Cerium properties

Although rare-earth ions are mosdy trivalent, lanthanides can exist in the divalent or tetravalent state when the electronic configuration is close to the stable empty, half-fUed, or completely fiUed sheUs. Thus samarium, europium, thuUum, and ytterbium can exist as divalent cations in certain environments. On the other hand, tetravalent cerium, praseodymium, and terbium are found, even as oxides where trivalent and tetravalent states often coexist. The stabili2ation of the different valence states for particular rare earths is sometimes used for separation from the other trivalent lanthanides. The chemicals properties of the di- and tetravalent ions are significantly different. 

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. 

Hydrolysis is very extensive in Pu(IV) solutions, less so in Pu(Ill) and Pu(VI), and least in Pu(V). The chemical properties of Pu(IV) are somewhat similar to those of Ce(IV) and U(IV) (see Cerium AND cerium compounds). The hydrolysis thermodynamics of Pu(IV) have been assessed in perchlorate solutions (105). The first hydrolysis equiUbrium is... 

Antimony may be added to copper-base alloys such as naval brass. Admiralty Metal, and leaded Muntz metal in amounts of 0.02—0.10% to prevent dezincification. Additions of antimony to ductile iron in an amount of 50 ppm, preferably with some cerium, can make the graphite fliUy nodular to the center of thick castings and when added to gray cast iron in the amount of 0.05%, antimony acts as a powerflil carbide stabilizer with an improvement in both the wear resistance and thermal cycling properties (26) (see Carbides). 

Uses. In spite of unique properties, there are few commercial appUcations for monolithic shapes of borides. They are used for resistance-heated boats (with boron nitride), for aluminum evaporation, and for sliding electrical contacts. There are a number of potential uses ia the control and handling of molten metals and slags where corrosion and erosion resistance are important. Titanium diboride and zirconium diboride are potential cathodes for the aluminum Hall cells (see Aluminum and aluminum alloys). Lanthanum hexaboride and cerium hexaboride are particularly useful as cathodes ia electronic devices because of their high thermal emissivities, low work functions, and resistance to poisoning. 

In bulk form cerium is a reactive metal that has a high affinity for oxygen and sulfur. It has a face centered cubic crystal stmcture, mp 798°C, bp 3443°C, density 6.77 g/mL, and a metallic radius of 182 pm. Detailed chemical and physical property information can be found in the Hterature (1,2). 

Cerium metal has unique soHd-state properties and is the only material known to have a soHd—soHd critical point. Three aHotropes, a, P, y, are stable at or close to ambient conditions and have complex stmctural interrelationships. 

Lubrication Additive. Cerium fluoride, CeF, can be used as an additive to lubricant formulations to improve extreme pressure and antiwear behavior (43). The white soHd has a crystal stmcture that can be pictured as [CeF] layers separated by [F] atom sheets, a layer stmcture analogous to that of M0S2, a material that CeF resembles in properties. 

The case of cerium is of particular interest. Adzic et al. [43] examined the properties of a homologous series of alloys with a composition corresponding to La1 lCerNi355Co075Mn()4Al03 and measured their comparative performance as battery electrodes. A PCT diagram for this system is shown in Fig. 10. 

Zirconium. While almost any metal in the finely divided state exhibits pyrophoric properties, a few metals when abraded emit a shower of sparks of sufficient temp to ignite hydrocarbon vapors. Cerium is the best known metal of this kind for commercial purposes, such as gas lighter flints. For military purposes Zr is the most used. It has found applications in HE and armor-piercing incendiary ammo, the lining of shaped-charge rounds, and in incendiary cluster bombs (Ref 7, pp 100-01)... 

The valences of the rare-earth metals are calculated from their magnetic properties, as reported by Klemm and Bommer.14 It is from the fine work of these investigators that the lattice constants of the rare-earth metals have in the main been taken. The metals lutecium and ytterbium have only a very small paramagnetism, indicating a completed 4/ subshell and hence the valences 3 and 2, respectively (with not over 3% of trivalent ytterbium present in the metal). The observed paramagnetism of cerium at room temperature corresponds to about 20% Ce4+ and 80% Ce3+, that of praseodymium and that of neodymium to about 10% of the quadripositive ion in each case, and that of samarium to about 20% of the bipositive ion in equilibrium with the tripositive ion. 

The last of the lanthanides, this metal is also the hardest and the densest of them. It is a component of cerium mischmetal. Lutetium has some applications in optoelectronics. Shows great similarities to ytterbium. Its discoverer, Georges Urbain, carried out 15 000 fractional crystallizations to isolate pure lutetium (record ). The element has special catalytic properties (oil industry). 176Lu is generated artificially and is a good beta emitter (research purposes). 177Lu has a half-life of six days and is used in nuclear medicine. 

Results and Discussion. Of the 12 samples of starch graft copolymer synthesized, half were hydrolyzed to anionic polyelectrolytes. Synthesis data on these 6 samples are given in Table 2. These particular samples were chosen for hydrolysis because the samples can be intercompared to see the effect of synthesis variables on ultimate product properties. Samples 5, 8, and 11 have the same mole ratio of cerium ion to starch backbone, N, in their reaction mixture. Samples 7, 8, and 9 all have the same refctable mass per starch molecule,... 

Sardar, K., Playford, H.Y., Darton, R.J., Barney, E.R., Hannon, A.C., Tompsett, D., Fisher, J., Kashtiban, R.J., Sloan, J., Ramos, S., Cibin, G. and Walton, R.I. (2010) Nanocrystalline cerium-bismuth oxides synthesis, structural characterization, and redox properties. Chemistry of Materials, 22 6191-6201. 

A predominant feature of the atomic structure of the lanthanide group is the sequential addition of 14 electrons to the 4f subshell (Table 1). The /"electrons do not participate in bond formation and in ordinary aqueous solutions all of the lanthanides exhibit a principal (III) state. The common (III) state confers a similarity in chemical properties to all lanthanide elements. Some of the lanthanides can also exist in the (II) state (Nd, Sm, Eu, Tm, Yh) or in the (IV) state (Ce, Pr, Nd, Tb, Dy). Except for Ce(IV), Eu(II), and Yb(II), these unusual lanthanide oxidation states can only be prepared under drastic redox pressure and temperature conditions, and they are not stable in aqueous solutions. Cerium (IV) is a strong oxidizing agent... 

Cerium, an element in the lanthanide series, has a number of radioactive isotopes. Several of these are produced in abundance in nuclear fission reactions associated with nuclear industry operations or detonation of nuclear devices. This report summarizes our present knowledge of the relevant physical, chemical, and biological properties of radiocerium as a basis for establishing radiation protection guidelines. 

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