Atomic cerium

Jorge FE, de Castro EVR, Da SUva ABF. A universal Gaussian basis set for atoms cerium through lawrencium generated with the generator coordinate Hartree-Fock method. J Comp Chem. 1997 18(13) 1565-9. 

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). 

Cerium [7440-45-17, Ce, at no. 58, is the most abundant member of the series of elements known as lanthanides. Lanthanide (Ln) is a collective name for the fifteen elements from at no. 57 (La) to 71 (Lu), also called the 4f elements. Rare-earth (RE) metal is the collective name for elements 21 (Sc), 39 (Y), plus 57 (La) to 71 (Lu). The label /, /is used herein for elements having atomic numbers from 57 to and the label heavj for numbers - 64 to 71. 

Several instmmental methods are available for quantitative estimation of from moderate to trace amounts of cerium in other materials. X-ray fluorescence is widely available, versatile, and suitable for deterrninations of Ce, and any other Ln, at percent levels and lower in minerals and purer materials. The uv-excited visible luminescence of cerium is characteristic and can be used to estimate Ce content, at ppm levels, in a nonluminescing host. X-ray excited optical luminescence (15), a technique especially appropriate for Ln elements including cerium, rehes on emissions in the visible, and also measures ppm values. Atomic emission spectrometry is appHcable to most lanthanides, including Ce (16). The precise lines used for quantitative measurement must be chosen with care, but once set-up the technique is suitable for routine analyses. 

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. 

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. 

Accurate atomic weight values do not automatically follow from precise measurements of relative atomic masses, however, since the relative abundance of the various isotopes must also be determined. That this can be a limiting factor is readily seen from Table 1.3 the value for praseodymium (which has only 1 stable naturally occurring isotope) has two more significant figures than the value for the neighbouring element cerium which has 4 such isotopes. In the twelve years since the first edition of this book was published the atomic weight values of no fewer than 55 elements have been improved, sometimes spectacularly, e.g. Ni from 58.69( 1) to 58.6934(2). 

Mn(N03)4] , [Fe(N03)4] and [Sn(N03)4], which feature dodecahedral coordination about the metal [Ce(N03)5] in which the 5 bidentate nitrate groups define a trigonal bipyramid leading to tenfold coordination of cerium (Fig. 11.17b) [Ce(N03)6] and [Th(N03)6] , which feature nearly regular icosahedral (p. 141) coordination of the metal by 12 O atoms and many lanthanide and uranyl [U02] complexes. It seems, therefore, that the size of the metal centre is not necessarily a dominant factor. 

Cerium is the most abundant rare earth metal. Pure cerium ignites when scratched by even a soft object. It has four known isotopes l36Ce (atomic mass = 135.907 amu), 138Ce (atomic mass = 137.905 amu), 140Ce (atomic mass = 139.905 amu), and 142Ce (atomic mass = 141.909 amu). Ce-140 and Ce-142 are fairly abundant. Which is the more abundant isotope ... 

The diastereoselectivity of the reaction may be rationalized by assuming a chelation model, which has been developed in the addition of Grignard reagents to enantiomerically pure a-keto acetals7,8. Cerium metal is fixed by chelation between the N-atom, the methoxy O-atom and one of the acetal O-atoms leading to a rigid structure in the transition state of the reaction (see below). Hence, nucleophilic attack from the Si-face of the C-N double bond is favored4. 

M(0H)2SOi, H2O where M=Zr (8), Hf (12) also have been determined and reveal the presence of almost planar zigzag chains of metal atoms joined by double hydroxide bridges. The single exception to this trend toward formation of double hydroxy-bridged metal dimers or chains is the compound which is best described as CeOSOif,H20 (17). However, even in this structure the cerium ions form chains which are linked by bridging oxide ions. 

The explanation appears to be related to current work on mixed-valent cerium compounds. Plutonium-americium alloys also show this behavior. Considerations based upon the plutonium atomic volume in the solids show the greatest promise of explaining this irregularity. 

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 rare earth elements (R) are those from atomic numbers 57-71, emanating as a particular series from the parent element lanthanum (atomic no. 57). The set of 14 elements from cerium (58) through lutetium (71) inclusive are commonly known as the lanthanoid (or lanthanide Ln) series. The rare earths form a bridge at the... 

Roman numerals in parentheses indicate the oxidation or valence states. These are the effective ionic charges of cerium atoms and ions or as they exist in chemical compounds. 

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... 

Hirano, S., Koyanagi, T. and Saiki, M. (1973). The physico-chemical behaviour of radioactive cerium in seawater, page 47 in Radioactive Contamination of the Marine Environment, IAEA Publication No. STI/PUB/313 (International Atomic Energy Agency, Vienna). 

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