; b.p. 4788°C; sp. gr. 11.72; valence +2(?), +3(?), +4. Discovered by Berzelius in 1828. Thorium occurs in thorite (ThSiO4) and in thorianite (ThO2 + UO2). Large deposits of thorium minerals have been reported in New England and elsewhere, but these have not yet been exploited. Thorium is now thought to be about three times as abundant as uranium and about as abundant as lead or molybdenum. The metal is a source of nuclear power. There is probably more energy available for use from thorium in the minerals of the earth’s crust than from both uranium and fossil fuels. Any sizable demand for thorium as a nuclear fuel is still several THE ELEMENTS (continued) 4-32 years in the future. Work has been done in developing thorium cycle converter-reactor systems. Several prototypes, including the HTGR (hightemperature gas-cooled reactor) and MSRE (molten salt converter reactor experiment), have operated. While the HTGR reactors are efficient, they are not expected to become important commercially for many years because of certain operating difficulties. Thorium is recovered commercially from the mineral monazite, which contains from 3 to 9% ThO2 along with rare-earth minerals. Much of the internal heat the earth produces has been attributed to thorium and uranium. Several methods are available for producing thorium metal: it can be obtained by reducing thorium oxide with calcium, by electrolysis of anhydrous thorium chloride in a fused mixture of sodium and potassium chlorides, by calcium reduction of thorium tetrachloride mixed with anhydrous zinc chloride, and by reduction of thorium tetrachloride with an alkali metal. Thorium was originally assigned a position in Group IV of the periodic table. Because of its atomic weight, valence, etc., it is now considered to be the second member of the actinide series of elements. When pure, thorium is a silvery-white metal which is air-stable and retains its luster for several months. When contaminated with the oxide, thorium slowly tarnishes in air, becoming gray and finally black. The physical properties of thorium are greatly influenced by the degree of contamination with the oxide. The purest specimens often contain several tenths of a percent of the oxide. High-purity thorium has been made. Pure thorium is soft, very ductile, and can be cold-rolled, swaged, and drawn. Thorium is dimorphic, changing at 1400°C from a cubic to a body-centered cubic structure. Thorium oxide has a melting point of 3300°C, which is the highest of all oxides. Only a few elements, such as tungsten, and a few compounds, such as tantalum carbide, have higher melting points. Thorium is slowly attacked by water, but does not dissolve readily in most common acids, except hydrochloric. Powdered thorium metal is often pyrophoric and should be carefully handled. When heated in air, thorium turnings ignite and burn brilliantly with a white light. The principal use of thorium has been in the preparation of the Welsbach mantle, used for portable gas lights. These mantles, consisting of thorium oxide with about 1% cerium oxide and other ingredients, glow with a dazzling light when heated in a gas flame. Thorium is an important alloying element in magnesium, imparting high strength and creep resistance at elevated temperatures. Because thorium has a low work-function and high electron emission, it is used to coat tungsten wire used in electronic equipment. The oxide is also used to control the grain size of tungsten used for electric lamps; it is also used for high-temperature laboratory crucibles. Glasses containing thorium oxide have a high refractive index and low dispersion. Consequently, they find application in high quality lenses for cameras and scientific instruments. Thorium oxide has also found use as a catalyst in the conversion of ammonia to nitric acid, in petroleum cracking, and in producing sulfuric acid. Thorium has not found many uses due to its radioactive nature and its handling and disposal problems. Thirty isotopes of thorium are known with atomic masses ranging from 210 to 237. All are unstable. 232Th occurs naturally and has a half-life of 1.4 × 1010 years. It is an alpha emitter. 232Th goes through six alpha and four beta decay steps before becoming the stable isotope 208Pb. 232Th is sufficiently radioactive to expose a photographic plate in a few hours. Thorium disintegrates with the production of “thoron” (220Rn), which is an alpha emitter and presents a radiation hazard. Good ventilation of areas where thorium is stored or handled is therefore essential. Thorium metal (99.8%) costs about $25/g.

Answer 67

Protactinium — (Gr. protos, first), Pa; at. wt. 231.03588(2); at. no. 91; m.p. 1572°C; sp. gr. 15.37 (calc.); valence 4 or 5. The first isotope of element 91 to be discovered was 234Pa, also known as UX2, a short-lived member of the naturally occurring 238U decay series. It was identified by K. Fajans and O. H. Gohring in 1913 and they named the new element brevium. When the longer-lived isotope 231Pa was identified by Hahn and Meitner in 1918, the name protoactinium was adopted as being more consistent with the characteristics of the most abundant isotope. Soddy, Cranson, and Fleck were also active in this work. The name protoactinium was shortened to protactinium in 1949. In 1927, Grosse prepared 2 mg of a white powder, which was shown to be Pa2O5. Later, in 1934, from 0.1 g of pure Pa2O5 he isolated the element by two methods, one of which was by converting the oxide to an iodide and “cracking” it in a high vacuum by an electrically heated filament by the reaction 2PaI 2Pa + 5I 5 2 Protactinium has a bright metallic luster which it retains for some time in air. The element occurs in pitchblende to the extent of about 1 part 231Pa to 10 million of ore. Ores from Congo-Kinshasa have about 3 ppm. Protactinium has twenty-eight isotopes and isomers, the most common of which is 231Pr with a half-life of 32,500 years. A number of protactinium compounds are known, some of which are colored. The element is superconductive below 1.4 K. The element is a dangerous toxic material and requires precautions similar to those used when handling plutonium. In 1959 and 1961, it was announced that the Great Britain Atomic Energy Authority extracted by a 12-stage process 125 g of 99.9% protactinium, the world’s only stock of the metal for many years to come. The extraction was made from 60 tons of waste material at a cost of about $500,000. Protactinium is one of the rarest and most expensive naturally occurring elements.

