Crystal cerium

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. 

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). 

The fluorite stmcture, which has a large crystal lattice energy, is adopted by Ce02 preferentially stahi1i2ing this oxide of the tetravalent cation rather than Ce202. Compounds of cerium(IV) other than the oxide, ceric fluoride [10060-10-3] CeF, and related materials, although less stable can be prepared. For example ceric sulfate [13590-82-4] Ce(S0 2> certain double salts are known. 

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 role of cerium in these lighting phosphors is not as the emitting atom but rather as the sensitizer. The initial step in the lighting process is the efficient absorption of the 254 nm emission Ce ", with broad absorption bands in the uv, is very suitable. This absorbed energy is then transferred to the sublattice within the crystalline phosphor eventually the activator ion is fed and emission results. Cerium, as a sensitizer ion, is compatible in crystal lattices with other lanthanide ions, such as Eu and Tb, the usual activator atoms. 

Cerium is one of the most widely used activators, which improve the working characteristics of many scintillators. Determination of the valence state of cerium in single crystals of alkaline and rare-earth borates allows to establish the nature of activator centers for purposeful influence on the scintillation efficiency of the matrix. 

To determine of Ce(IV) in acid soluble single crystals, a simple and sensitive method is proposed. The method is based on the reaction of tropeoline 00 oxidation by cerium(IV) in sulfuric acid solution with subsequent measurement of the light absorption decrease of the solution. The influence of the reagent concentration on the analysis precision is studied. The procedure for Ce(IV) determination in ammonium dihydrophosphate doped by cerium is elaborated. The minimal determined concentration of cerium equal to 0.04 p.g/ml is lower than that of analogous methods by a factor of several dozens. The relative standard deviation does not exceed 0.1. 

The total cerium content in the single crystal samples on the basis of rare-earth elements is determined by photometry after Ce(III) oxidation by ammonium persulfate. The Ce(III) content is calculated from the difference. Comparison of the determination results of the total cerium content obtained by photometric and atomic emission methods for Li GdlBO ljiCe demonstrated the elaborated procedure precision and systematic error absence. 

Procedure (copper in crystallised copper sulphate). Weigh out accurately about 3.1 g of copper sulphate crystals, dissolve in water, and make up to 250 mL in a graduated flask. Shake well. Pipette 50 mL of this solution into a small beaker, add an equal volume of ca AM hydrochloric acid. Pass this solution through a silver reductor at the rate of 25 mL min i, and collect the filtrate in a 500 mL conical flask charged with 20 mL 0.5M iron(III) ammonium sulphate solution (prepared by dissolving the appropriate quantity of the analytical grade iron(III) salt in 0.5M sulphuric acid). Wash the reductor column with six 25 mL portions of 2M hydrochloric acid. Add 1 drop of ferroin indicator or 0.5 mL N-phenylanthranilic acid, and titrate with 0.1 M cerium(IV) sulphate solution. The end point is sharp, and the colour imparted by the Cu2+ ions does not interfere with the detection of the equivalence point. 

The crystal structures of Hf 2 (OH) 2 (S0O 3 (H2O) i, (14) and Ce2(0H)2(S0i,)3 (H20)it (14) also have been determined and found to be isomorphous to the zirconium compound. The cell constants for this series of four isomorphous compounds reflect the effect of the ionic radii on the dimensions of the unit cell. The values for these cell constants are in Table II. Thus, the cell constants for the zirconium and hafnium compounds are nearly identical and smaller than the cell constants for the cerium and plutonium compounds which are also nearly identical. This trend is exactly that followed by the ionic radii of these elements. 

The agreement is also satisfactory for lithium and sodium sulfide. The oxide was used in calculating the lithium radius, 0.60 A., for in this compound it is safe to assume that the anions are not in mutual contact. It is further highly pleasing to note that even in zirconium and cerium oxide, containing quadrivalent cations, our theoretical radii are substantiated by the experimental inter-atomic distances for this makes it probable that even in these crystals the ions are not greatly deformed. 

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. 

Powder XR diffraction spectra confirm that all materials are single phase solid solutions with a cubic fluorite structure. Even when 10 mol% of the cations is substituted with dopant the original structure is retained. We used Kim s formula (28) and the corresponding ion radii (29) to estimate the concentration of dopant in the cerium oxide lattice. The calculated lattice parameters show that less dopant is present in the bulk than expected. As no other phases are present in the spectrum, we expect dopant-enriched crystal surfaces, and possibly some interstitial dopant cations. However, this kind of surface enrichment cannot be determined by XR diffraction owing to the lower ordering at the surface. 

Now the possible explanation for the greater degradation of phenol by the cerium doped copper crystals than those of either cobalt or manganese ions could... 

The crystal structure of the cerium sandwich complex (31) (34) shows it to be similar to that of the related Cclv bis(octaethylporphyrinate) complex (Fig. 7) (83, 84). 

The rare earth (RE) ions most commonly used for applications as phosphors, lasers, and amplifiers are the so-called lanthanide ions. Lanthanide ions are formed by ionization of a nnmber of atoms located in periodic table after lanthanum from the cerium atom (atomic number 58), which has an onter electronic configuration 5s 5p 5d 4f 6s, to the ytterbium atom (atomic number 70), with an outer electronic configuration 5s 5p 4f " 6s. These atoms are nsnally incorporated in crystals as divalent or trivalent cations. In trivalent ions 5d, 6s, and some 4f electrons are removed and so (RE) + ions deal with transitions between electronic energy sublevels of the 4f" electroiuc configuration. Divalent lanthanide ions contain one more f electron (for instance, the Eu + ion has the same electronic configuration as the Gd + ion, the next element in the periodic table) but, at variance with trivalent ions, they tand use to show f d interconfigurational optical transitions. This aspect leads to quite different spectroscopic properties between divalent and trivalent ions, and so we will discuss them separately. 

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