Thoria

Titration in NaCl, lOol was lower than in NaClO4 on both sides of the PZC Cpotential, 0.001 M Na salts C1O4=C1 [615]. 

Coagulation One sample (PZC at pH 5.9) Li Na K Cs and IO3 BrOj NO3 CIO3 Cl Br=I=ClO4 three other samples (PZC at pH 5) showed a reversed cation affinity series, and the anion affinity series were similar, although in two samples the difference between NO3, CIO3, Cl, and Br was insignificant [3005]. 

Electrokinetic potential, 0.001 M K salts NO3 Cl CIO4 [2145]. A coagulation study was also carried out. 

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The ketones are readily prepared, for example, acetophenone from benzene, acetyl chloride (or acetic anhydride) and aluminium chloride by the Friedel and Crafts reaction ethyl benzyl ketones by passing a mixture of phenylacetic acid and propionic acid over thoria at 450° and n-propyl- p-phenylethylketone by circulating a mixture of hydrocinnamic acid and n-butyric acid over thoria (for further details, see under Aromatic Ketones, Sections IV,136, IV,137 and IV,141). 

By dropping au aromatic acid either alone or mixed with an aliphatic acid into a tube containing a thoria catalyst deposited on pumice and heated to 400-450°. This method is generally employed for the preparation of mixed aromatic - aliphatic ketones. Excess of the aUphatic acid is usually present since this leads to by-products which are easily separated and also tends to increase the yield of the desired ketone at the expense of the symmetrical ketone of the aromatic acid. Thus —... 

Use the apparatus described in Section 111,72 and adjust the furnace for a working temperature of 400-450°. Although a manganous oxide catalyst gives satisfactory results, thoria is more convenient in practice. 

The mixture of carbon monoxide and hydrogen is enriched with hydrogen from the water gas catalytic (Bosch) process, ie, water gas shift reaction, and passed over a cobalt—thoria catalyst to form straight-chain, ie, linear, paraffins, olefins, and alcohols in what is known as the Fisher-Tropsch synthesis. 

Tungsten with the addition of as much as 5% thoria is used for thermionic emission cathode wires and as filaments for vibration-resistant incandescent lamps. Tungsten—rhenium alloys are employed as heating elements and thermocouples. Tantalum and niobium form continuous soHd solutions with tungsten. Iron and nickel are used as ahoy agents for specialized appHcations. 

Dispersions of flake aluminum powders having surface oxide up to 14 wt % Al O have been pressed, sintered, and worked to a material known as sintered aluminum powder (SAP). This product exhibits high strength at elevated temperatures. Nickel containing small additions of thoria, known as TD-nickel, is also a high temperature cermet. 

Thoria-dispersed nickel products are obtained by precipitating basic nickel compounds, whereby thoria particles of ca 100 nm are coated with layers of nickel to the extent that the product has a 2% thoria dispersion. 

Dispersion-strengthened copper is made by dispersing a thoria or alumina phase through copper powder. The resulting P/M product retains its strength at elevated temperatures. It is used, for example, as the conductor or lead wine that supports the hot filament inside incandescent lamps. 

Beryllia and Thoria. These are specialty oxides for highly specialized appHcations that require electrical resistance and high thermal conductivity. BeryUia is highly toxic and must be used with care. Both are very expensive and are used only in small quantities. 

Industrial refractories are by thek very nature stable materials and usually do not constitute a physiological hazard. This is not so, however, for unusual refractories that might contain heavy metals or radioactive oxides, such as thoria and urania, or to bkiders or additives that may be toxic. 

The addition of thoria to a Re—W ahoy produces a material having 74 wt % W, 24 wt % Re, and 2% Th02 that is used for heated cathodes in electron tubes. This material has good ducthity and high resistance to breaking by mechanical shock. 

Nickel—rhenium ahoys containing thoria or other additives have been developed for use as cathodes on electrovacuum devices. Rhenium is found to improve the strength properties substantiahy. At 1000°C the strength of a 90 wt % Ni—10% Re ahoy exceeds the strength of a Ni—V cathode material by 90%. Rigidity is exceeded by a factor of 150 to 200%. 

