Scandium earths

The element was discovered by Nilson in 1878 in the minerals euxenite and gadolinite, which had not yet been found anywhere except in Scandinavia. By processing 10 kg of euxenite and other residues of rare-earth minerals, Nilson was able to prepare about 2g of highly pure scandium oxide. Later scientists pointed out that Nilson s scandium was idenhcal with Mendeleev s ekaboron. 

Scandium is apparently much more abundant (the 23rd most) in the sun and certain stars than on earth (the 50th most abundant). It is widely distributed on earth, occurring in very minute quantities in over 800 mineral species. The blue color of beryl (aquamarine variety) is said to be due to scandium. It occurs as a principal component in the rare mineral thortveihte, found in Scandinavia and Malagasy. It is also found in the residues remaining after the extrachon of tungsten from Zinnwald wolframite, and in wiikite and bazzite. 

Scandium is a silver-white metal which develops a slightly yellowish or pinkish cast upon exposure to air. A relatively soft element, scandium resembles yttrium and the rare-earth metals more than it resembles aluminum or titanium. 

Lanthanides is the name given collectively to the fifteen elements, also called the elements, ranging from lanthanum. La, atomic number 57, to lutetium, Lu, atomic number 71. The rare earths comprise lanthanides, yttrium, Y, atomic number 39, and scandium. Sc, atomic number 21. The most abundant member of the rare earths is cerium, Ce, atomic number 58 (see Ceriumand cerium compounds). 

Some nut trees accumulate mineral elements. Hickory nut is notable as an accumulator of aluminum compounds (30) the ash of its leaves contains up to 37.5% of AI2O2, compared with only 0.032% of aluminum oxide in the ash of the Fnglish walnut s autumn leaves. As an accumulator of rare-earth elements, hickory greatly exceeds all other plants their leaves show up to 2296 ppm of rare earths (scandium, yttrium, lanthanum, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium). The amounts of rare-earth elements found in parts of the hickory nut are kernels, at 5 ppm shells, at 7 ppm and shucks, at 17 ppm. The kernel of the Bra2d nut contains large amounts of barium in an insoluble form when the nut is eaten, barium dissolves in the hydrochloric acid of the stomach. 

Calcium metal is an excellent reducing agent for production of the less common metals because of the large free energy of formation of its oxides and hahdes. The following metals have been prepared by the reduction of their oxides or fluorides with calcium hafnium (22), plutonium (23), scandium (24), thorium (25), tungsten (26), uranium (27,28), vanadium (29), yttrium (30), zirconium (22,31), and most of the rare-earth metals (32). 

The person whose name is most closely associated with the periodic table is Dmitri Mendeleev (1836-1907), a Russian chemist. In writing a textbook of general chemistry, Mendeleev devoted separate chapters to families of elements with similar properties, including the alkali metals, the alkaline earth metals, and the halogens. Reflecting on the properties of these and other elements, he proposed in 1869 a primitive version of today s periodic table. Mendeleev shrewdly left empty spaces in his table for new elements yet to be discovered. Indeed, he predicted detailed properties for three such elements (scandium, gallium, and germanium). By 1886 all of these elements had been discovered and found to have properties very similar to those he had predicted. 

Rare earth metals and scandium trifluoromethanesulfonates (lanthanide and scandium triflates) are strong Lewis acids that are quite effective as catalysts in... 

Quaternary chalcogenides of the type A Ln M X, containing three metal elements from different blocks of the Periodic Table (A is an alkali or alkaline earth metal, Ln is an /-block lanthanide or scandium, M is a p-block main group or a r/-block transition metal, and X is S or Se) are also known [65]. 

The element scandium (Sc) is in group 3 (above La and Y), and its radius is appreciably smaller than that of any other rare-earth element. Scandium is uncommon, probably because of both the... 

In that one percent, iron, sodium, calcium, rare elements like scandium, and even elements not found on earth, like technetium, have been discovered. These elements and many others can be identified in the atmospheres of stars by spectroscopy, a method of analyzing the light emitted by our sun and other stars. Each element, whether on the earth or outside of it, always produces a certain, characteristic pattern of colored lines of light when... 

Stevenson, P. C. and Nervik, W. C. (1961). The Radiochemistry of the Rare Earths, Scandium, Yttrium and Actinium, Report No. NAS-NS-3020 (National Technical Information Service, Springfield, Virginia). 

The preparations of rare-earth trihalides can be found in various books (2-8) and in Taylor s review (2 ). This review, however, did not include the preparation of scandium and yttrium trihalides, and only covered the preparation of the trifluorides very briefly. We have reviewed the preparation of all the trihalides (including scandium and yttrium) from Taylor s review up to June 1979 and have also included some methods and references missed by Taylor. Although we have mentioned all the methods available for the preparation of the trihalides, emphasis has been placed on the methods used since Taylor s review, and these have been referenced fully, whereas for the other methods, Taylor s review is recommended as a source of references. 

There appear to be no enthalpies of solution of rare-earth tribromides published in the available literature.2 However, Bommer and Hohmann reported a value of -230.5 kj mol-1 (at 20°C) for the enthalpy of solution of scandium tribromide in water (180). This value may be compared with -197.1 kj mol-1 for the chloride, and an estimate (from the published Lnl3 series, q.v.) of —240 to -250 kj mol-1 for the iodide. The markedly more negative values for the heavier ha-... 

The dependence of the solubility of LaCl3-7H20 on acid concentration at 25°C is indicated in Table XIX (205). The dependence at 50°C is the same. The dependence of solubilities of trichlorides of scandium (263), yttrium (264,265), and several rare-earth elements (265) on hydrochloric acid concentration has been established at 0°C. 