Answer 68

Uranium — (Planet Uranus), U; at. wt. 238.0289(1); at. no. 92; m.p. 1135°C; b.p. 4131°C; sp. gr. ~18.95; valence 2, 3, 4, 5, or 6. Yellow-colored glass, containing more than 1% uranium oxide and dating back to 79 A.D., has been found near Naples, Italy. Klaproth recognized an unknown element in pitchblende and attempted to isolate the metal in 1789. The metal apparently was first isolated in 1841 by Peligot, who reduced the anhydrous chloride with potassium. Uranium is not as rare as it was once thought. It is now considered to be more plentiful than mercury, antimony, silver, or cadmium, and is about as abundant as molybdenum or arsenic. It occurs in numerous minerals such as pitchblende, uraninite, carnotite, autunite, uranophane, davidite, and tobernite. It is also found in phosphate rock, lignite, monazite sands, and can be recovered commercially from these sources. Large deposits of uranium ore occur in Utah, Colorado, New Mexico, Canada, and elsewhere. Uranium can be made by reducing uranium halides with alkali or alkaline earth metals or by reducing uranium oxides by calcium, aluminum, or carbon at high temperatures. The metal can also be produced by electrolysis of KUF5 or UF4, dissolved in a molten mixture of CaCl2 and NaCl. High-purity uranium can be prepared by the thermal decomposition of uranium halides on a hot filament. Uranium exhibits three crystallographic modifications as follows: Uranium is a heavy, silvery-white metal which is pyrophoric when finely divided. It is a little softer than steel, and is attacked by cold water in a finely divided state. It is malleable, ductile, and slightly paramagnetic. In air, the metal becomes coated with a layer of oxide. Acids dissolve the metal, but it is unaffected by alkalis. Uranium has twenty three isotopes, one of which is an isomer and all of which are radioactive. Naturally occurring uranium contains 99.2745% by weight 238U, 0.720% 235U, and 0.0055% 234U. Studies show that the percentage weight of 235U in natural uranium varies by as much as 0.1%, depending on the source. The U.S.D.O.E. has adopted the value of 0.711 as being their “official” percentage of 235U in natural uranium. Natural uranium is sufficiently radioactive to expose a photographic plate in an hour or so. Much of the internal heat of the earth is thought to be α688°C→β776°C→γ THE ELEMENTS (continued) 4-34 attributable to the presence of uranium and thorium. 238U with a half-life of 4.46 × 109 years, has been used to estimate the age of igneous rocks. The origin of uranium, the highest member of the naturally occurring elements — except perhaps for traces of neptunium or plutonium — is not clearly understood, although it has been thought that uranium might be a decay product of elements of higher atomic weight, which may have once been present on earth or elsewhere in the universe. These original elements may have been formed as a result of a primordial “creation,” known as “the big bang,” in a supernova, or in some other stellar processes. The fact that recent studies show that most trans-uranic elements are extremely rare with very short half-lives indicates that it may be necessary to find some alternative explanation for the very large quantities of radioactive uranium we find on earth. Studies of meteorites from other parts of the solar system show a relatively low radioactive content, compared to terrestrial rocks. Uranium is of great importance as a nuclear fuel. 238U can be converted into fissionable plutonium by the following reactions: This nuclear conversion can be brought about in “breeder” reactors where it is possible to produce more new fissionable material than the fissionable material used in maintaining the chain reaction. 235U is of even greater importance, for it is the key to the utilization of uranium. 235U, while occurring in natural uranium to the extent of only 0.72%, is so fissionable with slow neutrons that a self-sustaining fission chain reaction can be made to occur in a reactor constructed from natural uranium and a suitable moderator, such as heavy water or graphite, alone. 235U can be concentrated by gaseous diffusion and other physical processes, if desired, and used directly as a nuclear fuel, instead of natural uranium, or used as an explosive. Natural uranium, slightly enriched with 235U by a small percentage, is used to fuel nuclear power reactors for the generation of electricity. Natural thorium can be irradiated with neutrons as follows to produce the important isotope 233U. While thorium itself is not fissionable, 233U is, and in this way may be used as a nuclear fuel. One pound of completely fissioned uranium has the fuel value of over 1500 tons of coal. The uses of nuclear fuels to generate electrical power, to make isotopes for peaceful purposes, and to make explosives are well known. The estimated world-wide production of the 437 nuclear power reactors in operation in 1998 amounted to about 352,000 Megawatt hours. In 1998 the U.S. had about 107 commercial reactors with an output of about 100,000 Megawatt-hours. Some nuclear-powered electric generating plants have recently been closed because of safety concerns. There are also serious problems with nuclear waste disposal that have not been completely resolved. Uranium in the U.S.A. is controlled by the U.S. Nuclear Regulatory Commission, under the Department of Energy. Uses are being found for the large quantities of “depleted” uranium, now available, where uranium-235 has been lowered to about 0.2%. Depleted uranium has been used for inertial guidance devices, gyrocompasses, counterweights for aircraft control surfaces, ballast for missile reentry vehicles, and as a shielding material for tanks, etc. Concerns, however, have been raised over its low radioactive properties. Uranium metal is used for X-ray targets for production of high-energy X-rays. The nitrate has been used as photographic toner, and the acetate is used in analytical chemistry. Crystals of uranium nitrate are triboluminescent. Uranium salts have also been used for producing yellow “vaseline” glass and glazes. Uranium and its compounds are highly toxic, both from a chemical and radiological standpoint. Finely divided uranium metal, being pyrophoric, presents a fire hazard. The maximum permissible total body burden of natural uranium (based on radiotoxicity) is 0.2 μCi for soluble compounds. Recently, the natural presence of uranium and thorium in many soils has become of concern to homeowners because of the generation of radon and its daughters (see under Radon). Uranium metal is available commercially at a cost of about $6/g (99.7%) in air-tight glass under argon.

