The rare earth metals

5 The 3rd group metals a summary of their atomic and physical properties 5.5.5.1 The rare earth metals. A summary of the main atomic and physical properties of the rare earth metals has been collected in Tables 5.11-5.13. To complete the information and the presentation of the entire series of lanthanides the data relevant to Eu and Yb have been included in these tables. However, the same data are reported also in Table 5.7 in comparison with those of the other typical divalent metals (the alkaline earth metals). As for the properties of liquid rare earth metals and alloys see Van Zytveld (1989). 

Element Temperature Stability range/°C Pressure/GPa Crystal structure Lattice parameters/pm Atomic volume pm3/106 Molar volume/ cm3/mol Density/ g/cm3 

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Scandium is a silver-white metal which develops a slightly yellowish or pinkish cast upon exposure to air. A relatively soft element, scandium resembles yttrium and the rare-earth metals more than it resembles aluminum or titanium. 

Lanthanum is silvery white, malleable, ductile, and soft enough to be cut with a knife. It is one of the most reactive of the rare-earth metals. It oxidizes rapidly when exposed to air. Cold water attacks lanthanum slowly, while hot water attacks it much more rapidly. 

Cerium is an iron-gray lustrous metal. It is malleable, and oxidizes very readily at room temperature, especially in moist air. Except for europium, cerium is the most reactive of the rare-earth metals. It decomposes slowly in cold water and rapidly in hot water. 

As with other rare-earth metals, except for lanthanum, europium ignites in air at about 150 to I8O0C. Europium is about as hard as lead and is quite ductile. It is the most reactive of the rare-earth metals, quickly oxidizing in air. It resembles calcium in its reaction with water. Bastnasite and monazite are the principal ores containing europium. 

Europium is one of the rarest and most costly of the rare-earth metals. It is priced about about 7500/kg. 

The element occurs along with other rare-earth elements in a variety of minerals. Monazite and bastnasite are the two principal commercial sources of the rare-earth metals. It was prepared in relatively pure form in 1931. 

From gadolinite, a mineral named for Gadolin, a Finnish chemist. The rare earth metal is obtained from the mineral gadolinite. Gadolinia, the oxide of gadolinium, was separated by Marignac in 1880 and Lecoq de Boisbaudran independently isolated it from Mosander s yttria in 1886. 

It is easy to reduce anhydrous rare-earth hatides to the metal by reaction of mote electropositive metals such as calcium, lithium, sodium, potassium, and aluminum. Electrolytic reduction is an alternative in the production of the light lanthanide metals, including didymium, a Nd—Pt mixture. The rare-earth metals have a great affinity for oxygen, sulfur, nitrogen, carbon, silicon, boron, phosphoms, and hydrogen at elevated temperature and remove these elements from most other metals. 

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. 

Metallurgy. The strong affinity for oxygen and sulfur makes the rare-earth metals useflil in metallurgy (qv). Mischmetal acts as a trap for these Group 16 (VIA) elements, which are usually detrimental to the properties of steel (qv) or cast iron (qv). Resistance to high temperature oxidation and thermomechanical properties of several metals and alloys are thus significantly improved by the addition of small amounts of mischmetal or its siUcide (16,17). 

R. J. Elliott, ed.. Magnetic Properties of the Rare Earth Metals, Plenum Press, London, 1972. 

Group 3 (IIIB) and Inner Transition-Metal Perchlorates. The rare-earth metal perchlorates of yttrium and lanthanum have been reported (53). Tetravalent cerium perchlorate [14338-93-3] 06(0.04)4, and uranium perchlorate have also been identified (54). 

Calcium metal is an excellent reducing agent for production of the less common metals because of the large free energy of formation of its oxides and hahdes. The following metals have been prepared by the reduction of their oxides or fluorides with calcium hafnium (22), plutonium (23), scandium (24), thorium (25), tungsten (26), uranium (27,28), vanadium (29), yttrium (30), zirconium (22,31), and most of the rare-earth metals (32). 

Bohr s quantum numbers (n, l, m) have fully entered chemistry, and every chemistry student learns about the symbols Is, 2s, 2p, 3s, 3p, 3d etc. It is hence a startling fact that the simple energy rule has not entered any major chemistry textbooks, as far as I know, and it is still this rule which gives the first explanation of the occurrence of the transition metals, the rare-earth metals, and the over-all structure of the electronic shells of atoms, (p.334). 

The valences of the rare-earth metals are calculated from their magnetic properties, as reported by Klemm and Bommer.14 It is from the fine work of these investigators that the lattice constants of the rare-earth metals have in the main been taken. The metals lutecium and ytterbium have only a very small paramagnetism, indicating a completed 4/ subshell and hence the valences 3 and 2, respectively (with not over 3% of trivalent ytterbium present in the metal). The observed paramagnetism of cerium at room temperature corresponds to about 20% Ce4+ and 80% Ce3+, that of praseodymium and that of neodymium to about 10% of the quadripositive ion in each case, and that of samarium to about 20% of the bipositive ion in equilibrium with the tripositive ion. 

