Lanthanum, separation

Garcia, R., Pinel, C., and Lemaire, M., Ionic Imprinting Effect in Gadolinum/Lanthanum Separation, Tetrahedron Lett., 39, 8651, 1998. 

Garda, R. Pinel, C. Madic, C. Lemaire, M. Ionic imprinting effect in gadohnium/lanthanum separation. Tetrahedron Lett. 1998, 39, 8651-8654. 

Reference has been made already to the existence of a set of inner transition elements, following lanthanum, in which the quantum level being filled is neither the outer quantum level nor the penultimate level, but the next inner. These elements, together with yttrium (a transition metal), were called the rare earths , since they occurred in uncommon mixtures of what were believed to be earths or oxides. With the recognition of their special structure, the elements from lanthanum to lutetium were re-named the lanthanons or lanthanides. They resemble one another very closely, so much so that their separation presented a major problem, since all their compounds are very much alike. They exhibit oxidation state -i-3 and show in this state predominantly ionic characteristics—the ions. 

Gr. neos, new, and didymos, twin) 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. 

Separation Processes. The product of ore digestion contains the rare earths in the same ratio as that in which they were originally present in the ore, with few exceptions, because of the similarity in chemical properties. The various processes for separating individual rare earth from naturally occurring rare-earth mixtures essentially utilize small differences in acidity resulting from the decrease in ionic radius from lanthanum to lutetium. The acidity differences influence the solubiUties of salts, the hydrolysis of cations, and the formation of complex species so as to allow separation by fractional crystallization, fractional precipitation, ion exchange, and solvent extraction. In addition, the existence of tetravalent and divalent species for cerium and europium, respectively, is useful because the chemical behavior of these ions is markedly different from that of the trivalent species. 

This tread has iaflueaced the supply and availability of cerium, particularly ia comparison to the availability of lanthanum-rich cerium-poor materials. The iacrease ia La demand for ECC catalysts up to the mid-1980s, together with the need to separate out cerium ia order to make the La-rich Ce-poor compositions increasingly preferred, led to a glut of Ce-based raw materials at that time. Ia 1991, the La-rich Ce-poor portioa of the raw material was ia excess supply over demand. 

The anode material in SOF(7s is a cermet (rnetal/cerarnic composite material) of 30 to 40 percent nickel in zirconia, and the cathode is lanthanum rnanganite doped with calcium oxide or strontium oxide. Both of these materials are porous and mixed ionic/electronic conductors. The bipolar separator typically is doped lanthanum chromite, but a metal can be used in cells operating below 1073 K (1472°F). The bipolar plate materials are dense and electronically conductive. 

Yttrium and lanthanum are both obtained from lanthanide minerals and the method of extraction depends on the particular mineral involved. Digestions with hydrochloric acid, sulfuric acid, or caustic soda are all used to extract the mixture of metal salts. Prior to the Second World War the separation of these mixtures was effected by fractional crystallizations, sometimes numbered in their thousands. However, during the period 1940-45 the main interest in separating these elements was in order to purify and characterize them more fully. The realization that they are also major constituents of the products of nuclear fission effected a dramatic sharpening of interest in the USA. As a result, ion-exchange techniques were developed and, together with selective complexation and solvent extraction, these have now completely supplanted the older methods of separation (p. 1228). In cases where the free metals are required, reduction of the trifluorides with metallic calcium can be used. 

A circular TLC spectrophotometric method for the determination of lanthanum and yttrium at concentration level of 0.01 to 1.0% in molybdenum-based alloys has also been developed. It involves the separation of lanthanum and yttrium on cellulose layers impregnated with 0.2-Mtrioctylamine using aqueous HCl as developer, extraction from sorbent layer, and determination by spectrophotometry [69]. 

Americium metal has been obtained by heating americium oxide, Am203, with lanthanum at 1,200 °C americium, which is more volatile than other actinides, volatilizes and can readily be separated from other actinides. Am02 can be obtained by igniting most trivalent americium compounds (Budavari 1996 Cotton and Wilkinson 1980 UIC 1997). 

ScF3 and LaF3. Both separate and multilayer scandium and lanthanum fluoride films have been grown from nitrates and lanthanum chloride and sodium and ammonium fluorides. XPS analysis revealed that the films were stoichiometric and that the films contained both hydroxide groups and water.129... 

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