Answer 69

Neptunium — (Planet Neptune), Np; at. wt. (237); at. no. 93; m.p. 644°C; sp. gr. 20.25 (20°C); valence 3, 4, 5, and 6. Neptunium was the first synthetic transuranium element of the actinide series discovered; the isotope 239Np was produced by McMillan and Abelson in 1940 at Berkeley, California, as the result of bombarding uranium with cyclotron-produced neutrons. The isotope 237Np (half-life of 2.14 × 106 years) is currently obtained in gram quantities as a by-product from nuclear reactors in the production of plutonium. Twenty-three isotopes and isomers of neptunium are now recognized. Trace quantities of the element are actually found in nature due to transmutation reactions in uranium ores produced by the neutrons which are present. Neptunium is prepared by the reduction of NpF3 with barium or lithium vapor at about 1200°C. Neptunium metal has a silvery appearance, is chemically reactive, and exists in at least three structural modifications: α-neptunium, orthorhombic, density 20.25 g/cm3, β-neptunium (above 280°C), tetragonal, density (313°C) 19.36 g/cm3; γ-neptunium (above 577°C), cubic, density (600°C) 18.0 g/cm3. Neptunium has four ionic oxidation states in solution: Np+3 (pale purple), analogous to the rare earth ion Pm+3, Np+4 (yellow green); NpO+ (green blue); and NpO++ (pale pink). These latter oxygenated species are in contrast to the rare earths which exhibit only simple ions of the (II), (III), and (IV) oxidation states in aqueous solution. The element forms tri- and tetrahalides such as NpF3, NpF4, NpCl4, NpBr3, NpI3, and oxides of various compositions such as are found in the uraniumoxygen system, including Np3O8 and NpO2.

Answer 70

Plutonium — (Planet pluto), Pu; at. wt. (244); at. no. 94; sp. gr. (α modification) 19.84 (25°C); m.p. 640°C; b.p. 3228°C; valence 3, 4, 5, or 6. Plutonium was the second transuranium element of the actinide series to be discovered. The isotope 238Pu was produced in 1940 by Seaborg, McMillan, Kennedy, and Wahl by deuteron bombardment of uranium in the 60-inch cyclotron at Berkeley, California. Plutonium also exists in trace quantities in naturally occurring uranium ores. It is formed in much the same manner as neptunium, by irradiation of natural uranium with the neutrons which are present. By far of greatest importance is the isotope Pu239, with a half-life of 24,100 years, produced in extensive quantities in nuclear reactors from natural uranium: Nineteen isotopes of plutonium are now known. Plutonium has assumed the position of dominant importance among the transuranium elements because of its successful use as an explosive ingredient in nuclear weapons and the place which it holds as a key material in the development of industrial use of nuclear power. One kilogram is equivalent to about 22 million kilowatt hours of heat energy. The complete detonation of a kilogram of plutonium produces an explosion equal to about 20,000 tons of chemical explosive. Its importance depends on the nuclear property of being readily fissionable with neutrons and its availability in quantity. The world’s nuclear-power reactors are now producing about 20,000 kg of plutonium/yr. By 1982 it was estimated that about 300,000 kg had accumulated. The various nuclear applications of plutonium are well known. 238Pu has been used in the Apollo lunar missions to power seismic and other equipment on the lunar surface. As with neptunium and uranium, plutonium metal can be prepared by reduction of the trifluoride with alkaline-earth metals. The metal has a silvery appearance and takes on a yellow tarnish when slightly oxidized. It is chemically reactive. A relatively large piece of plutonium is warm to the touch because of the energy given off in alpha decay. Larger pieces will produce enough heat to boil water. The metal readily dissolves in concentrated hydrochloric acid, hydroiodic acid, or perchloric acid with formation of the Pu+3 ion. The metal exhibits six allotropic modifications having various crystalline structures. The densities of these vary from 16.00 to 19.86 g/cm3. Plutonium also exhibits four ionic valence states in aqueous solutions: Pu+3(blue lavender), Pu+4 (yellow brown), PuO+ (pink?), and PuO+2 (pink orange). The ion PuO+ is unstable in aqueous solutions, disproportionating into Pu+4 and PuO+2. The Pu+4 thus formed, however, oxidizes the PuO+ into PuO+2, itself being reduced to Pu+3, giving finally Pu+3 and PuO+2. Plutonium forms binary compounds with oxygen: PuO, PuO2, and intermediate oxides of variable composition; with the halides: PuF3, PuF4, PuCl3, PuBr3, PuI3; with carbon, nitrogen, and silicon: PuC, PuN, PuSi2. Oxyhalides are also well known: PuOCl, PuOBr, PuOI. Because of the high rate of emission of alpha particles and the element being specifically absorbed by bone marrow, plutonium, as well as all of the other transuranium elements except neptunium, are radiological poisons and must be handled with very special equipment and precautions. Plutonium is a very dangerous radiological hazard. Precautions must also be taken to prevent the unintentional formation of a critical mass. Plutonium in liquid solution is more likely to become critical than solid plutonium. The shape of the mass must also be considered where criticality is concerned. Plutonium-239 is available to authorized users from the O.R.N.L. at a cost of about $4.80/mg (99.9%) plus packing costs.

