Rare earth metal chlorides

An interesting selectivity in the transfer of alkyl groups (n-Alk>Me) is observed in these addition reactions. The regioselectivity of the reaction of crotylmagnesium chloride (213) with benzaldehyde strongly depends on the presence of various rare-earth metal chlorides. The a- to y ratio of products can be switched to the opposite by using only another metal salt. Yttrium trichloride gives exclusively y-product, while neodymium trichloride leads to 89% of the a-attack (with 92% of ( )-isomer) (equation 142) °. 

Phases in the alkali metal-rare earth metal-chloride, bromide and iodide systems... 

Fused Salt Electrolysis. Only light RE metals (La to Nd) can be produced by molten salt electrolysis because these have a relatively low melting point compared to those of medium and heavy RE metals. Deposition of an alloy with another metal, Zn for example, is an alternative. The feed is a mixture of anhydrous RE chlorides and fluorides. The materials from which the electrolysis cell is constmcted are of great importance because of the high reactivity of the rare-earth metals. Molybdenum, tungsten, tantalum, or alternatively iron with ceramic or graphite linings are used as cmcible materials. Carbon is frequently used as an anode material. 

In the case of molten salts, the functional electrolytes are generally oxides or halides. As examples of the use of oxides, mention may be made of the electrowinning processes for aluminum, tantalum, molybdenum, tungsten, and some of the rare earth metals. The appropriate oxides, dissolved in halide melts, act as the sources of the respective metals intended to be deposited cathodically. Halides are used as functional electrolytes for almost all other metals. In principle, all halides can be used, but in practice only fluorides and chlorides are used. Bromides and iodides are thermally unstable and are relatively expensive. Fluorides are ideally suited because of their stability and low volatility, their drawbacks pertain to the difficulty in obtaining them in forms free from oxygenated ions, and to their poor solubility in water. It is a truism that aqueous solubility makes the post-electrolysis separation of the electrodeposit from the electrolyte easy because the electrolyte can be leached away. The drawback associated with fluorides due to their poor solubility can, to a large extent, be overcome by using double fluorides instead of simple fluorides. Chlorides are widely used in electrodeposition because they are readily available in a pure form and... 

The metallothermic reduction of the oxides by La produces the metals Sm, Eu, Tm, Yb, all having high vapour pressures. The reaction goes to completion due to the removal of the rare earths by volatilization from the reaction chamber (lanthanum has a low vapour pressure). The remaining rare earth metals (Sc, La, Ce, Pr, Nd, Y, Gd, Tb, Dy, Ho, Er, Lu) can be obtained by quantitative conversion of the oxides in fluorides, followed by reduction with Ca. The metallothermic reduction of the anhydrous rare earth chlorides could be also used to obtain La, Ce, Pr and Nd. The molten electrolysis can be applied to obtain only the first four lanthanide metals, La, Ce, Pr and Nd, because of the high reactivity of the materials that limits the operating temperatures to 1100°C or lower. 

Compressed oxygen, and fresh and recycled ethylene, are heated, mixed, and then passed through a reactor with fixed beds of catalyst— silver oxide deposited on alumina pellets. In recent years the catalyst has been improved by the addition of promoters and inhibitors. (Promoters—in this case compounds of alkali or alkaline rare earth metals—enhance the activity of the catalyst inhibitors—in this case chlorine compounds—chloroethane, or vinyl chloride, reduce its rate of activity decline.)... 

This well known alloy produced by fused chloride electrolysis of the light lanthanide elements constitutes over 90% of the rare earth metals (RE3 l s) consumed for steeLnaking in the western world. It is estimated that approximately 3,000 metric tons of mischmetal, worth about 35 million, are added to liquid steel every year,... 

Dry hydrogen sulphide interacts with selenium oxychloride with the formation of yellow selenium sulphide and evolution of hydrogen chloride. There is a development of heat which dissociates the selenium sulphide into sulphur and red selenium. Sulphur dioxide has no action on the hot anhydrous oxychloride, but if water is present there is a deposition of selenium. Sulphur trioxide is soluble in selenium oxychloride, forming a thick solution which is a very powerful solvent for the oxides of the rare earth metals. When the oxychloride is brought into contact with finely divided barium sulphate, the latter is at once peptised and becomes gelatinous in appearance,1 but when subsequently treated with water the sulphate immediately changes back to the ordinary form. 

Early in 1827 when Mosander [158] first prepared rare earth metals by the reduction of their chlorides with potassium in a hydrogen atmos-... 

Fluorides are preferred to chlorides because of the hygroscopic nature of the latter. Daane and Spedding showed that all the rare earth metals... 

The use of solvating extractants in the recovery of gold and platinum-group metals (PGM) was described in the previous section. These extractants have also found some specialized applications in the extractive metallurgy of base metals. For example, they have been used in the recovery of uranium, the separation of zirconium and hafnium, the separation of niobium and tantalum, the removal of iron from solutions of cobalt and nickel chlorides, and in the separation of the rare-earth metals from one another. 

Manipulation. A concentrated solution of the anhydrous rare earth chloride J in ethyl alcohol (20 to 30 g. chloroform per 100 ml. absolute ethanol) is electrolyzed using a 110-volt direct current with the cell in series with a variable resistance. The current density should not exceed 0.05 to Fig. i.—Ceil for 0.1 amp. per square centimeter in order to eaXamargam8.rare Prevent dispersion of the mercury. The solution is electrolyzed for 15 to 40 hours. Under these conditions, a liquid to pasty amalgam is obtained containing 1 to 3 per cent of rare earth metal by weight. Results of typical runs are given in the accompanying table. 

Rare earth chlorides, anhydrous, 28 Rare earth metals, 18 amalgams, concentration of, 17 Rhenium, metallic, 175 by reduction of ammonium per-rhenate, 177... 

Classical Friedel-Crafts catalysts such as BF3 etherate or Bronstedt acids, which are applied in stoichiometric amounts or even in excess, still have their value, because they are relatively inexpensive yet powerful catalysts for C-H transformation at arenes and, most importantly, they are often successful when modern catalysts fail. Gold(III) chloride, at less than 1 %, has impressive reactivity under very moderate reaction conditions and its selectivity is exceptionally good. Friedel-Crafts type reactions with this catalyst are, however, restricted to very electron-rich arenes. Further studies should concentrate on increasing the electrophilicity of gold catalysts. New catalysts have emerged, for instance based on ruthenium and rhenium, which promise broad applicability based on alternative mechanisms. Catalysts based on rare earth metals are discussed in the next chapter. 

Although heterobimetallic complexes with alkylated rare-earth metal centers were proposed to promote 1,3-diene polymerization via an allyl insertion mechanism, details of the polymerization mechanism and of the structure of the catalytically active center(s) are rare [58,83,118-125]. Moreover, until now, the interaction of the cationizing chloride-donating reagent with alkylated rare-earth metal centers is not well-understood. Lanthanide carboxylate complexes, which are used in the industrial-scale polymerization of butadiene and isoprene, are generally derived from octanoic, versatic, and... 

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