Cerium metal, solid

C (190-196) and by the thermal decomposition of the trifluoride at 800°C in air (191, 197, 198). The lanthanum compound itself may also be prepared by hydrolysis of the trifluoride (199) and by the reaction of the oxide with molten sodium fluoride (200). On treatment with CFCI3 (201), it is converted back to the trifluoride. The cerium analog has been prepared from Ce02 by reaction with CeF3 at 2750°C (202) or with CeF3 and cerium metal at 900°C in a nickel tube (203). The infrared spectra of these solids have been reported (204). 

The maximum in catalytic activity observed for the multiphase region of the phase diagram necessarily arises from interactions between the separate phases. The bismuth rich and cerium rich solid solutions can readily form coherent interfaces at the phase boundaries due to the structural similarities between the two phases which can permit epitaxial nucleation and growth. A good lattice match exists between the [010] faces of the compounds, this match is displayed in Figure 6. We have also shown that regions of an [010] face of a Ce doped bismuth molybdate crystal resembles cerium molybdate compos tionally. This means that the interface between the two compounds need not have sharp composition gradients. It is structurally possible for the Bi-rich phase to possess a metal stiochiometry at the surface that matches that of the Ce-rich phase. 

In these systems, two types of rare earth carbides have been confirmed to exist the rare earth dicarbides and the rare earth sesquicarbides. The existence of the monocarbides of cerium and praseodymium (Warf 1955, Brewer and Krikorian 1956, Dancy et al. 1962) has been discredited. It was found on the basis of an X-ray study (Spedding et al. 1958) that the earlier reported cerium monocarbide was most probably a solid solution of carbon in cerium the lattice parameter reported by Brewer and Krikorian (1956) for the cerium monocarbide was identical with that of cerium metal saturated with carbon. 

FIGURE 4 The measured equation of state of cerium metal to 208 GPa at room temperature. The solid curve drawn through the collapsed phases above 1 GPa is the MUEOS fit (Vohra... 

Villain, J., l959, J. Phys. Chem. Solids 11, 303. Waber, J.T. and A.C. Switendick, 1965, Results of augmented plane wave calculation of the band structure of cerium metal. Proceedings of the Fifth Rare Earth Research Conference, Ames, Iowa, 1%5, Book II. pp. 75-88. 

Cerium metal is discussed in ch. 4 and only a brief mention of its high pressure behavior will be made here (for references see the list in ch. 4). Cerium can exist at atmospheric pressure in the fee (y) or dhep (iS) form and undergoes an isostructural transition near 100 K to another fcc-form referred to as o-Ce. The y-a Ce transition occurs at 7 kbar at room temperature and this transition is accompanied by about 8% volume decrease. This is one of the most widely studied transitions as a function of pressure and temperature and is believed to involve a valence change from 3 towards a higher valence state (3.7 ). The y to a transition line terminates at a critical point the very first example in which a solid - solid transition was shown to exhibit a liquid-vapor-like critical point. A pressure-induced phase transition near 50 kbar, initially reported to be yet another isostructural transition has been shown to be from fee (a-Ce) to an orthorhombic phase with the a-U structure. Stager and Drickamer (1964) have reported a pronounced resistance anomaly near 120 kbar indicative of a phase transition, but the nature of this transition is unknown. The fusion behavior of Ce is again unique in that it exhibits a minimum. 

The compound cerium oxide (either Ce Oj or CeO ) is used to coat the inside of ovens because it was discovered that food cannot stick to oven walls that are coated with cerium oxide. Cerium compounds are used as electrodes in high-intensity lamps and film projectors used by the motion picture industry. Cerium is also used in the manufacturing and polishing of high-refraction lenses for cameras and telescopes and in the manufacture of incandescent lantern mantles. It additionally acts as a chemical reagent, a misch metal, and a chemical catalyst. Cerium halides are an important component of the textile and photographic industries, as an additive to other metals, and in automobile catalytic converters. Cerium is also used as an alloy to make special steel for jet engines, solid-state instruments, and rocket propellants. 

Misch metal, an alloy of cerium with other lanthanides is a pyrophoric substance and is used to make gas lighters and ignition devices. Some other applications of the metal or its alloys are in solid state devices rocket propellant compositions as getter in vacuum tubes and as a diluent for plutonium in nuclear fuel. 

Figure 4.29 Electronic absorption spectra of Ce(OEP)2 (solid line) and Ce2(OEP)3 (dashed Une) [42]. (Reprinted with permission from J.W. Buchler, et al., Metal complexes with tetrapyrrole ligands. 40. Cerium(IV) bis(octaethylporphyrinate) and dicerium(III) tris(octaethylporphyrinate) parents of a new family of lanthanoid double-decker and triple-decker molecules, Journal of the American Chemical...

Ceda-based oxides can be obtained by the decomposition of some compound precursor, such as hydroxide, nitrate, halides, sulfates, carbonates, formates, oxalates, acetates, and citrates.For example, nanosize or porous cerium oxide particles have been prepared at low temperatures by pyrolysis of amorphous citrate," which is prepared by the evaporation of the solvent from the aqueous solution containing cerium nitrate (or oxalate) and citric acid. In the case of mixed oxides, the precursor containing some cations in the same solid salts is prepared. In the same manner of ceria particles, the precursors complexing some cations with citrates are useful to synthsize ceria-zirconia mixed oxides and their derivatives. Also. Ce02-Ln203 solid solutions, where Ln = La. Pr, Sm. Gd. and Tb, have been synthesized from the precursors obtained by the evaporation of nitrate solutions at 353 K in air from an intimate mixture of their respective metal nitrates. The precursors are dried and then heated at 673 K to remove niU ates, followed by calcination at 1073 K for 12h. 

Thermal deactivation involves processes such as diffusion and solid-state reaction. In early three-way catalysts where both the active metal and ceria were dispersed onto high-surface-area Y-A1203, loss of contact between them, due to sintering of either one or both, could effectively eliminate oxygen storage. The temperature required for ceria to sinter, somewhat above 800°C, was typically not attained under normal operating conditions, although relatively harsh conditions, with temperatures well in excess of 800°C under rich exhaust gas, did exist in heavy-duty truck operation, and in this case, reaction between ceria and alumina at times produced stable, inert cerium aluminate. 

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