Rare metal oxides

Figure 6.1 shows AG, the free energy change involved in the formation of various rare metal oxides, plotted against temperature. Similarly the... 

INTRODUCTION OF RARE METAL SALT Anhydrous rare metal chlorides are usually hygroscopic and therefore difficult to introduce into a melt without producing deleterious oxychlorides as a result of hydrolysis in moist air. This has been overcome for some metal chlorides by producing them in situ in the melt. A suspension of the rare metal oxide in the inert alkali metal chloride melt is chlorinated directly at a suitable temperature, in the presence of a reducing agent such... 

Working electrodes for use in electrochemistry are normally solid, with rare exceptions mercury electrodes are one of those in which the electrode material is liquid at room temperature. In general, electrode materials are conductors or semiconductors constituted by the above-cited substrates (metals, carbon and derivates) or even by some polymers rarely metal oxides (despite their special use in some cases). Typically working electrodes are constructed in cylindrical form for manufacturing, with connections made by conductive silver glue and a metal wire/rod as copper, avoiding an exposure of such conductive metal with the eleetrolyte. 

CoF is used for the replacement of hydrogen with fluorine in halocarbons (5) for fluorination of xylylalkanes, used in vapor-phase soldering fluxes (6) formation of dibutyl decalins (7) fluorination of alkynes (8) synthesis of unsaturated or partially fluorinated compounds (9—11) and conversion of aromatic compounds to perfluorocycHc compounds (see Fluorine compounds, organic). CoF rarely causes polymerization of hydrocarbons. CoF is also used for the conversion of metal oxides to higher valency metal fluorides, eg, in the assay of uranium ore (12). It is also used in the manufacture of nitrogen fluoride, NF, from ammonia (13). 

Re OPe . The final step in the chemical processing of rare earths depends on the intended use of the product. Rare-earth chlorides, usually electrolytically reduced to the metallic form for use in metallurgy, are obtained by crystallisation of aqueous chloride solutions. Rare-earth fluorides, used for electrolytic or metaHothermic reduction, are obtained by precipitation with hydrofluoric acid. Rare-earth oxides are obtained by firing hydroxides, carbonates or oxalates, first precipitated from the aqueous solution, at 900°C. 

Other THF polymerization processes that have been disclosed in papers and patents, but which do not appear to be in commercial use in the 1990s, include catalysis by boron trifluoride complexes in combination with other cocatalysts (241—245), modified montmorrillonite clay (246—248) or modified metal oxide composites (249), rare-earth catalysts (250), triflate salts (164), and sulfuric acid or Aiming sulfuric acid with cocatalysts (237,251—255). 

SoHd lubricants ate added to help control high friction characteristics in high speed or heavy-duty appHcations where high temperatures are generated. Molybdenum disulfide [1317-33-5] M0S2, may be used alone or in a complex compound formed by grinding with fine natural graphite, and zinc sulfide [1314-98-3] ZnS. Other compounds include calcium fluoride, cryoHte [15096-52-3] Na AlF, rare-earth oxides, and metal sulfides, eg, iron, antimony, or zinc (see LUBRICATION AND LUBRICANTS). 

In 1794 the Finnish chemist J. Gadolin, while examining a mineral that had recently been discovered in a quarry at Ytterby, near Stockholm, isolated what he thought was a new oxide (or earth ) which A. G. Ekeberg in 1797 named yttria. In fact it was a mixture of a number of metal oxides from which yttrium oxide was separated by C. G. Mosander in 1843. This is actually part of the fascinating story of the rare earths to which we shall return in Chapter 30. The first sample of yttrium metal, albeit very impure, was obtained by F. Wohler in 1828 by the reduction of the trichloride by potassium. 

The performance of different types of chlorination processes is discussed comprehensively in overview [31]. It should be mentioned that carbon tetrachloride can also be applied successfully in the chlorination of rare refractory metal oxides, including tantalum oxide. 

The first experiments on the plasma chemical decomposition of fluoride solutions containing tantalum or niobium to obtain tantalum and niobium oxides were reported about fifteen years ago [524]. Subsequent publications were devoted to further development and expansion of the method for other refractory rare metals such as titanium and zirconium [525 - 532]. 

Rare earth metals, as well as alkali earth metals, can be used as oxygen getters in the purification of tantalum powder. Osaku and Komukai [608] developed a method for the production of tantalum and niobium metal powder by a two-step reduction of their oxides. The second step was aimed at reducing the oxygen content and was performed by thermal treatment with the addition of rare metals. The powder obtained by the described method is uniform, had a low oxygen level and was suitable for application in the manufacturing of tantalum capacitors. 