The very long period is closely similar to the second long period, except for the interpolation of the rare-earth metals. It is interesting that a straight line can be passed through the points for barium, the two bivalent rare-earth metals, and the tetrahedral radii of the heavier elements. 

A review article entitled "Bulky amido ligands in rare-earth chemistry Syntheses, structures, and catalysis" has been published by Roesky. Benzamidinate ligands are briefly mentioned in this contexD The use of bulky benzamidinate ligands in organolanthanide chemistry was also briefly mentioned in a review article by Okuda et al. devoted to "Cationic alkyl complexes of the rare-earth metals S mthesis, structure, and reactivity." Particularly mentioned in this article are reactions of neutral bis(alkyl) lanthanide benzamidinates with [NMe2HPh][BPh4] which result in the formation of thermally robust ion pairs (Scheme 55). ... 

The crystal structures of the borides of the rare earth metals (M g) are describedand phase equilibria in ternary and higher order systems containing rare earths and B, including information on structures, magnetic and electrical properties as well as low-T phase equilibria, are available. Phase equilibria and crystal structure in binary and ternary systems containing an actinide metal and B are... 

Most of the known borides are compounds of the rare-earth metals. In these metals magnetic criteria are used to decide how many electrons from each rare-earth atom contribute to the bonding (usually three), and this metallic valence is also reflected in the value of the metallic radius, r, (metallic radii for 12 coordination). Similar behavior appears in the borides of the rare-earth metals and r, becomes a useful indicator for the properties and the relative stabilities of these compounds (Fig. 1). The use of r, as a correlation parameter in discussing the higher borides of other metals is consistent with the observed distribution of these compounds among the five structural types pointed out above the borides of the actinides metals, U, Pu and Am lead to complications that require special comment. 

Almost all of the rare-earth metal/rare-earth metal tri-iodide systems, R/RI3, contain binary phases with the rare-earth element in an oxidation state lower than -1-3 ( reduced rare-earth metal iodides) [3, 7, 10-13]. More common is the oxidation state -i-2. Elements that form di-iodides RI2 are illustrated in Fig. 4.1. 

We were one of the first groups to report a ternary selenophosphate of a rare-earth metal [11-13]. Since that time, we have uncovered a host of rare-earth metal chalcophosphates [1, 13, 14] that complement the transition-metal compounds found by the Kanatzidis group [15-31]. Despite the host of publications in the area of metal chalcophosphate chemistry, there have only been our systematic studies of the quaternary phase space of the rare-earth metal chalcophosphates [1, 13, 14]. 

A detailed study of two rare-earth metals under one set of reaction conditions, for example, yielded the two composition phase diagrams, shown in Fig. 14.2, for the Fu and La thiophosphate systems [3]. To prepare these phase diagrams, we varied the alkah metal, the rare-earth metal, and the phosphorous concentration to kept the sulfur concentration constant We prepared similar studies in... 

We have developed a systematic study of quaternary chalco-gallates, indates (trielates) and chalco-silicates, and germinates (tetrelates) of the rare-earth metals. We have demonstrated that a series of new compounds could be formed in these families of materials [1, 3, 9, 10, 14, 81, 82]. There have been reports in the literature of a few examples of these types of materials, but there is sufficient evidence to support the fact that this area is wide open for exploring the likelihood for new rare-earth metal-based materials [83-90]. Our studies have focused on the gallium, indium, germanium and sihcon sulfides, selenides, and teUurides. 

RBa2Cu40g (R = Sm, Y, Er) Nuclear-quadrupole coupling parameters at the rare-earth metal and copper sites from Cu ( Zn) and Ga( Zn) Mossbauer emission spectroscopy, EEG tensor in comparison with point charge model, shows that holes in lattices are localized primarily at chain-oxygen sites... 

Examples of metals which are prepared by the metallothermic reduction of oxides include manganese, chromium, vanadium, zirconium, and niobium. In a manner similar to the production of magnesium by the Pidgeon process, some of the rare earth metals have been produced by the metallothermic reduction-distillation process. 

All the rare earth metals except samarium, europium, and ytterbium can be prepared in a pure form by reducing their trifluorides with calcium. Magnesium fluoride is less stable than the rare earth fluorides and so magnesium does not figure as a reductant. Lithium forms a fluoride which is stabler than some of the rare earth fluorides and thus finds some use as a reductant. 

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... 

This soft, silver white metal reacts with air and water. The oxide is applied in optical glasses with high refractive indices (special lenses for powerful cameras and telescopes). Used for special effects in optoelectronics and electronics. Lanthanum exhibits catalytic properties. It is a component of flint and battery electrodes. Lanthanum boride (LaB6) is the superior electron-emitter for electron microscopes. Lanthanum is the first of the series of 14 lanthanides, also called the "rare-earth" metals, whose inner N shells are filled with electrons. They do not belong on the "red list" of endangered species they are neither rare nor threatened with depletion. China is particularly rich in lanthanide ores. 

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