Answer 71

Americium — (the Americas), Am; at. wt. 243; at. no. 95; m.p. 1176°C; b.p. 2011°C; sp. gr. 13.67 (20°C); valence 2, 3, 4, 5, or 6. Americium was the fourth transuranium element to be discovered; the isotope 241Am was identified by Seaborg, James, Morgan, and Ghiorso late in 1944 at the wartime Metallurgical Laboratory of the University of Chicago as the result of successive neutron capture reactions by plutonium isotopes in a nuclear reactor: Since the isotope 241Am can be prepared in relatively pure form by extraction as a decay product over a period of years from strongly neutronbombarded plutonium, 241Pu, this isotope is used for much of the chemical investigation of this element. Better suited is the isotope 243Am due to its longer half-life (7.37 × 103 years as compared to 432.2 years for 241Am). A mixture of the isotopes 241Am, 242Am, and 243Am can be prepared by intense neutron irradiation of 241Am according to the reactions 241Am (n, γ) → 242Am (n, γ) → 243Am. Nearly isotopically pure 243Am can be prepared by a sequence of neutron bombardments and chemical separations as follows: neutron bombardment of 241Am yields 242Pu by the reactions 241Am (n, γ) → 242Am → 242Pu, after chemical separation the 242Pu can be transformed to 243Am via the reactions 242Pu (n, γ) → 243Pu → 243Am, and the 243Am can 239 Pu(n, γ )→240Pu(n, γ )→241Puβ→241Am THE ELEMENTS (continued) 4-4 be chemically separated. Fairly pure 242Pu can be prepared more simply by very intense neutron irradiation of 239Pu as the result of successive neutroncapture reactions. Seventeen radioactive isotopes and isomers are now recognized. Americium metal has been prepared by reducing the trifluoride with barium vapor at 1000 to 1200°C or the dioxide by lanthanum metal. The luster of freshly prepared americium metal is white and more silvery than plutonium or neptunium prepared in the same manner. It appears to be more malleable than uranium or neptunium and tarnishes slowly in dry air at room temperature. Americium is thought to exist in two forms: an alpha form which has a double hexagonal close-packed structure and a loosepacked cubic beta form. Americium must be handled with great care to avoid personal contamination. As little as 0.03 μCi of 241Am is the maximum permissible total body burden. The alpha activity from 241Am is about three times that of radium. When gram quantities of 241Am are handled, the intense gamma activity makes exposure a serious problem. Americium dioxide, AmO2, is the most important oxide. AmF3, AmF4, AmCl3, AmBr3, AmI3, and other compounds have been prepared. The isotope 241Am has been used as a portable source for gamma radiography. It has also been used as a radioactive glass thickness gage for the flat glass industry, and as a source of ionization for smoke detectors. Americum-243 (99%) is available from the Oak Ridge National Laboratory at a cost of about $750/g plus packing charges.

Answer 72

Curium — (Pierre and Marie Curie), Cm; at. wt. (247); at. no. 96; m.p. 1345°C; sp. gr. 13.51 (calc.); valence 3 and 4. Although curium follows americium in the periodic system, it was actually known before americium and was the third transuranium element to be discovered. It was identified by Seaborg, James, and Ghiorso in 1944 at the wartime Metallurgical Laboratory in Chicago as a result of helium-ion bombardment of 239Pu in the Berkeley, California, 60-inch cyclotron. Visible amounts (30 μg) of 242Cm, in the form of the hydroxide, were first isolated by Werner and Perlman of the University of California in 1947. In 1950, Crane, Wallmann, and Cunningham found that the magnetic susceptibility of microgram samples of CmF3 was of the same magnitude as that of GdF3. This provided direct experimental evidence for assigning an electronic configuration to Cm+3. In 1951, the same workers prepared curium in its elemental form for the first time. Sixteen isotopes of curium are now known. The most stable, 247Cm, with a half-life of 16 million years, is so short compared to the earth’s age that any primordial curium must have disappeared long ago from the natural scene. Minute amounts of curium probably exist in natural deposits of uranium, as a result of a sequence of neutron captures and β decays sustained by the very low flux of neutrons naturally present in uranium ores. The presence of natural curium, however, has never been detected. 242Cm and 244Cm are available in multigram quantities. 248Cm has been produced only in milligram amounts. Curium is similar in some regards to gadolinium, its rareearth homolog, but it has a more complex crystal structure. Curium is silver in color, is chemically reactive, and is more electropositive than aluminum. CmO2, Cm2O3, CmF3, CmF4, CmCl3, CmBr3, and CmI3 have been prepared. Most compounds of trivalent curium are faintly yellow in color. 242Cm generates about three watts of thermal energy per gram. This compares to one-half watt per gram of 238Pu. This suggests use for curium as a power source. 244Cm is now offered for sale by the O.R.N.L. at $185/mg plus packing charges. 248Cm is available at a cost of $160/μg, plus packing charges, THE ELEMENTS (continued) 4-10 from the O.R.N.L. Curium absorbed into the body accumulates in the bones, and is therefore very toxic as its radiation destroys the red-cell forming mechanism. The maximum permissible total body burden of 244Cm (soluble) in a human being is 0.3 μCi (microcurie).

Answer 73

Berkelium — (Berkeley, home of the University of California), Bk; at. wt. (247); at. no. 97; m.p. 1050°C; valence 3 or 4; sp. gr. 14 (est.). Berkelium, the eighth member of the actinide transition series, was discovered in December 1949 by Thompson, Ghiorso, and Seaborg, and was the fifth transuranium element synthesized. It was produced by cyclotron bombardment of milligram amounts of 241Am with helium ions at Berkeley, California. The first isotope produced had a mass number of 243 and decayed with a half-life of 4.5 hours. Thirteen isotopes are now known and have been synthesized. The existence of 249Bk, with a half-life of 320 days, makes it feasible to isolate berkelium in weighable amounts so that its properties can be investigated with macroscopic quantities. One of the first visible amounts of a pure berkelium compound, berkelium chloride, was produced in 1962. It weighed 3 billionth of a gram. Berkelium probably has not yet been prepared in elemental form, but it is expected to be a silvery metal, easily soluble in dilute mineral acids, and readily oxidized by air or oxygen at elevated temperatures to form the oxide. X-ray diffraction methods have been used to identify the following compounds: BkO2, BkO3, BkF3, BkCl, and BkOCl. As with other actinide elements, berkelium tends to accumulate in the skeletal system. The maximum permissible body burden of 249Bk in the human skeleton is about 0.0004 μg. Because of its rarity, berkelium presently has no commercial or technological use. Berkelium most likely resembles terbium with respect to chemical properties. Berkelium-249 is available from O.R.N.L. at a cost of $185/μg plus packing charges.