The 3rd group of the Periodic Table (the 1st column within the block of the transition elements) contains the metals scandium, yttrium, lanthanum, and actinium. Lanthanum (atomic number 57) may be considered the earliest member of the family of metals, called lanthanides (general symbol Ln), forming, inside the principal transition series, an inner transition series (up to atomic number 71). Scandium and yttrium together with the lanthanides are also called rare earth metals (general symbol R). 

Within the lanthanides the first ones from La to Eu are the so-called light lanthanides, the other are the heavy ones. Together with the heavy lanthanides it may be useful to consider also yttrium the atomic dimensions of this element and some general characteristics of its alloying behaviour are indeed very similar to those of typical heavy lanthanides, such as Dy or Ho. An important subdivision within the lanthanides, or more generally within the rare earth metals, is that between the divalent ones (europium and ytterbium which have been described together with other divalent metals in 5.4) and the trivalent ones (all the others, scandium and yttrium included). 

A modified rare earth catalyst (30) which is based on a polystyrene backbone as depicted in Scheme 4.15 can be applied even in neat water. It is attached via a hydrophobic oligomeric linker which creates a nonpolar reaction environment and acts as a surfactant for the substrates. The reaction of 4-phenyl-2-butanone with tetraallyltin in water using 1.6 mol% of the scandium catalyst (30) afforded the corresponding homoallylalcohol in a yield of 95%. Interestingly, when using other solvents (dichloromethane, acetonitrile, benzene, ethanol, DMF) the yields decreased drastically, indicating a much higher reaction rate in water [98]. 

ISOTOPES There are 28 isotopes of scandium, ranging from scandium-36 to scandium-57. Scandium-45 is the only stable isotope and contains about 100% of the natural scandium found in the Earth s crust. The remaining isotopes are radioactive with half-lives ranging from nanoseconds to a few minutes to a few hours to a few days, and therefore, they are not found naturally in the Earth s crust. The radioactive isotopes of scandium are produced in nuclear reactors. 

Scandium is a soft, lightweight, silvery-white metal that does not tarnish in air, but over time, it turns yellowish-pink. It resists corrosion. Scandium reacts vigorously with acids, but not water. Scandium has some properties similar to the rare-earth elements. Although its position in group 3 places it at the head of the 17 elements of the lanthanide series of rare-earth metals, scandium, as a metal, is not usually considered a rare-earth. Scandiums melting point is l,54l°C, its boiling point is 2836°C, and its density is 2.989 glctn . 

Although scandium is chemically similar to rare-earths, it no longer is considered to be one of them. Scandium is the 42nd most abundant element found in the Earths crust, making up about 0.0025% of the Earths crust. It is widely distributed at 5 ppm on the Earth. (It is about as abundant as lithium, as listed in group 1.) Scandium is even more prevalent in the sun and several other stars than it is on Earth. 

Interestingly, salts other than tin(ll) bis-(2-ethylhexanoate) such as scandium and tin trifluoromethanesulfonate [41 3], zinc octoate [44, 45], and aluminum acetyl acetonate [45] were reported to mediate the ROP of lactones. As far as scandium trifluoromethanesulfonate is concerned, the main advantage is the increase of its Lewis acidity enabling the polymerization to be carried out at low temperatures with acceptable kinetics. Later, faster kinetics were obtained by extending the process to scandium trifluoromethanesulfonimide [Sc(NTf2)3] and scandium nonafluorobutanesulfonimide [Sc(NNf2)3] and to other rare earth metal catalysts (metal=Tm, Sm, Nd) [46]. 

Recently, rare-earth metal complexes have attracted considerable attention as initiators for the preparation of PLA via ROP of lactides, and promising results were reported in most cases [94—100]. Group 3 members (e.g. scandium, yttrium) and lanthanides such as lutetium, ytterbium, and samarium have been frequently used to develop catalysts for the ROP of lactide. The principal objectives of applying rare-earth complexes as initiators for the preparation of PLAs were to investigate (1) how the spectator ligands would affect the polymerization dynamics (i.e., reaction kinetics, polymer composition, etc.), and (2) the relative catalytic efficiency of lanthanide(II) and (III) towards ROPs. 

In most recovery processes, scandium oxide is converted to its fluoride salt. The fluoride salt is the end product. The fluoride is converted to metallic scandium by heating with calcium in a tantalum crucible at elevated temperatures. A similar reduction is carried out with most rare earths. The metal is purified by distillation at 1,650 to 1,700°C under high vacuum in a tantalum crucible. 

Scandium metal reacts rapidly with most acids hberating hydrogen and forming salts upon evaporation of the solution. Scandium, however, is not attacked by 1 1 mixture of concentrated nitric acid and 48% hydrofluoric acid. A similar behavior is exhibited by yttrium and heavy rare earth metals. 

The chemical properties of yttrium are more similar to those of rare earths than to scandium. However, unlike the rare earths, yttrium exhibits only one valence state, -i-3. 

Another approach to the "greening of catalysts has been the use of rare-earth compounds known as inflates. The term inflate is an abbreviation for the trifluoromethanesulfonate (SO3CF3) cation. Some typical triflates that have been used in research include the lanthanides, scandium, and hafnium. These triflates act as Lewis acids (electron acceptors) and can, therefore, be substituted for stronger mineral acids (such as sulfuric acid) with undesirable environmental... 

Lars Fredrik Nilson, 1840-1899. Professor of analytical chemistry at the University of Upsala and at the Agricultural Academy at Stockholm. Discoverer of scandium His researches on soils and fertilizers transformed the barren plains of his native island into an agricultural region With Otto Pettersson he investigated the rare earths and prepared metallic titanium. 

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