The examination and analysis of minerals have provided x-ray emission spectrography with a challenge and an opportunity. This situation has arisen because of a great growth of interest in uranium and thorium minerals in the rare-earth oxides and in metals such as tantalum and niobium, or hafnium and zirconium. On the whole, x-ray emission spectrography has met the challenge successfully, and the investigations that prove this also demonstrate the versatility and the value of the method.70"72... 

The relatively high cost and lack of domestic supply of noble metals has spurred considerable efforts toward the development of nonnoble metal catalysts for automobile exhaust control. A very large number of base metal oxides and mixtures of oxides have been considered, especially the transition metals, such as copper, chromium, nickel, manganese, cobalt vanadium, and iron. Particularly prominent are the copper chromites, which are mixtures of the oxides of copper and chromium, with various promoters added. These materials are active in the oxidation of CO and hydrocarbons, as well as in the reduction of NO in the presence of CO (55-59). Rare earth oxides, such as lanthanum cobaltate and lanthanum lead manganite with Perovskite structure, have been investigated for CO oxidation, but have not been tested and shown to be sufficiently active under realistic and demanding conditions (60-63). Hopcalities are out-... 

The raw materials needed to supply about ten million new automobiles a year do not impose a difficult problem except in the case of the noble metals. Present technology indicates that each car may need up to ten pounds of pellets, two pounds of monoliths, or two pounds of metal alloys. The refractory oxide support materials are usually a mixture of silica, alumina, magnesia, lithium oxide, and zirconium oxide. Fifty thousand tons of such materials a year do not raise serious problems (47). The base metal oxides requirement per car may be 0.1 to 1 lb per car, or up to five thousand tons a year. The current U.S. annual consumption of copper, manganese, and chromium is above a million tons per year, and the consumption of nickel and tungsten above a hundred thousand tons per year. The only important metals used at the low rate of five thousand tons per year are cobalt, vanadium, and the rare earths. 

In this method " - the melt eontains boric oxide and the metal oxide in a suitable electrolyte, usually an alkali or alkaline-earth halide or fluoroborate. The cell is operated at 700-1000 C depending on electrolyte composition. To limit corrosion, the container serving as cathode is made of mild steel or of the metal whose boride is sought. The anode is graphite or Fe. Numerous borides are prepared in this way, e.g., alkaline-earth and rare-earth hexaborides " and transition-metal borides, e.g, TiBj NijB, NiB and TaB... 

The reduction of a metal oxide by a mixture of B and C is easier than the reduction by the borothermic process described above. The rate of reduction depends on the removal of CO, so operation under vacuum increases the rate and allows the reaction to proceed at a lower T than the borothermic process. The metal oxide may be volatile and the borides can be contaminated by C. Accordingly, this method is not suitable for preparing pure alkaline-earth and rare-earth hexaborides because in all cases borocarbides of formula MBg C, (e.g., M = Sr, Eu, Yb) are formed . 

Storage are the fresh and 75 h aged Pd ly TWCs (Cl and C2), and it is likely that rare earth oxides do contribute to oxygen up es in those catalysts. Interestingly, the C1 and C2 catalysts are the only pair which show a correlation between oxygen uptake and noble metal dispersion (i-e. the oxygen titrated by the first CO pulse drops from 35.5 to 27.2 /i-mol O/g-cat. as the dispersion drops from 10.8% (Cl) to 3.5% (C2)). 

The Oxidative Transformation of Methane over the Nickel-based Catalysts Modified by Alkali Metal Oxide and Rare Earth Metal Oxide... 

The large amounts of natural gas (mainly methane) found worldwide have led to extentive research programs in the area of the direct conversion of methane [1-3]. Ihe oxidative transformation of methane (OTM) is an important route for the effective utilization of the abundant natural gas resources. How to increase catalyst activity is a common problem on the activation of methane. The oxidation of methane over transition m al oxides is always high active, but its main product is CO2, namely the product of deep oxidation. It is because transition metal oxides have high oxidative activity. So, they were usually used as the main corrqtonent of catalysts for the conqilete oxidation of alkane[4]. The strong oxidative activity of CH4 over tran on metal oxides such as NiO indicates that the activation of C-H bond over transition metal oxides is much easier than that over alkaline earth metal oxides and rare earth metal oxides. Furthermore, the activation of C-H bond is the key step of OTM reaction. It is the reason that we use transition metal oxides as the mam conq>onent of the OTM catalysts. However, we have to reahze that the selectivity of OTM over transition metal oxides is poor. 

We expected to control the direction of OTM reaction over NiO by sur ce modification, namely making use of the interaction between NiO and other conq>onents to beget a synergistic effect. In this paper, two completely different behaviors of the oxidative transformation of methane were performed over the nickel-based catalysts because of the different modifications by alkali metal oxide and rare earth metal oxide and the different interactions between nickel and supports. Furthermore, the two completely different reactions were related with the acid-base properties of catalysts and the states of nickel present. 

---