Answer 74

Californium — (State and University of California), Cf; at. wt. (251); m.p. 900°C; at. no. 98. Californium, the sixth transuranium element to be discovered, was produced by Thompson, Street, Ghioirso, and Seaborg in 1950 by bombarding microgram quantities of 242Cm with 35 MeV helium ions in the Berkeley 60-inch cyclotron. Californium (III) is the only ion stable in aqueous solutions, all attempts to reduce or oxidize californium (III) having failed. The isotope 249Cf results from the beta decay of 249Bk while the heavier isotopes are produced by intense neutron irradiation by the reactions: followed by The existence of the isotopes 249Cf, 250Cf, 251Cf, and 252Cf makes it feasible to isolate californium in weighable amounts so that its properties can be investigated with macroscopic quantities. Californium-252 is a very strong neutron emitter. One microgram releases 170 million neutrons per minute, which presents biological hazards. Proper safeguards should be used in handling californium. Twenty isotopes of californium are now recognized. 249Cf and 252Cf have half-lives of 351 years and 900 years, respectively. In 1960 a few tenths of a microgram of californium trichloride, CfCl3, californium oxychloride, CfOCl, and californium oxide, Cf2O3, were first prepared. Reduction of californium to its metallic state has not yet been accomplished. Because californium is a very efficient source of neutrons, many new uses are expected for it. It has already found use in neutron moisture gages and in well-logging (the determination of water and oil-bearing layers). It is also being used as a portable neutron source for discovery of metals such as gold or silver by on-the-spot activation analysis. 252Cf is now being offered for sale by the Oak Ridge National Laboratory (O.R.N.L.) at a cost of $60/μg and 249Cf at a cost of $185/μg plus packing charges. It has been suggested that californium may be produced in certain stellar explosions, called supernovae, for the radioactive decay of 254Cf (55-day half-life) agrees with the characteristics of the light curves of such explosions observed through telescopes. This suggestion, however, is questioned. Californium is expected to have chemical properties similar to dysprosium.

Answer 75

Einsteinium — (Albert Einstein [1879–1955]), Es; at. wt. (252); m.p. 860°C (est.); at. no. 99. Einsteinium, the seventh transuranic element of the actinide series to be discovered, was identified by Ghiorso and co-workers at Berkeley in December 1952 in debris from the first large thermonuclear explosion, which took place in the Pacific in November 1952. The isotope produced was the 20-day 253Es isotope. In 1961, a sufficient amount of einsteinium was produced to permit separation of a macroscopic amount of 253Es. This sample weighed about 0.01 μg. A special magnetic-type balance was used in making this determination. 253Es so produced was used to produce mendelevium. About 3 μg of einsteinium has been produced at Oak Ridge National Laboratories by irradiating for several years kilogram quantities of 239Pu in a reactor to produce 242Pu. This was then fabricated into pellets of plutonium oxide and aluminum powder, and loaded into target rods for an initial 1-year irradiation at the Savannah River Plant, followed by irradiation in a HFIR (High Flux Isotopic Reactor). After 4 months in the HFIR the targets were removed for chemical separation of the einsteinium from californium. Nineteen isotopes and isomers of einsteinium are now recognized. 254Es has the longest half-life (276 days). Tracer studies using 253Es show that einsteinium has chemical properties typical of a heavy trivalent, actinide element. Einsteinium is extremely radioactive. Great care must be taken when handling it.

Answer 76

Fermium — (Enrico Fermi [1901–1954], nuclear physicist), Fm; at. wt. [257]; at. no. 100; m.p. 1527°C. Fermium, the eighth transuranium element of the actinide series to be discovered, was identified by Ghiorso and co-workers in 1952 in the debris from a thermonuclear explosion in the Pacific in work involving the University of California Radiation Laboratory, the Argonne National Laboratory, and the Los Alamos Scientific Laboratory. The isotope produced was the 20-hour 255Fm. During 1953 and early 1954, while discovery of elements 99 and 100 was withheld from publication for security reasons, a group from the Nobel Institute of Physics in Stockholm bombarded 238U with 16O ions, and isolated a 30-min α-emitter, which they ascribed to 250100, without claiming discovery of the element. This isotope has since been identified positively, and the 30-min half-life confirmed. The chemical properties of fermium have been studied solely with tracer amounts, and in normal aqueous media only the (III) oxidation state appears to exist. The isotope 254Fm and heavier isotopes can be produced by intense neutron irradiation of lower elements such as plutonium by a process of successive neutron capture interspersed with beta decays until these mass numbers and atomic numbers are reached. Twenty isotopes and isomers of fermium are known to exist. 257Fm, with a half-life of about 100.5 days, is the longest lived. 250Fm, with a half-life of 30 min, has been shown to be a product of decay of Element 254102. It was by chemical identification of 250Fm that production of Element 102 (nobelium) was confirmed. Fermium would probably have chemical properties resembling erbium.

Answer 77

Mendelevium — (Dmitri Mendeleev [1834–1907]), Md; at. wt. (258); at. no. 101; m.p. 827°C; valence +2, +3. Mendelevium, the ninth transuranium element of the actinide series to be discovered, was first identified by Ghiorso, Harvey, Choppin, Thompson, and Seaborg early in 1955 as a result of the bombardment of the isotope 253Es with helium ions in the Berkeley 60-inch cyclotron. The isotope produced was 256Md, which has a half-life of 78 min. This first identification was notable in that 256Md was synthesized on a one-atom-at-a-time basis. Nineteen isotopes and isomers are now recognized. 258Md has a half-life of 51.5 days. This isotope has been produced by the bombardment of an isotope of einsteinium with ions of helium. It now appears possible that eventually enough 258Md can be made so that some of its physical properties can be determined. 256Md has been used to elucidate some of the chemical properties of mendelevium in aqueous solution. Experiments seem to show that the element possesses a moderately stable dipositive (II) oxidation state in addition to the tripositive (III) oxidation state,which is characteristic of actinide elements.

