Cerium Element

In some versions of the periodic table, the lanthanoids begin with cerium (element 58) and the actinoids begin with thorium (element 90). 

Starting from 1913 scientists from various countries had been searching intensely for the elusive rare-earth element and it seemed strange that they had not found it earlier. Indeed, the elements of the first half of the rare-earth family known as the cerium elements (from lanthanum to gadolinium) had been shown by geochemists to be more abundant in nature than the yttrium elements of the second half of the family (from terbium to lutecium). But all the yttrium elements had been found while an empty box had remained in the cerium group between neodymium and samarium. 

Greek lanthanein, to lie hidden) Mosander in 1839 extracted a new earth lanthana, from impure cerium nitrate and recognized the new element. 

Cerium was named for the asteroid Ceres, which was discovered in 1801. The element was discovered two years later in 1803 by Klaproth and by Berzelius and Hisinger. In 1875 Hillebrand and Norton prepared the metal. 

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). 

Comparing the relative abundance of the rare earths and the other elements Hsted in Table 1, the rare earths are not so rare. Cerium, the most abundant of the rare-earth elements is roughly as abundant as tin thuHum, the least abundant, is more common than cadmium or silver. Over 200... 

High Temperature Corrosion. The rate of oxidation of magnesium adoys increases with time and temperature. Additions of berydium, cerium [7440-45-17, lanthanum [7439-91-0] or yttrium as adoying elements reduce the oxidation rate at elevated temperatures. Sulfur dioxide, ammonium fluoroborate [13826-83-0] as wed as sulfur hexafluoride inhibit oxidation at elevated temperatures. 

Sihca is reduced to siUcon at 1300—1400°C by hydrogen, carbon, and a variety of metallic elements. Gaseous siUcon monoxide is also formed. At pressures of >40 MPa (400 atm), in the presence of aluminum and aluminum haUdes, siUca can be converted to silane in high yields by reaction with hydrogen (15). SiUcon itself is not hydrogenated under these conditions. The formation of siUcon by reduction of siUca with carbon is important in the technical preparation of the element and its alloys and in the preparation of siUcon carbide in the electric furnace. Reduction with lithium and sodium occurs at 200—250°C, with the formation of metal oxide and siUcate. At 800—900°C, siUca is reduced by calcium, magnesium, and aluminum. Other metals reported to reduce siUca to the element include manganese, iron, niobium, uranium, lanthanum, cerium, and neodymium (16). 

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. 

Whereas certain rocks of igneous origin formed by melting and recrystallization can include minerals enriched in the lanthanides (4), cerium is usually present as a trace element rather than as an essential component. Only a few minerals in which cerium is an essential stmcture-defining component occur in economically significant deposits. Two minerals supply the world s cerium, bastnasite [68909-13-7] LnFCO., and monazite [1306-41 -8] (Ln,Th)PO. ... 

An alternative process for opening bastnasite is used ia Chiaa high temperature roastiag with sulfuric acid followed by an aqueous leach produces a solution containing the Ln elements. Ln is then precipitated by addition of sodium chloride as a mixed sulfate. Controlled precipitation of hydroxide can remove impurities and the Ln content is eventually taken up ia HCl. The initial cerium-containing product, oace the heavy metals Sm and beyond have been removed, is a light lanthanide (La, Ce, Pr, and Nd) rare-earth chloride. 

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. 

C cerium concentrate glass polishing, glass decolorizing dominant element... 

Dehydrogenation, Ammoxidation, and Other Heterogeneous Catalysts. Cerium has minor uses in other commercial catalysts (41) where the element s role is probably related to Ce(III)/Ce(IV) chemistry. Styrene is made from ethylbenzene by an alkah-promoted iron oxide-based catalyst. The addition of a few percent of cerium oxide improves this catalyst s activity for styrene formation presumably because of a beneficial interaction between the Fe(II)/Fe(III) and Ce(III)/Ce(IV) redox couples. The ammoxidation of propjiene to produce acrylonitrile is carried out over catalyticaHy active complex molybdates. Cerium, a component of several patented compositions (42), functions as an oxygen and electron transfer through its redox couple. 

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. 

Figure 8 X-ray elemental imaging in a field-emission STEM (a) EDS data of Pd /Ce /alumina catalyst particle poisoned with SO2 and (b) 128 X 128 digital STEM images formed using X-ray counts collected at each image pixel for aluminum, palladium, cerium, and sulfur. (Courtesy of North-Holland Publishers) ...

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). 

Of the remaining 26 undiscovered elements between hydrogen and uranium, 11 were lanthanoids which Mendeleev s system was unable to characterize because of their great chemical similarity and the new numerological feature dictated by the filling of the 4f orbitals. Only cerium, terbium and erbium were established with certainty in 1871, and the others (except promethium, 1945) were separated and identified in the period 1879 -1907. The isolation of the (unpredicted) noble gases also occurred at this time (1894-8). 

Scandium is very widely but thinly distributed and its only rich mineral is the rare thortveitite, Sc2Si20v (p. 348), found in Norway, but since scandium has only small-scale commercial use, and can be obtained as a byproduct in the extraction of other materials, this is not a critical problem. Yttrium and lanthanum are invariably associated with lanthanide elements, the former (Y) with the heavier or Yttrium group lanthanides in minerals such as xenotime, M "P04 and gadolinite, M M SijOio (M = Fe, Be), and the latter (La) with the lighter or cerium group lanthanides in minerals such as monazite, M P04 and bastnaesite, M C03F. This association of similar metals is a reflection of their ionic radii. While La is similar in size to the early lanthanides which immediately follow it in the periodic table, Y , because of the steady fall in ionic radius along the lanthanide series (p. 1234), is more akin to the later lanthanides. 

To avoid this confusion, and because many of the elements are actually far from rare, the terms lanthanide , lanthanon and lanthanoid have been introduced. Even now, however, there is no general agreement about the position of La, i.e, whether the group is made up of the elements La to Lu or Ce to Lu. Throughout this chapter the term lanthanide and the general symbol, Ln, will be used to refer to the fourteen elements cerium to lutetium inclusive, the Group 3 elements, scandium, yttrium and lanthanum having already been dealt with in Chapter 20. 

Apart from the unstable (half-life 2.623 y) of which traces occur in uranium ores, the lanthanides are actually not rare. Cerium (66 ppm in the earth s crust) is the twenty-sixth most abundant of all elements, being half as abundant as Cl and 5 times as abundant as Pb. Even Tm (0.5 ppm), the rarest after Pm, is rather more abundant in the earth s crust than is iodine. 

Other detrimental factors which should to be taken into account in the materials selection process include temperature cycling and the presence of halide gases. Specialist alloys containing rare earth element additions such as cerium, lanthanum and yttrium have been developed for use in certain environments up to 130°C. 

Discussion. Molybdates [Mo(VI)] are quantitatively reduced in 2M hydrochloric acid solution at 60-80 °C by the silver reductor to Mo(V). The reduced molybdenum solution is sufficiently stable over short periods of time in air to be titrated with standard cerium(IV) sulphate solution using ferroin or /V-phenylanthranilic acid as indicator. Nitric acid must be completely absent the presence of a little phosphoric(V) acid during the reduction of the molybdenum(VI) is not harmful and, indeed, appears to increase the rapidity of the subsequent oxidation with cerium(IV) sulphate. Elements such as iron, copper, and vanadium interfere nitrate interferes, since its reduction is catalysed by the presence of molybdates. 

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