Ha2ards encountered with tungsten may be caused by substances associated with the production and use of tungsten, eg. As, Sb, Pb, and other impurities in tungsten ores, Co aerosols and dust in the carbide industry, and thoria used in welding electrodes. Lanthanum is being promoted as a substitute for thoria in this appHcation. 

N. D. Veigel and co-workers. Development of a Chromium-Thoria Alloy, NASA Report. CR-72901, Mar. 10,1971. 

When esters are passed with ammonia over a contact catalyst such as alumina or thoria at 400—500°C, nitriles are obtained via dehydration of the intermediate amides ... 

An ethyl acetate yield of 24% is obtained using a copper oxide catalyst with 0.1—0.2% thoria at 350°C. Dehydration. Ethyl alcohol can be dehydrated to form ethylene or ethyl ether. 

The vapor-phase esterification of ethanol has also been studied extensively (363,364), but it is not used commercially. The reaction can be catalyzed by siUca gel (365,366), thoria on siUca or alumina (367), zirconium dioxide (368), and by xerogels and aerogels (369). Above 300°C the dehydration of ethanol becomes appreciable. Ethyl acetate can also be produced from acetaldehyde by the Tischenko reaction (370—372) using an aluminum alkoxide catalyst and, with some difficulty, by the boron trifluoride-catalyzed direct esterification of ethylene with organic acids (373). 

The minerals on which the work was performed during the nineteenth century were indeed rare, and the materials isolated were of no interest outside the laboratory. By 1891, however, the Austrian chemist C. A. von Welsbach had perfected the thoria gas mantle to improve the low luminosity of the coal-gas flames then used for lighting. Woven cotton or artificial silk of the required shape was soaked in an aqueous solution of the nitrates of appropriate metals and the fibre then burned off and the nitrates converted to oxides. A mixture of 99% ThOz and 1% CeOz was used and has not since been bettered. CeOz catalyses the combustion of the gas and apparently, because of the poor thermal conductivity of the ThOz, particles of CeOz become hotter and so brighter than would otherwise be possible. The commercial success of the gas mantle was immense and produced a worldwide search for thorium. Its major ore is monazite, which rarely contains more than 12% ThOz but about 45% LnzOz. Not only did the search reveal that thorium, and hence the lanthanides, are more plentiful than had previously been thought, but the extraction of the thorium produced large amounts of lanthanides for which there was at first little use. 

In 1789 M. H. Klaproth examined pitchblende, thought at the time to be a mixed oxide ore of zinc, iron and tungsten, and showed that it contained a new element which he named uranium after the recendy discovered planet, Uranus. Then in 1828 J. J. Berzelius obtained an oxide, from a Norwegian ore now known as thorite he named this thoria after the Scandinavian god of war and, by reduction of its tetrachloride with potassium, isolated the metal thorium. The same method was subsequendy used in 1841 by B. Peligot to effect the first preparation of metallic uranium. 

Alloys with thoria (Th02> are used for TIG (Tungsten Inert Gas) welding electrodes and in electronic applications where its increased electron emission properties and high temperature strength prove advantageous. 

The first definite production of plutonium metal was made in November, 1943 by Baumbach and coworkers (1958). Approximately 35 micrograms of PuFi in a small thoria crucible in a high vacuum was reacted with barium metal at 1400 C to yield plutonium metal. The metal was found to have a silvery lustre, a density of about 16 grams j>er cubic centimeter and it rapidly absorbed hydrogen at about 210 C to form a black powder subsequently identified as PUH3 (a proof that metal had been produced). 

Zirconium carbide is a highly refractory compound with excellent properties but, unlike titanium carbide, it has found only limited industrial importance except as coating for atomic-fuel particles (thoria and urania) for nuclear-fission power plants.l " ] This lack of applications may be due to its high price and difficulty in obtaining it free of impurities. 

Other refractory oxides that can be deposited by CVD have excellent thermal stability and oxidation resistance. Some, like alumina and yttria, are also good barriers to oxygen diffusion providing that they are free of pores and cracks. Many however are not, such as zirconia, hafnia, thoria, and ceria. These oxides have a fluorite structure, which is a simple open cubic structure and is particularly susceptible to oxygen diffusion through ionic conductivity. The diffusion rate of oxygen in these materials can be considerable. 

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