Answer 78

Nobelium — (Alfred Nobel, discoverer of dynamite), No; at. wt. [259]; at. no. 102; valence +2, +3. Nobelium was unambiguously discovered and identified in April 1958 at Berkeley by A. Ghiorso, T. Sikkeland, J. R. Walton, and G. T. Seaborg, who used a new double-recoil technique. A heavy-ion linear accelerator (HILAC) was used to bombard a thin target of curium (95% 244Cm and 4.5% 246Cm) with 12C ions to produce 102254 according to the 246Cm (12C, 4n) reaction. Earlier in 1957 workers of the U.S., Britain, and Sweden announced the discovery of an isotope of Element 102 with a 10-min half-life at 8.5 MeV, as a result of bombarding 244Cm with 13C nuclei. On the basis of this experiment the name nobelium was assigned and accepted by the Commission on Atomic Weights of the International Union of Pure and Applied Chemistry. The acceptance of the name was premature, for both Russian and American efforts now completely rule out the possibility of any isotope of Element 102 having a half-life of 10 min in the vicinity of 8.5 MeV. Early work in 1957 on the search for this element, in Russia at the Kurchatov Institute, was marred by the assignment of 8.9 ± 0.4 MeV alpha radiation with a half-life of 2 to 40 sec, which was too indefinite to support claim to discovery. Confirmatory experiments at Berkeley in 1966 have shown the existence of 254102 with a 55-s half-life, 252102 with a 2.3-s half-life, and 257102 with a 25-s half-life. Twelve isotopes are now recognized, one of which — 255102 has a half-life of 3.1 min. In view of the discover’s traditional right to name an element, the Berkeley group, in 1967, suggested that the hastily given name nobelium, along with the symbol No, be retained.

Answer 79

Lawrencium — (Ernest O. Lawrence [1901–1958], inventor of the cyclotron), Lr; at. no. 103; at. mass no. [262]; valence + 3(?). This member of the 5f transition elements (actinide series) was discovered in March 1961 by A. Ghiorso, T. Sikkeland, A. E. Larsh, and R. M. Latimer.A 3-μg californium target, consisting of a mixture of isotopes of mass number 249, 250, 251, and 252, was bombarded with either 10B or 11B. The electrically charged transmutation nuclei recoiled with an atmosphere of helium and were collected on a thin copper conveyor tape which was then moved to place collected atoms in front of a series of solid-state detectors. The isotope of element 103 produced in this way decayed by emitting an 8.6-MeV alpha particle with a half-life of 8 s. In 1967, Flerov and associates of the Dubna Laboratory reported their inability to detect an alpha emitter with a halflife of 8 s which was assigned by the Berkeley group to 257103. This assignment has been changed to 258Lr or 259Lr. In 1965, the Dubna workers found THE ELEMENTS (continued) 4-18 a longer-lived lawrencium isotope, 256Lr, with a half-life of 35 s. In 1968, Ghiorso and associates at Berkeley were able to use a few atoms of this isotope to study the oxidation behavior of lawrencium. Using solvent extraction techniques and working very rapidly, they extracted lawrencium ions from a buffered aqueous solution into an organic solvent, completing each extraction in about 30 s. It was found that lawrencium behaves differently from dipositive nobelium and more like the tripositive elements earlier in the actinide series. Ten isotopes of lawrencium are now recognized.

Answer 80

Rutherfordium — (named for Ernest Rutherford [1871–1937], New Zealand, Canadian, and British physicist); Rf; at. wt. [261]; at. no. 104. In 1964, workers of the Joint Nuclear Research Institute at Dubna (Russia) bombarded plutonium with accelerated 113 to 115 MeV neon ions. By measuring fission tracks in a special glass with a microscope, they detected an isotope that decays by spontaneous fission. They suggested that this isotope, which has a half-life of 0.3 ± 0.1 s, might be 260104, produced by the following reaction: 94 242 10 Pu+22Ne→260 104 + 4n Element 104, the first transactinide element, is expected to have chemical properties similar to those of hafnium. It would, for example, form a relatively volatile compound with chlorine (a tetrachloride). The Soviet scientists have performed experiments aimed at chemical identification, and have attempted to show that the 0.3-s activity is more volatile than that of the relatively nonvolatile actinide trichlorides. This experiment does not fulfill the test of chemically separating the new element from all others, but it provides important evidence for evaluation. New data, reportedly issued by Soviet scientists, have reduced the half-life of the isotope they worked with from 0.3 to 0.15 s. The Dubna scientists suggest the name kurchatovium and symbol Ku for Element 104, in honor of Igor Vasilevich Kurchatov (1903—1960), late Head of Soviet Nuclear Research. The Dubna Group also has proposed the name dubnium for Element 104. In 1969, Ghiorso, Nurmia, Harris, K. A. Y. Eskola, and P. L. Eskola of the University of California at Berkeley reported they had positively identified two, and possibly three, isotopes of Element 104. The group also indicated that after repeated attempts so far they have been unable to produce isotope 260104 reported by the Dubna groups in 1964. The discoveries at Berkeley were made by bombarding a target of 249Cf with 12C nuclei of 71 MeV, and 13C nuclei of 69 MeV. The combination of 12C with 249Cf followed by instant emission of four neutrons produced Element 257104. This isotope has a half-life of 4 to 5 s, decaying by emitting an alpha particle into 253No, with a half-life of 105 s. The same reaction, except with the emission of three neutrons, was thought to have produced 258104 with a half-life of about 1/100 s. Element 259104 is formed by the merging of a 13C nuclei with 249Cf, followed by emission of three neutrons. This isotope has a half-life of 3 to 4 s, and decays by emitting an alpha particle into 255No, which has a half-life of 185 s. Thousands of atoms of 257104 and 259104 have been detected. The Berkeley group believe their identification of 258104 was correct. Eleven isotopes of Element 104 have now been identified. The Berkeley group proposed for the new element the name rutherfordium (symbol Rf), in honor of Ernest Rutherford. This name was formally adapted by IUPAC in August 1997.

