Cerium, oxidation

At the beginning of the twentieth century, the incandescent mantle, utilising the candoluminescence of a mixture of thorium (95% weight) and cerium oxides was developed. The pyrophoricity of rare-earth metals led to the invention of the lighter flint made through the alloying of iron and mischmetal. Since that time, numerous other appHcations have developed to coincide with the availabiUty of the rare-earth compounds on an industrial scale and having a controlled purity. 

A typical analysis of the iasoluble cerium coaceatrate portioa is by wt % Ce02, - 62 other La oxides, - 10 CaO, 6 other oxides, - 4 and F - 10. The loss on ignition is about 8 wt %. Cerium oxide readily takes F ions iato the lattice. The charge difference is then matched by some Ln " replacing... 

Cerium Oxide. The most stable oxide of cerium is cerium dioxide [1306-38-3] Ce02, also called ceria or ceric oxide. When cerium salts are calcined in air or if oxygen is present, this tetravalent Ce(IV) oxide is formed, cerium sesquioxide [1345-13-7] can be prepared in strongly reducing... 

Hydroxide. Freshly precipitated cerous hydroxide [15785-09-8] Ce(OH)2, is readily oxidized by air or oxygenated water, through poorly defined violet-tinged mixed valence intermediates, to the tetravalent buff colored ceric hydroxide [12014-56-17, Ce(OH)4. The precipitate, which can prove difficult to filter, is amorphous and on drying converts to hydrated ceric oxide, Ce02 2H20. This commercial material, cerium hydrate [23322-64-7] behaves essentially as a reactive cerium oxide. 

Nitrate. Cerium(III) nitrate hexahydrate [10294-41 -4] Ce(N03) 6H20, is a commercially available soluble salt of cerium, and because of ready decomposition to the oxide, it is used, for example, when a porous sohd is to be impregnated with cerium oxide. The nitrate is very soluble in water, up to about 65 wt %. It is also soluble in a wide range of polar organic solvents such as ketones, alcohols, and ethers. 

The cerium concentrate derived from bastnasite is an excellent polish base, and the oxide derived direcdy from the natural ratio rare-earth chloride, as long as the cerium oxide content is near or above 50 wt %, provides an adequate glass poHsh. The polishing activity of the latter is better than the Ce02 Ln0 ratio suggests. Materials prepared prior to any Ln purification steps are sources for the lowest cost poHshes available used to treat TV face plates, mirrors, and the like. For precision optical polishing the higher purity materials are preferred. 

In addition to platinum and related metals, the principal active component ia the multiflmctioaal systems is cerium oxide. Each catalytic coaverter coataias 50—100 g of finely divided ceria dispersed within the washcoat. Elucidatioa of the detailed behavior of cerium is difficult and compHcated by the presence of other additives, eg, lanthanum oxide, that perform related functions. Ceria acts as a stabilizer for the high surface area alumina, as a promoter of the water gas shift reaction, as an oxygen storage component, and as an enhancer of the NO reduction capability of rhodium. 

The tendency for high surface area gamma-alumina to siater and lose that cmcial area duriag high temperature operatioa is retarded by the intimate additioa of several perceat of cerium oxide. The mechanism is stiU under debate but may iavolve a surface LN—aluminate species on the alumina. 

Cerium oxide acts as a catalytic oxidizer in a spinel-based additive (38) that aids SO2 to SO conversion and promotes the required sulfate formation. Bastnasite itself is the most economical source of cerium and can be used directly at 1% as the capture additive (39). 

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. 

At a much earlier stage in the research and development cycle, fluidized-bed processes use porous sorbents containing copper oxide (82), cerium oxide (83), and other metal oxides (84). 

In an actual exhaust system controlled by the signal of the oxygen sensor, stoichiometry is never maintained, rather, it cycles periodically rich and lean one to three times per second, ie, one-half of the time there is too much oxygen and one-half of the time there is too Httle. Incorporation of cerium oxide or other oxygen storage components solves this problem. The ceria adsorbs O2 that would otherwise escape during the lean half cycle, and during the rich half cycle the CO reacts with the adsorbed O2 (32,44,59—63). The TWC catalyst effectiveness is dependent on the use of Rh to reduce NO and... 

Fillers can also be used to promote or enhance the thermal stability of the silicone adhesive. Normal silicone systems can withstand exposure to temperatures of 200 C for long hours without degradation. However, in some applications the silicone must withstand exposure to temperatures of 280 C. This can be achieved by adding thermal stabilizers to the adhesive formulations. These are mainly composed of metal oxides such as iron oxide and cerium oxide, copper organic complexes, or carbon black. The mechanisms by which the thermal stabilization occurs are discussed in terms of radical chemistry. 

The main sources of infrared radiation used in spectrophotometers are (1) a nichrome wire wound on a ceramic support, (2) the Nernst glower, which is a filament containing zirconium, thorium and cerium oxides held together by a binder, (3) the Globar, a bonded silicon carbide rod. These are heated electrically to temperatures within the range 1200- 2000 °C when they will glow and produce the infrared radiation approximating to that of a black body. 

Ceric Oxide (Cerium Dioxide, Cerium Oxide, Ceria). CeOj, mw 172.13, white powd, mp ca 2600°, d 7.132g/cc at 23°. Sol in coned sulfuric and nitric acids, insol in dil acids and w. Prepn is by dissolving CeCOj in 16N HNOa contg 3% H202 and then evapg off the nitrate soln followed by thermal decompn. The yield is 97.6% of 99.8% pure Ce02, The oxide is used in optics, electronics, as a diluent in nuclear fuels (as... 

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. 

E. S. Shedd, J. D. Merchaw and T. A. Henrie, Continous Electrowinning of Cerium Metal from Cerium Oxides, U. S. Bureau of Mines, Rept. Invst. No. 6362,1964. 

If the glass is to be sterilized by irradiation, a special formulation containing cerium oxide must be used to prevent discoloration of the container. 

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. 

Cerium oxides are outstanding oxide materials for catalytic purposes, and they are used in many catalytic applications, for example, for the oxidation of CO, the removal of SOx from fluid catalytic cracking flue gases, the water gas shift reaction, or in the oxidative coupling reaction of methane [155, 156]. Ceria is also widely used as an active component in the three-way catalyst for automotive exhaust pollution control,... 

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