Answer 81

Dubnium — (named after the Joint Institute of Nuclear Research in Dubna, Russia). Db; at.wt. [262]; at.no. 105. In 1967 G. N. Flerov reported that a Soviet team working at the Joint Institute for Nuclear Research at Dubna may have produced a few atoms of 260105 and 261105 by bombarding 243Am with 22Ne. Their evidence was based on time-coincidence measurements of alpha energies. More recently, it was reported that early in 1970 Dubna scientists synthesized Element 105 and that by the end of April 1970 “had investigated all the types of decay of the new element and had determined its chemical properties.” In late April 1970, it was announced that Ghiorso, Nurmia, Harris, K. A. Y. Eskola, and P. L. Eskola, working at the University of California at Berkeley, had positively identified Element 105. The discovery was made by bombarding a target of 249Cf with a beam of 84 MeV nitrogen nuclei in the Heavy Ion Linear Accelerator (HILAC). When a 15N nuclear is absorbed by a 249Cf nucleus, four neutrons are emitted and a new atom of 260105 with a half-life of 1.6 s is formed. While the first atoms of Element 105 are said to have been detected conclusively on March 5, 1970, there is evidence that Element 105 had been formed in Berkeley experiments a year earlier by the method described. Ghiorso and his associates have attempted to confirm Soviet findings by more sophisticated methods without success. In October 1971, it was announced that two new isotopes of Element 105 were synthesized with the heavy ion linear accelerator by A. Ghiorso and co-workers at Berkeley. Element 261105 was produced both by bombarding 250Cf with 15N and by bombarding 249Bk with 16O. The isotope emits 8.93-MeV α particles and decays to 257Lr with a half-life of about 1.8 s. Element 262105 was produced by bombarding 249Bk with 18O. It emits 8.45 MeV α particles and decays to 258Lr with a half-life of about 40 s. Nine isotopes of Dubnium are now recognized. Soon after the discovery the names Hahnium and Joliotium, named after Otto Hahn and Jean-Frederic Joliot and Mme. Joliot-Curie, were suggested as names for Element 105. The IUPAC in August 1997 finally resolved the issue, naming Element 105 Dubnium with the symbol Db. Dubnium is thought to have properties similar to tantalum.

Answer 82

Seaborgium — (named for Glenn T. Seaborg [1912–1999], American chemist and nuclear physicist). Sg; at. wt. [263]; at no. 106. The discovery of Seaborgium, Element 106, took place in 1974 almost simultaneously at the Lawrence-Berkeley Laboratory and at the Joint Institute for Nuclear Research at Dubna, Russia. The Berkeley Group, under direction of Ghiorso, used the Super-Heavy Ion Linear Accelerator (Super HILAC) as a source of heavy 18O ions to bombard a 259-μg target of 249Cf. This resulted in the production and positive identification of 263106, which decayed with a halflife of 0.9 ± 0.2 s by the emission of alpha particles as follows: 263106α→259104α→255Noα→. The Dubna Team, directed by Flerov and Organessian, produced heavy ions of 54Cr with their 310-cm heavy-ion cyclotron to bombard 207Pb and 208Pb and found a product that decayed with a half-life of 7 ms. They assigned 259106 to this isotope. It is now thought seven isotopes of Seaborgium have been identified. Two of the isotopes are believed to have half-lives of about 30 s. Seaborgium most likely would have properties resembling tungsten. The IUPAC adopted the name Seaborgium in August 1997. Normally the naming of an element is not given until after the death of the person for which the element is named; however, in this case, it was named while Dr. Seaborg was still alive.

Answer 83

Bohrium — (Named after Niels Bohr [1885-1962], Danish atomic and nuclear physicist.) Bh; at.wt. [262]. at.no. 107. Bohrium is expected to have chemical properties similar to rhenium. This element was synthesized and unambiguously identified in 1981 using the Universal Linear Accelerator (UNILAC) at the Gesellschaft für Schwerionenforschung (G.S.I.) in Darmstadt, Germany. The discovery team was led by Armbruster and Münzenberg. The reaction producing the element was proposed and applied earlier by a Dubna Group led by Oganessian in 1976. A target of 209Bi was bombarded by a beam of 54Cr ions. In 1983 experiments at Dubna using the 157-inch cyclotron, produced 262107 by the reaction 209Bi + 54Cr. The alpha decay of 246Cf, the sixth member in the decay chain of 262107, served to establish a 1-neutron reaction channel. The IUPAC adopted the name Bohrium with the symbol Bh for Element 107 in August 1997. Five isotopes of bohrium are now recognized. One isotope of bohrium appears to have a relatively long life of 15 seconds. Work on this relatively long-lived isotope has been performed with the 88-inch cyclotron at the Lawrence-Berkeley National Laboratory.

Answer 84

Hassium — (named for the German state, Hesse) Hs, at.wt. [265]; at.no. 108. This element was first synthesized and identified in 1964 by the same G.S.I. Darmstadt Group who first identified Bohrium and Meitnerium. Presumably this element has chemical properties similar to osmium. Isotope 265108 was produced using a beam of 58Fe projectiles, produced by the Universal Linear Accelerator (UNILAC) to bombard a 208Pb target. Discovery of Bohrium and Meitnerium was made using detection of isotopes with odd proton and neutron numbers. Elements having even atomic numbers have been thought to be less stable against spontaneous fusion than odd elements. The production of 265108 in the same reaction as was used at G.S.I. was confirmed at Dubna with detection of the seventh member of the decay chain 253Es. Isotopes of Hassium are believed to decay by spontaneous fission, explaining why 109 was produced before 108. Isotope 265108 and 266108 are thought to decay to 261106, which in turn decay to 257104 and 253102. The IUPAC adopted the name Hassium after the German state of Hesse in September 1997. In June 2001 it was announced that hassium is now the heaviest element to have its chemical properties analyzed. A research team at the UNILAC heavy-ion accelerator in Darmstadt, Germany built an instrument to detect and analyze hassium. Atoms of curium-248 were collided with atoms of magnesium-26, producing about 6 atoms of hassium with a halflife of 9 sec. This was sufficiently long to obtain data showing that hassium atoms react with oxygen to form hassium oxide molecules. These condensed at a temperature consistent with the behavior of Group 8 elements. This experiment appears to confirm hassium’s location under osmium in the periodic table.

Answer 85

Meitnerium — (named for Lise Meitner [1878–1968], Austrian-Swedish physicist and mathematician), Mt; at. wt [266]; at. no. 109. On August 29, 1992, Element 109 was made and identified by physicists at the Heavy Ion Research Laboratory (G.S.I.), Darmstadt, Germany, by bombarding a target of 209Bi with accelerated nuclei of 58Fe. The production of Element 109 has been extremely small. It took a week of target bombardment (1011 nuclear encounters) to produce a single atom of 109. Oganessian and his team at Dubna in 1994 repeated the Darmstadt experiment using a tenfold irradiation dose. One fission event from seven alpha decays of 109 was observed, thus indirectly confirming the existence of isotope 266109. In August 1997, the IUPAC adopted the name meitnerium for this element, honoring L. Meitner. Four isotopes of meitnerium are now recognized.

Answer 86

Element 110 — In 1987 Oganessian, et al., at Dubna, claimed discovery of this element. Their experiments indicated the spontaneous fissioning nuclide 272110 with a half-life of 10 ms. More recently a group led by Armbruster at G.S.I. in Darmstadt, Germany, reported evidence of 269110, which was produced by bombarding lead for many days with more than 1018 nickel atoms. A detector searched each collision for Element 110’s distinct decay sequence. On November 9, 1994, evidence of 110 was detected. In 2003 IUPAC approved the name darmstadtium, symbol Ds, for Element 110. Seven isotopes of Element 110 are now recognized.

Answer 87

Element 111 — On December 20, 1994, scientists at GSI Darmstadt, Germany announced they had detected three atoms of a new element with 111 protons and 161 neutrons. This element was made by bombarding 83Bi with 28Ni. Signals of Element 111 appeared for less than 0.002 sec, then decayed into lighter elements including Element 268109 and Element 264107. These isotopes had not previously been observed. A name for Element 111 has not been suggested although IUPAC has suggested a temporary name of Unununium, with the symbol Uuu. Element 111 is expected to have properties similar to gold. Also see element 115.

Answer 88

Element 112 — In late February 1996, Siguard Hofmann and his collaborators at GSI Darmstadt announced their discovery of Element 112, having 112 protons and 165 neutrons, with an atomic mass of 277. This element was made by bombarding a lead target with high-energy zinc ions. A single nucleus of Element 112 was detected, which decayed after less than 0.001 sec by emitting an α particle, consisting of two protons and two neutrons. This created Element 110273, which in turn decayed by emitting an α particle to form a new isotope of Element 108 and so on. Evidence indicates that nuclei with 162 neutrons are held together more strongly than nuclei with a smaller or larger number of neutrons. This suggests a narrow “peninsula” of relatively stable isotopes around Element 114. GSI scientists are experimenting to bombard targets with ions heavier than zinc to produce Elements 113 and 114. A name has not yet been suggested for Element 112, although the IUPAC suggested the temporary name of ununbium, with the symbol of Uub, when the element was discovered. Element 112 is expected to have properties similar to mercury.

Answer 89

Element 114 — (Ununquadium) Symbol Uuq. Element 114 is the first new element to be discovered since 1996. This element was found by a Russian–American team, including Livermore researchers, by bombarding a sheet of plutonium with a rare form of calcium hoping to make the atoms stick together in a new element. Radiation showed that the new element broke into smaller pieces. Data of radiation collected at the Russian Joint Institute for Nuclear Research in November and December 1998, were analyzed in January 1999. It was found that some of the heavy atoms created when 114 decayed lived up to 30 seconds, which was longer than ever seen before, for such a heavy element. This isotope decayed into a previously unknown isotope of Element 112, which itself lasted 15 minutes. That isotope, in turn, decayed to a previously undiscovered isotope of Element 108, which survived 17 minutes. Isotopes of these and those with longer life-times have been predicted for some time by theorists. It appears that these isotopes are on the edge of the “island of stability”, and that some of the isotopes in this region might last long enough for studies of their nuclear behavior and for a chemical evaluation to be made. No name has yet been suggested for Element 114; however, the temporary name of ununquadium with symbol Uuq may be used.

Answer 90

Element 115— (Ununpentium) On February 2, 2004, it was reported that Element 115 had been discovered at the Joint Institute for Nuclear Research (JINR) in Dubna, Russia. Four atoms of this element were produced by JINR physicists and collaborators from the Lawrence Livermore (California) Laboratory using a 248-MeV beam of calcium-48 ions striking a target of americium-243 atoms. The nuclei of these atoms are said to have a life of 90 milliseconds. The relatively long lifetime of Element 115 suggests that these experiments might be getting closer to the “island of stability” long sought to exist by some nuclear physicists. These atoms were thought to decay first to Element 113 by the emission of an alpha particle, then decaying further to Element 111 by alpha emission again, and then by three more alpha decay processes to Element 105 (dubnium), which after a long delay from the time of the initial interaciton, fissioned. This experiment entailed separating four atoms from trillions of other atoms. A gas-filled separator, employing chemistry, was important in this experiment. Names for Elements 115, Element 113, and Element 111 have not yet been chosen.

Answer 91

Element 118— (Ununoctium) Symbol Uuo. In June 1999 it was announced that Elements 118 and 116 had been discovered at the Lawrence Berkeley National Laboratory. A lead target was bombarded for more than 10 days with roughly 1 quintillion krypton ions. The team reported that three atoms of Element 118 were made, which quickly decayed into Elements 116, 114, and elements of lower atomic mass. It was said that the isotopes of Element 118 lasted only about 200 milliseconds, while the isotope of Element 116 lasted only 1.2 milliseconds. It was hoped that these elements might be members of “an island of stability”, which had long been sought. At that time it was hoped that a target of bismuth might be bombarded with krypton ions to make Element 119, which, in turn, would decay into Elements 117, 115, and 113.

Elements - CRC Handbook Definitions Flashcards

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